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Sample records for sterically hindered o-iminobenzoquinone

  1. Metal-Free Approaches to Sterically-Hindered Bonds

    Science.gov (United States)

    Dunham, Veronica Vin-yi

    Developing methods to perform cross coupling reactions by means of catalysis is highly desirable in chemistry. Many industries in today's society, such as the petroleum, agriculture, pharmaceutical, electronics, and polymer industry, use catalysis to some extent whether it is to make molecules that offer crop protection or toward the synthesis of the active ingredient of a medication. It is noteworthy that over 90% of chemicals are made through catalytic processes and that the catalyst market reached $17 billion in 2014, which demonstrates the demand for such methods. While transition metal catalysts have advantages such as low catalyst loading, broad reactivity, and that they have been well studied, some disadvantages are that they can be relatively expensive and sometimes air sensitive which can make them challenging to use. Organocatalysis, specifically noncovalent catalysis operating through hydrogen bond donating interactions, offers an environmentally-friendly alternative to transition metal catalysis. Our lab utilizes organocatalysis as a strategy to synthesize challenging, sterically-hindered bonds. Nitrimines have been identified as powerful coupling partners for the sustainable construction of new sterically congested carbon-carbon and carbon-heteroatom bonds. Using urea catalysis, a metal-free method to synthesize previously inaccessible enamines has been developed. Conventional routes to synthesize enamines as important building blocks toward target molecules generally require Lewis/Bronsted acids or expensive transition metals; however, these methods are often unsuccessful when stericallyhindered substrates are used. To address this synthetic challenge, it was hypothesized that hydrogen bonding interactions between a urea organocatalyst and nitrimine would generate a reactive species suited for the effective carbon-nitrogen coupling with amines to give the desired enamine products. This reaction provides high yields (up to 99%) of enamines using a

  2. A protocol for amide bond formation with electron deficient amines and sterically hindered substrates

    DEFF Research Database (Denmark)

    Due-Hansen, Maria E; Pandey, Sunil K; Christiansen, Elisabeth

    2016-01-01

    A protocol for amide coupling by in situ formation of acyl fluorides and reaction with amines at elevated temperature has been developed and found to be efficient for coupling of sterically hindered substrates and electron deficient amines where standard methods failed.......A protocol for amide coupling by in situ formation of acyl fluorides and reaction with amines at elevated temperature has been developed and found to be efficient for coupling of sterically hindered substrates and electron deficient amines where standard methods failed....

  3. In vitro circumvention of cisplatin resistance by the novel sterically hindered platinum complex AMD473.

    Science.gov (United States)

    Holford, J.; Sharp, S. Y.; Murrer, B. A.; Abrams, M.; Kelland, L. R.

    1998-01-01

    A novel sterically hindered platinum complex, AMD473 [cis-aminedichloro(2-methylpyridine) platinum (II)], has been selected for phase I clinical trials due to commence in 1997. AMD473 was rationally designed to react preferentially with nucleic acids over sulphur ligands such as glutathione. This report documents the in vitro circumvention of acquired cisplatin resistance mechanisms in human ovarian carcinoma (HOC) cell lines by AMD473. In a panel of 11 HOC cell lines, AMD473 showed intermediate growth inhibition potency (mean IC50 of 8.1 microM) in comparison to cisplatin (mean IC50 of 2.6 microM) and carboplatin (mean IC50 of 20.3 microM). AMD473 showed only a 30.7-fold increase in IC50 value from the most sensitive to the most resistant HOC cell line, whereas for cisplatin it was 117.9-fold and for carboplatin 119.7-fold. AMD473 also showed significantly (P or = 14 h for AMD473) after equitoxic doses were exposed to HOC cells for 2 h. AMD473 ICLs in the CH1 HOC cell line were slowly formed and showed no visible signs of being repaired 24 h after removal of drug. This was paralleled by a slower, longer lasting induction of p53 protein by equitoxic doses of AMD473 in HOC cell lines with wild-type p53. This new class of sterically hindered platinum compound, selected for clinical trial in 1997, may therefore elicit improved clinical response in intrinsically and acquired cisplatin-resistant tumours in the clinic. Images Figure 9 PMID:9472630

  4. Metal coordination by sterically hindered heterocyclic ligands, including 2-vinylpyridine, assessed by investigation of cobaloximes.

    Science.gov (United States)

    Siega, Patrizia; Randaccio, Lucio; Marzilli, Patricia A; Marzilli, Luigi G

    2006-04-17

    Structural and 1H NMR data have been obtained for cobaloximes with the bulkiest substituted pyridines reported so far. We have isolated in noncoordinating solvents the complexes CH3Co(DH)2L (methylcobaloxime, where DH = the monoanion of dimethylglyoxime) with L = sterically hindered N-donor ligands: quinoline, 4-CH3quinoline, 2,4-(CH3)2pyridine, and 2-R-pyridine (R = CH3, OCH3, CH2CH3, CH=CH2). We have found that the Co-N(ax) bond is very long in the structurally characterized complexes. In particular, CH3Co(DH)2(4-CH3quinoline) has a longer Co-N(ax) bond (2.193(3) A) than any reported for methylcobaloximes. The main cause of the long bonds is unambiguously identified as the steric bulk of L by the fairly linear relationship found for Co-N(ax) distance vs CCA (calculated cone angle, CCA, a computed measure of bulk) over an extensive series of methylcobaloximes. The linear relationship improves if L basicity (quantified by pKa) is taken into account. In anhydrous CDCl3 at 25 degrees C, all complexes except the 2-aminopyridine adduct exhibit 1H NMR spectra consistent with partial dissociation of L to form the methylcobaloxime dimer. 1H NMR experiments at -20 degrees C allowed us to assess qualitatively the relative binding ability of L as follows: 2,4-(CH3)2pyridine > 4-CH3quinoline approximately = quinoline approximately = 2-CH3pyridine > 2-CH3Opyridine > 2-CH3CH2pyridine > 2-CH2=CHpyridine. The broadness of the 1H NMR signals at 25 degrees C suggests a similar order for the ligand exchange rate. The lack of dissociation by 2-aminopyridine is attributed to an intramolecular hydrogen bond between the NH2 group and an oxime O atom. The weaker than expected binding of 2-vinylpyridine relative to the Co-N(ax) bond length is attributed to rotation of the 2-vinyl group required for this bulky ligand to bind to the metal center, a conclusion supported by pronounced changes in 2-vinylpyridine signals upon coordination.

  5. Sterically hindered solvent extractants

    International Nuclear Information System (INIS)

    Solka, J.L.; Reis, A.H. Jr.; Mason, G.W.; Lewey, S.M.; Peppard, D.F.

    1978-01-01

    Di-t-pentylphosphinic acid, [C(CH 3 ) 2 (CH 2 CH 3 )] 2 PO(OH), H[Dt-PeP], has been shown by single-crystal X-ray diffraction data to be dimeric in the solid state. H[Dt-PeP] crystallizes in the centro-symmetric orthorhombic space group, Cmca, with unit cell parameters, a = 17.694(7), b = 11.021(4), and c = 13.073(5) A, and Z = 8, indicating that the molecule must conform to a crystallographic mirror plane or 2-fold axis. A measured density of 1.088 g/cm 3 is in good agreement with a calculated value of 1.074 g/cm 3 for a unit cell volume of 2549.3(A) 3 and a formula weight of 206.25 g. A total of 646 three-dimensional X-ray data were collected on an automated XRD-490 G.E. diffractometer. The structure was solved using a combination of direct methods, Patterson, Fourier, and least-squares refinement techniques. Refinement of the data indicates that H[Dt-PeP] is dimeric, and contains a mirror plane in which the hydrogen-bonded, eight-membered ring lies. A structural disorder involving principally the ethylene carbon but affecting the methyl carbons as well precluded a precise determination of the carbon positions and severely reduced the precision of the final refinement. In the liquid-liquid extraction system consisting of a solution of H[Dt-PeP] in benzene vs an acidic aqueous chloride phase, the extraction of UO 2 2+ follows the stoichiometry: UO 2 sub(A) 2+ + 2(HY) 2 subO = UO 2 (HY 2 ) 2 sub(O) + 2Hsub(A) + where (HY) 2 represents the dimer of H[Dt-PeP] and A and O represent the mutually equilibrated aqueous and organic phases. The expression for the distribution ratio, k, for UO 2 2+ is given. (author)

  6. Dye stability and performances of dye-sensitized solar cells with different nitrogen additives at elevated temperatures - Can sterically hindered pyridines prevent dye degradation?

    Energy Technology Data Exchange (ETDEWEB)

    Tuyet Nguyen, Phuong; Lund, Torben [Department of Science, Systems and Models, Roskilde University, 4000 Roskilde (Denmark); Rand Andersen, Anders [University of Southern Denmark, Institute of Sensors, Signals and Electrotechnics (SENSE), Niels Bohrs Alle 1, 5230 Odense M (Denmark); Danish Technological Institute, Plastics Technology, Gregersensvej 2630 Taastrup (Denmark); Morten Skou, Eivind [University of Southern Denmark, Department of Chemical Engineering, Biotechnology and Enviromental Technology, Niels Bohrs Alle 1, 5230 Odense M (Denmark)

    2010-10-15

    The homogeneous kinetics of the nucleophilic substitution reactions between the ruthenium dye N719 and eight pyridines and 1-methylbenzimidazole have been investigated in 3-methoxypropionitrile at 100 C. The half lives of N719 with the additives 4-tert-butylpyridine (0.5 M) and 1-methylbenzimidazole (0.5 M) were 57 and 160 h, respectively. Sterically hindered pyridines like 2,6-lutidine did not react with N719. The efficiencies of dye-sensitized solar cells (DSC, area=8.0 cm{sup 2}) prepared with 1-methylbenzimidazole (MBI), 4-tert-butylpyridine (4-TBP), 2,6-lutidine and without any additive were 7.1%, 6.2%, 6.0% and 4.8%, respectively. The cells were stored in dark at 85 C and their I-V curves and impedance spectra were measured at regular time intervals. The N719 dye degradation in the cells were monitored by a new dye extraction protocol combined with analysis of the dye extract by HPLC coupled to mass spectrometry. After 300 h storage in dark at 85 C 40% of the initial amount of N719 dye was degraded in DSC cells prepared with MBI and the efficiency was decreased to 40% of its initial value. DSC cells prepared with 2,6-lutidine or no additives showed smaller thermal dye and efficiency stability at elevated temperatures than DSC cells prepared with the none sterically hindered additives MBI and 4-TBP. In the cells prepared with 2,6-lutidine or no additive higher contents of the iodo products [RuL{sub 2}(NCS)(iodide)]{sup +} and [RuL{sub 2}(3-MPN)(iodide)]{sup +} were found than in cells prepared with 4-TBP and MBI. It is suggested that sterically hindered pyridines have smaller complexation constants with I{sub 3}{sup -} than unsterically hindered additives. This may explain the observed faster nucleophilic substitution rates of uncomplexed I{sub 3}{sup -} with N719 in DSC cells prepared with sterically hindered pyridines. The EIS analysis showed that the lifetime of the injected electrons in the TiO{sub 2}{tau}{sub eff} is reduced by a thermally induced change

  7. Controlled and Efficient Polymerization of Conjugated Polar Alkenes by Lewis Pairs Based on Sterically Hindered Aryloxide-Substituted Alkylaluminum

    Directory of Open Access Journals (Sweden)

    Xiaojun Wang

    2018-02-01

    Full Text Available Reported herein is the development of an effective strategy for controlled and efficient Lewis pair polymerization of conjugated polar alkenes, including methyl methacrylate (MMA, n-butyl methacrylate (nBuMA, and γ-methyl-α-methylene-γ-butyrolactone (γMMBL, by the utilization of sterically encumbered Al(BHT2Me (BHT: 2,6-di-tert-butyl-4-methylphenol as a Lewis acid that shuts down intramolecular backbiting termination. In combination with a selected N-heterocyclic carbene (NHC as a Lewis base, the polymerization of MMA exhibited activity up to 3000 h−1 TOF and an acceptable initiation efficiency of 60.6%, producing polymers with high molecular weight (Mn up to 130 kg/mol and extremely narrow dispersity (Đ = 1.06~1.13. This controlled polymerization with a living characteristic has been evidenced by chain-extension experiments and chain-end analysis, and enabled the synthesis of well-defined diblock copolymers.

  8. Extraction of UO22+ by two highly sterically hindered (X1) (X2) PO(OH) extractants from an aqueous chloride phase

    International Nuclear Information System (INIS)

    Mason, G.W.; Lewey, S.M.; Gilles, D.M.; Peppard, D.F.

    1978-01-01

    The comparative extraction behaviour of tracer-level UO 2 2+ into benzene solutions of two highly sterically hindered extractants, di(2,6-di-iso-propylphenyl) phosphoric acid, HD(2,6-i-PPHI)P and di-tertiary-butyl phosphinic acid, H[Dt-BP], vs an aqueous 1.0 F (NaCl + HCl) phase was studied. The extraction of UO 2 2+ in both systems is directly second-power dependent upon extractant concentration and inversely second-power dependent upon hydrogen ion concentration, the stoichiometry of extraction being UOsub(2A) 2+ + 2(HY)sub(2O) = UO 2 (HY 2 )sub(2O) + 2Hsub(A) + . The expression for the distribution ratio, K is K = Ksub(s)F 2 /[H + ] 2 the general expression for the extraction of any metallic species being K - Ksub(s)Fsup(a)/[H + ]sup(b) where Ksub(s) is a constant characteristic of the system, F the concentration in formality units of extractant in the organic phase, [H + ] the concentration of hydrogen ion in the aqueous phase, and a and b the respective extractant and hydrogen-ion dependencies. Both extractants have a high degree of steric hindrance. The HD(2,6-i-PPHI)P is the more highly acidic, the pKsub(A) value, in 75% ethanol, being 3.2. The pKsub(A), previously reported, for H[Dt-BP] is 6.26. The Ksub(s) for UO 2 2+ in the system HY in benzene diluent vs an aqueous 1.0 F (NaCl + HCl) phase is 2 x 10 4 for H[Dt-BP] and 3 x 10 -1 for HD(2,6-i-PPHI)P; the ratio of the Ksub(s) values nearly 7 x 10 3 , favours the less acidic extractant. For comparative purposes, the Ksub(s) values for UO 2 2+ and for Am 3+ and Eu 3+ in other (X 1 )(X 2 )PO(OH), in benzene diluent, vs 1.0 F (NaCl + HCl) systems are presented. The variations are discussed in terms of the pKsub(A) of the extractant and the steric hindrance within the extractant. (author)

  9. Mercury(II) and methylmercury(II) complexes of novel sterically hindered thiolates: 13C and 199Hg NMR studies and the crystal and molecular structures of [MeHg(SC6H2-2,4,6-Pri3)], [Hg(SC6H4-2-SiMe3)2], [Hg(2-SC5H3N-3-SiMe3)2], and [Hg{(2-SC6H4)2SiMe2}]2

    International Nuclear Information System (INIS)

    Block, E.; Brito, M.; Gernon, M.; McGowty, D.; Kang, Hyunkyu; Zubieta, J.

    1990-01-01

    Several series of complexes of the types [MeHg(SR)] and [Hg(SR) 2 ] have been synthesized, where the ligands are members of new classes of sterically hindered thiolates, including (triorganosilyl)methanethiols, 2-(triorganosilyl)benzenethiols, 3-(triorganosilyl)pyridine-2-thiols, and bis(2-mercaptophenyl) derivatives. Detailed 1 H, 13 C, and 199 Hg NMR studies revealed several general trends. The 199 Hg chemical shifts moved upfield in the order [MeHg(SR)] 2 ] 2 ] 2 ]. For the [MeHg(SR)] series of complexes, 1 J(Hg-C) correlates with δ( 13 C(methyl)) and with the type of thiolate ligand. Anomalous behavior is observed for oligomeric species. There is only a limited correlation of δ( 199 Hg) with steric cone angles for a subset of the complexes. Crystal data for the complexes are reported. 86 refs., 7 figs., 11 tabs

  10. Flow carbonylation of sterically hindered ortho-substituted iodoarenes

    Directory of Open Access Journals (Sweden)

    Carl J. Mallia

    2016-07-01

    Full Text Available The flow synthesis of ortho-substituted carboxylic acids, using carbon monoxide gas, has been studied for a number of substrates. The optimised conditions make use of a simple catalyst system compromising of triphenylphosphine as the ligand and palladium acetate as the pre-catalyst. Carbon monoxide was introduced via a reverse “tube-in-tube” flow reactor at elevated pressures to give yields of carboxylated products that are much higher than those obtained under normal batch conditions.

  11. Substituent effects in heterogeneous catalysis--5. The steric hindrance of bulky alkyl substituents in cyclohexanone hydrogenation

    Energy Technology Data Exchange (ETDEWEB)

    Chihara, T; Tanaka, K

    1979-02-01

    The steric hindrance of bulky alkyl substituents in cyclohexanone hydrogenation was demonstrated by the reactivities of 2-isopropyl and 2-tert.-butyl cyclohexanone relative to cyclohexanone in individual and competitive hydrogenation at 30/sup 0/C over alumina-supported ruthenium, rhodium, and platinum catalysts. The results indicate that the ketone adsorption onto the catalyst is sterically hindered by the alkyl substitution significantly more than the surface reaction which follows the adsorption.

  12. Molecular properties of conjugates formed by synthetic hydrophilic polymers and sterically hindered phenols

    Czech Academy of Sciences Publication Activity Database

    Domnina, N. S.; Sergeeva, O. Yu.; Koroleva, A. N.; Rakitina, O. V.; Dobrun, L. A.; Filippov, Sergey K.; Mikhailova, M. E.; Lezov, A. V.

    2010-01-01

    Roč. 52, č. 9 (2010), s. 900-906 ISSN 0965-545X Institutional research plan: CEZ:AV0Z40500505 Keywords : antioxidant * conjugates * light scattering Subject RIV: CD - Macromolecular Chemistry Impact factor: 0.659, year: 2010

  13. Synthesis of Electron-Rich Sterically Hindered P-1 Phosphazene Bases by the Staudinger Reaction

    Czech Academy of Sciences Publication Activity Database

    Alexandrova, Anastasia; Mašek, Tomáš; Polyakova, Svetlana; Císařová, I.; Saame, J.; Leito, I.; Lyapkalo, Ilya

    -, č. 9 (2013), s. 1811-1823 ISSN 1434-193X Institutional research plan: CEZ:AV0Z40550506 Keywords : phosphazenes * phosphazides * Staudinger reaction * azides * basicity * structure-activity relationships Subject RIV: CC - Organic Chemistry Impact factor: 3.154, year: 2013

  14. Sustainable steric stabilization of colloidal titania nanoparticles

    Science.gov (United States)

    Elbasuney, Sherif

    2017-07-01

    A route to produce a stable colloidal suspension is essential if mono-dispersed particles are to be successfully synthesized, isolated, and used in subsequent nanocomposite manufacture. Dispersing nanoparticles in fluids was found to be an important approach for avoiding poor dispersion characteristics. However, there is still a great tendency for colloidal nanoparticles to flocculate over time. Steric stabilization can prevent coagulation by introducing a thick adsorbed organic layer which constitutes a significant steric barrier that can prevent the particle surfaces from coming into direct contact. One of the main features of hydrothermal synthesis technique is that it offers novel approaches for sustainable nanoparticle surface modification. This manuscript reports on the sustainable steric stabilization of titanium dioxide nanoparticles. Nanoparticle surface modification was performed via two main approaches including post-synthesis and in situ surface modification. The tuneable hydrothermal conditions (i.e. temperature, pressure, flow rates, and surfactant addition) were optimized to enable controlled steric stabilization in a continuous fashion. Effective post synthesis surface modification with organic ligand (dodecenyl succinic anhydride (DDSA)) was achieved; the optimum surface coating temperature was reported to be 180-240 °C to ensure DDSA ring opening and binding to titania nanoparticles. Organic-modified titania demonstrated complete change in surface properties from hydrophilic to hydrophobic and exhibited phase transfer from the aqueous phase to the organic phase. Exclusive surface modification in the reactor was found to be an effective approach; it demonstrated surfactant loading level 2.2 times that of post synthesis surface modification. Titania was also stabilized in aqueous media using poly acrylic acid (PAA) as polar polymeric dispersant. PAA-titania nanoparticles demonstrated a durable amorphous polymeric layer of 2 nm thickness. This

  15. Protein unfolding with a steric trap.

    Science.gov (United States)

    Blois, Tracy M; Hong, Heedeok; Kim, Tae H; Bowie, James U

    2009-10-07

    The study of protein folding requires a method to drive unfolding, which is typically accomplished by altering solution conditions to favor the denatured state. This has the undesirable consequence that the molecular forces responsible for configuring the polypeptide chain are also changed. It would therefore be useful to develop methods that can drive unfolding without the need for destabilizing solvent conditions. Here we introduce a new method to accomplish this goal, which we call steric trapping. In the steric trap method, the target protein is labeled with two biotin tags placed close in space so that both biotin tags can only be bound by streptavidin when the protein unfolds. Thus, binding of the second streptavidin is energetically coupled to unfolding of the target protein. Testing the method on a model protein, dihydrofolate reductase (DHFR), we find that streptavidin binding can drive unfolding and that the apparent binding affinity reports on changes in DHFR stability. Finally, by employing the slow off-rate of wild-type streptavidin, we find that DHFR can be locked in the unfolded state. The steric trap method provides a simple method for studying aspects of protein folding and stability in native solvent conditions, could be used to specifically unfold selected domains, and could be applicable to membrane proteins.

  16. Sustainable steric stabilization of colloidal titania nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Elbasuney, Sherif, E-mail: sherif_basuney2000@yahoo.com

    2017-07-01

    Graphical abstract: Controlled surface properties of titania nanoparticles via surface modification, flocculation from aqueous phase (a), stabilization in aqueous phase (b), extraction to organic phase (c). - Highlights: • Complete change in surface properties of titania nanoparticles from hydrophilic to hydrophobic. • Harvesting the formulated nanoparticles from the aqueous phase to the organic phase. • Exclusive surface modification in the reactor during nanoparticle synthesis. • Sustainable stabilization of titania nanoparticles in aqueous media with polar polymeric dispersant. - Abstract: A route to produce a stable colloidal suspension is essential if mono-dispersed particles are to be successfully synthesized, isolated, and used in subsequent nanocomposite manufacture. Dispersing nanoparticles in fluids was found to be an important approach for avoiding poor dispersion characteristics. However, there is still a great tendency for colloidal nanoparticles to flocculate over time. Steric stabilization can prevent coagulation by introducing a thick adsorbed organic layer which constitutes a significant steric barrier that can prevent the particle surfaces from coming into direct contact. One of the main features of hydrothermal synthesis technique is that it offers novel approaches for sustainable nanoparticle surface modification. This manuscript reports on the sustainable steric stabilization of titanium dioxide nanoparticles. Nanoparticle surface modification was performed via two main approaches including post-synthesis and in situ surface modification. The tuneable hydrothermal conditions (i.e. temperature, pressure, flow rates, and surfactant addition) were optimized to enable controlled steric stabilization in a continuous fashion. Effective post synthesis surface modification with organic ligand (dodecenyl succinic anhydride (DDSA)) was achieved; the optimum surface coating temperature was reported to be 180–240 °C to ensure DDSA ring opening

  17. Crystal structures of three sterically congested disilanes

    Directory of Open Access Journals (Sweden)

    Kothanda Rama Pichaandi

    2017-03-01

    Full Text Available In the three sterically congested silanes, C24H38Si2 (1 (1,1,2,2-tetraisopropyl-1,2-diphenyldisilane, C24H34Br4Si2 (2 [1,1,2,2-tetrakis(2-bromopropan-2-yl-1,2-diphenyldisilane] and C32H38Si2 (3 (1,2-di-tert-butyl-1,1,2,2-tetraphenyldisilane, the Si—Si bond length is shortest in (1 and longest in (2, with (3 having an intermediate value, which parallels the increasing steric congestion. A comparison of the two isopropyl derivatives, (1 and 2, shows a significant increase in the Si—C(ipso distance with the introduction of bromine. Also, in the brominated compound 2, attractive intermolecular Br...Br interactions exist with Br...Br separations ca 0.52 Å shorter than the sum of the van der Waals radii. In compound 2, one of the bromoisopropyl groups is rotationally disordered in an 0.8812 (9:0.1188 (9 ratio. Compound 3 exhibits `whole molecule' disorder in a 0.9645 (7:0.0355 (7 ratio with the Si—Si bonds in the two components making an angle of ca 66°.

  18. 13C and 1H nuclear magnetic resonance of methyl-substituted acetophenones and methyl benzoates: steric hindrance and inhibited conjugation.

    Science.gov (United States)

    Budesínský, Milos; Kulhánek, Jirí; Böhm, Stanislav; Cigler, Petr; Exner, Otto

    2004-10-01

    The 1H and 13C NMR spectra of 14 methyl-substituted acetophenones and 14 methyl-substituted methyl benzoates were assigned and interpreted with respect to the conformation of the C(ar)-C(O) bond. The substituent effects are proportional in the two series and can be divided into polar and steric: each has different effects on the 13C SCS of the individual atoms. In the case of C atoms C(O), C(1) and CH3(CO), the steric effects were quantitatively separated by comparing SCS in the ortho and para positions. The steric effects are proportional for the individual C atoms and also to steric effects estimated from other physical quantities. However, they do not depend simply on the angle of torsion phi of the functional group as anticipated hitherto. A better description distinguishes two classes of compounds: sterically not hindered or slightly hindered planar molecules and strongly sterically hindered, markedly non-planar. In order to confirm this reasoning without empirical correlations, the J(C,C) coupling constants were measured for three acetophenone derivatives labeled with 13C in the acetyl methyl group. The constants confirm unambiguously the conformation of 2-methylacetophenone; their zero values are in accord with the conformation of 2,6-dimethylacetophenone. The zero values in the unsubstituted acetophenone are at variance with previous erroneous report but all J(C,C) values are in accord with calculations at the B3LYP/6-311++G(2d,2p)//B3LYP/6-311+G(d,p) level. Copyright 2004 John Wiley & Sons, Ltd.

  19. Synthesis of Heavy Fluorous Ruthenium Metathesis Catalysts Using the Stereoselective Addition of Polyfluoroalkyllithium to Sterically Hindered Diimines

    Czech Academy of Sciences Publication Activity Database

    Hošek, J.; Rybáčková, M.; Čejka, J.; Cvačka, Josef; Kvíčala, J.

    2015-01-01

    Roč. 34, č. 13 (2015), s. 3327 -3334 ISSN 0276-7333 Institutional support: RVO:61388963 Keywords : ring-closing metathesis * form tetrasubstituted olefins * N-heterocyclic carbene Subject RIV: CC - Organic Chemistry Impact factor: 4.186, year: 2015

  20. Sterically controlled mechanochemistry under hydrostatic pressure

    Science.gov (United States)

    Yan, Hao; Yang, Fan; Pan, Ding; Lin, Yu; Hohman, J. Nathan; Solis-Ibarra, Diego; Li, Fei Hua; Dahl, Jeremy E. P.; Carlson, Robert M. K.; Tkachenko, Boryslav A.; Fokin, Andrey A.; Schreiner, Peter R.; Galli, Giulia; Mao, Wendy L.; Shen, Zhi-Xun; Melosh, Nicholas A.

    2018-02-01

    Mechanical stimuli can modify the energy landscape of chemical reactions and enable reaction pathways, offering a synthetic strategy that complements conventional chemistry. These mechanochemical mechanisms have been studied extensively in one-dimensional polymers under tensile stress using ring-opening and reorganization, polymer unzipping and disulfide reduction as model reactions. In these systems, the pulling force stretches chemical bonds, initiating the reaction. Additionally, it has been shown that forces orthogonal to the chemical bonds can alter the rate of bond dissociation. However, these bond activation mechanisms have not been possible under isotropic, compressive stress (that is, hydrostatic pressure). Here we show that mechanochemistry through isotropic compression is possible by molecularly engineering structures that can translate macroscopic isotropic stress into molecular-level anisotropic strain. We engineer molecules with mechanically heterogeneous components—a compressible (‘soft’) mechanophore and incompressible (‘hard’) ligands. In these ‘molecular anvils’, isotropic stress leads to relative motions of the rigid ligands, anisotropically deforming the compressible mechanophore and activating bonds. Conversely, rigid ligands in steric contact impede relative motion, blocking reactivity. We combine experiments and computations to demonstrate hydrostatic-pressure-driven redox reactions in metal-organic chalcogenides that incorporate molecular elements that have heterogeneous compressibility, in which bending of bond angles or shearing of adjacent chains activates the metal-chalcogen bonds, leading to the formation of the elemental metal. These results reveal an unexplored reaction mechanism and suggest possible strategies for high-specificity mechanosynthesis.

  1. Unlocking the Sugar ‘Steric Gate’ of DNA Polymerases†

    OpenAIRE

    Brown, Jessica A.; Suo, Zucai

    2011-01-01

    To maintain genomic stability, ribonucleotide incorporation during DNA synthesis is controlled predominantly at the DNA polymerase level. A steric clash between the 2′-hydroxyl of an incoming ribonucleotide and a bulky active site residue, known as the ‘steric gate’, establishes an effective mechanism for most DNA polymerases to selectively insert deoxyribonucleotides. Recent kinetic, structural, and in vivo studies have illuminated novel features about ribonucleotide exclusion and the mechan...

  2. Unlocking the Sugar ‘Steric Gate’ of DNA Polymerases†

    Science.gov (United States)

    Brown, Jessica A.; Suo, Zucai

    2011-01-01

    To maintain genomic stability, ribonucleotide incorporation during DNA synthesis is controlled predominantly at the DNA polymerase level. A steric clash between the 2′-hydroxyl of an incoming ribonucleotide and a bulky active site residue, known as the ‘steric gate’, establishes an effective mechanism for most DNA polymerases to selectively insert deoxyribonucleotides. Recent kinetic, structural, and in vivo studies have illuminated novel features about ribonucleotide exclusion and the mechanistic consequences of ribonucleotide misincorporation on downstream events, such as the bypass of a ribonucleotide in a DNA template and the subsequent extension of the DNA lesion bypass product. These important findings are summarized in this review article. PMID:21226515

  3. Steric Maps to Evaluate the Role of Steric Hindrance on the IPr NHC Ligand

    KAUST Repository

    Poater, Albert

    2013-06-01

    Density functional theory (DFT) calculations were used to predict and rationalize the effect of the modification of the structure of the prototype 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene) (IPr) N-heterocyclic carbene (NHC) ligand. The modification consists in the substitution of the methyl groups of ortho isopropyl substituent with phenyl groups, and here we plan to describe how such significant changes effect the metal environment and therefore the related catalytic behaviour by simple steric maps. Bearing in mind that there is a significant structural difference between IPr and IPr* ligands, that translated in different reactivity for several olefin metathesis reactions, here by means of DFT we characterize where the NHC ligand plays a more active role and where it is a simple spectator, or at least its modification does not significantly change its catalytic role/performance. Furthermore, this communication endeavours to modify further the skeleton of the IPr NHC ligand. The optimization of these bulky new systems go to the limits of the DFT computational method.

  4. Survivors of Downsizing: Helpful and Hindering Experiences

    Science.gov (United States)

    Amundson, Norman E.; Borgen, William A.; Jordan, Sharalyn; Erlebach, Anne C.

    2004-01-01

    Thirty-one downsizing survivors from both the private and public sector were interviewed to determine incidents that either helped or hindered their transition through 1 or more organizational downsizings. A critical incident technique was used to analyze and organize the data around themes that emerged, themes were represented by both positive…

  5. When Higher Working Memory Capacity Hinders Insight

    Science.gov (United States)

    DeCaro, Marci S.; Van Stockum, Charles A., Jr.; Wieth, Mareike B.

    2016-01-01

    Higher working memory capacity (WMC) improves performance on a range of cognitive and academic tasks. However, a greater ability to control attention sometimes leads individuals with higher WMC to persist in using complex, attention-demanding approaches that are suboptimal for a given task. We examined whether higher WMC would hinder insight…

  6. Surface Topography Hinders Bacterial Surface Motility.

    Science.gov (United States)

    Chang, Yow-Ren; Weeks, Eric R; Ducker, William A

    2018-03-21

    We demonstrate that the surface motility of the bacterium, Pseudomonas aeruginosa, is hindered by a crystalline hemispherical topography with wavelength in the range of 2-8 μm. The motility was determined by the analysis of time-lapse microscopy images of cells in a flowing growth medium maintained at 37 °C. The net displacement of bacteria over 5 min is much lower on surfaces containing 2-8 μm hemispheres than on flat topography, but displacement on the 1 μm hemispheres is not lower. That is, there is a threshold between 1 and 2 μm for response to the topography. Cells on the 4 μm hemispheres were more likely to travel parallel to the local crystal axis than in other directions. Cells on the 8 μm topography were less likely to travel across the crowns of the hemispheres and were also more likely to make 30°-50° turns than on flat surfaces. These results show that surface topography can act as a significant barrier to surface motility and may therefore hinder surface exploration by bacteria. Because surface exploration can be a part of the process whereby bacteria form colonies and seek nutrients, these results help to elucidate the mechanism by which surface topography hinders biofilm formation.

  7. Elimination reactions. V. Steric effects in Hofmann elimination

    International Nuclear Information System (INIS)

    Coke, J.L.; Smith, G.D.; Britton, G.H. Jr.

    1975-01-01

    Earlier Hofmann elimination studies were extended, and the percent syn eliminations in several ring systems have been correlated using cis-d 1 and trans-d 1 models. The measurements of several syn and anti k/sub H//k/sub D/ kinetic isotope effects are reported. Results indicate that Hofmann elimination of N,N,N-trimethyl-3,3-dimethylcyclopentylammonium hydroxide goes by 97 percent syn mechanism to give 3,3-dimethylcyclopentene and by 70 + - 6 percent syn mechanism to give 4,4-dimethylcyclopentene. There appears to be severe steric interactions in the anti mechanism in the 3,3-dimethylcyclopentyl system. Results indicate that, for Hofmann pyrolysis of trimethylammonium hydroxides, cyclopentene is formed by a 39 +- 7 percent syn mechanism, cyclohexene is formed by a 2 + - 2 percent syn mechanism, and cycloheptene is formed by a 30 +- 2 percent syn mechanism. Steric effects on isotope effects and mechanisms are discussed. (U.S.)

  8. Non-Markovianity hinders Quantum Darwinism

    Science.gov (United States)

    Galve, Fernando; Zambrini, Roberta; Maniscalco, Sabrina

    2016-01-01

    We investigate Quantum Darwinism and the emergence of a classical world from the quantum one in connection with the spectral properties of the environment. We use a microscopic model of quantum environment in which, by changing a simple system parameter, we can modify the information back flow from environment into the system, and therefore its non-Markovian character. We show that the presence of memory effects hinders the emergence of classical objective reality, linking these two apparently unrelated concepts via a unique dynamical feature related to decoherence factors.

  9. Melting Can Hinder Impact-Induced Adhesion

    Science.gov (United States)

    Hassani-Gangaraj, Mostafa; Veysset, David; Nelson, Keith A.; Schuh, Christopher A.

    2017-10-01

    Melting has long been used to join metallic materials, from welding to selective laser melting in additive manufacturing. In the same school of thought, localized melting has been generally perceived as an advantage, if not the main mechanism, for the adhesion of metallic microparticles to substrates during a supersonic impact. Here, we conduct the first in situ supersonic impact observations of individual metallic microparticles aimed at the explicit study of melting effects. Counterintuitively, we find that under at least some conditions melting is disadvantageous and hinders impact-induced adhesion. In the parameter space explored, i.e., ˜10 μ m particle size and ˜1 km /s particle velocity, we argue that the solidification time is much longer than the residence time of the particle on the substrate, so that resolidification cannot be a significant factor in adhesion.

  10. Retinal Photoisomerization in Rhodopsin: Electrostatic and Steric Catalysis

    International Nuclear Information System (INIS)

    Tomasello, Gaia; Altoe, Piero; Stenta, Marco; Olaso-Gonzalez, Gloria; Garavelli, Marco; Orlandi, Giorgio

    2007-01-01

    Excited state QM(CASPT2//CASSCF)/MM(GAFF) calculations, by our recently developed code COBRAMM (Computations at Bologna Relating Ab-initio and Molecular Mechanic Methods), were carried out in rhodopsin to investigate on the steric and electrostatic effects in retinal photoisomerization catalysis due to the β-ionone ring and glutammate 181 (GLU 181), respectively. The excited state photoisomerization channel has been mapped and a new christallographyc structure (2.2 Aa resolution) has been used for this purpose. Two different set-ups have been used to evaluate the electrostatic effects of GLU 181 (which is very close to the central double bond of the chromophore): the first with a neutral GLU 181 (as commonly accepted), the second with a negatively charged (i.e. deprotonated) GLU 181 (as very recent experimental findings seem to suggest). On the other hand, β-ionone ring steric effects were evaluated by calculating the photoisomerization path of a modified chromophore, where the ring double bond has been saturated. Spectroscopic properties were calculated and compared with the available experimental data

  11. Overlearned responses hinder S-R binding.

    Science.gov (United States)

    Moeller, Birte; Frings, Christian

    2017-01-01

    Two mechanisms that are important for human action control are the integration of individual action plans (see Hommel, Müsseler, Aschersleben, & Prinz, 2001) and the automatization of overlearned actions to familiar stimuli (see Logan, 1988). In the present study, we analyzed the influence of automatization on action plan integration. Integration with pronunciation responses were compared for response incompatible word and nonword stimuli. Stimulus-response binding effects were observed for nonwords. In contrast, words that automatically triggered an overlearned pronunciation response were not integrated with pronunciation of a different word. That is, automatized response retrieval hindered binding effects regarding the retrieving stimulus and a new response. The results are a first indication of the way that binding and learning processes interact, and might also be a first step to understanding the more complex interdependency of the processes responsible for stimulus-response binding in action control and stimulus-response associations in learning research. (PsycINFO Database Record (c) 2016 APA, all rights reserved).

  12. Relationship structure-antioxidant activity of hindered phenolic compounds

    Directory of Open Access Journals (Sweden)

    Weng, X. C.

    2014-12-01

    Full Text Available The relationship between the structure and the antioxidant activity of 21 hindered phenolic compounds was investigated by Rancimat and DPPH· tests. 3-tert-butyl-5-methylbenzene-1,2-diol is the strongest antioxidant in the Rancimat test but not in the DPPH· test because its two hydroxyl groups have very strong steric synergy. 2,6-Ditert-butyl-4-hydroxy-methylphenol exhibits a strong antioxidant activity as 2,6-ditertbutyl- 4-methoxyphenol does in lard. 2,6-Ditert-butyl-4- hydroxy-methylphenol also exhibits stronger activity than 2-tert-butyl-4- methoxyphenol. The methylene of 2,6-ditert-butyl-4-hydroxy-methylphenol can provide a hydrogen atom to active free radicals like a phenolic hydroxyl group does because it is greatly activated by both the aromatic ring and hydroxyl group. Five factors affect the antioxidant activities of the phenolic compounds: how stable the phenolic compound free radicals are after providing hydrogen atoms; how many hy drogen atoms each of the phenolic compounds can provide; how fast the phenolic compounds provide hydrogen atoms; how easily the phenolic compound free radicals can combine with more active free radicals, and whether or not a new antioxidant can form after the phenolic compound provides hydrogen atoms.La relación entre estructura y la actividad antioxidante de 21 compuestos fenólicos con impedimentos estéricos fue investigado mediante ensayos con Rancimat y DPPH·. El 3-terc-butil-5-metilbenceno-1,2-diol es el antioxidante más potente en los ensayos mediante Rancimat pero no mediante ensayos con DPPH·, porque sus dos grupos hidroxilo tienen una fuerte sinergia estérica. El 2,6-Di-terc-butil-4-hidroxi-metil-fenol mostró una actividad antioxidante tan fuerte como el 2,6-di-ter-butil-4-metoxifenol en ensayos con manteca de cerdo. El 2,6-di-terc-butil-4-hidroxi-metilfenol también mostró una actividad más fuerte que el 2-terc-butil-4-metoxifenol. El grupo metileno del 2,6-di-ter-butil-4-hidroxi

  13. SAXS Study of Sterically Stabilized Lipid Nanocarriers Functionalized by DNA

    Science.gov (United States)

    Angelov, Borislav; Angelova, Angelina; Filippov, Sergey; Karlsson, Göran; Terrill, Nick; Lesieur, Sylviane; Štěpánek, Petr

    2012-03-01

    The structure of novel spontaneously self-assembled plasmid DNA/lipid complexes is investigated by means of synchrotron radiation small-angle X-ray scattering (SAXS) and Cryo-TEM imaging. Liquid crystalline (LC) hydrated lipid systems are prepared using the non-ionic lipids monoolein and DOPE-PEG2000 and the cationic amphiphile CTAB. The employed plasmid DNA (pDNA) is encoding for the human protein brain-derived neurotrophic factor (BDNF). A coexistence of nanoparticulate objects with different LC inner organizations is established. A transition from bicontinuous membrane sponges, cubosome intermediates and unilamelar liposomes to multilamellar vesicles, functionalized by pDNA, is favoured upon binding and compaction of pBDNF onto the cationic PEGylated lipid nanocarriers. The obtained sterically stabilized multicompartment nanoobjects, with confined supercoiled plasmid DNA (pBDNF), are important in the context of multicompartment lipid nanocarriers of interest for gene therapy of neurodegenerative diseases.

  14. SAXS Study of Sterically Stabilized Lipid Nanocarriers Functionalized by DNA

    International Nuclear Information System (INIS)

    Angelov, Borislav; Filippov, Sergey; Štepánek, Petr; Angelova, Angelina; Lesieur, Sylviane; Karlsson, Göran; Terrill, Nick

    2012-01-01

    The structure of novel spontaneously self-assembled plasmid DNA/lipid complexes is investigated by means of synchrotron radiation small-angle X-ray scattering (SAXS) and Cryo-TEM imaging. Liquid crystalline (LC) hydrated lipid systems are prepared using the non-ionic lipids monoolein and DOPE-PEG 2000 and the cationic amphiphile CTAB. The employed plasmid DNA (pDNA) is encoding for the human protein brain-derived neurotrophic factor (BDNF). A coexistence of nanoparticulate objects with different LC inner organizations is established. A transition from bicontinuous membrane sponges, cubosome intermediates and unilamelar liposomes to multilamellar vesicles, functionalized by pDNA, is favoured upon binding and compaction of pBDNF onto the cationic PEGylated lipid nanocarriers. The obtained sterically stabilized multicompartment nanoobjects, with confined supercoiled plasmid DNA (pBDNF), are important in the context of multicompartment lipid nanocarriers of interest for gene therapy of neurodegenerative diseases.

  15. Steric-electronic effects in malarial peptides inducing sterile immunity

    Energy Technology Data Exchange (ETDEWEB)

    Moreno-Vranich, Armando [Fundacion Instituto de Inmunologia de Colombia (FIDIC), Bogota (Colombia); Patarroyo, Manuel E., E-mail: mepatarr@mail.com [Fundacion Instituto de Inmunologia de Colombia (FIDIC), Bogota (Colombia); Universidad Nacional de Colombia, Bogota (Colombia)

    2012-07-13

    Highlights: Black-Right-Pointing-Pointer Is it evident that the residues position are relevant regarding of {phi} angular value. Black-Right-Pointing-Pointer The geometry considered for detailing the alterations undergone by HABPs. Black-Right-Pointing-Pointer The inter planar interactions ruled by clashes between the atoms making them up. -- Abstract: Conserved Plasmodium falciparum high activity binding peptides' (HABPs) most relevant proteins involved in malaria parasite invasion are immunologically silent; critical binding residues must therefore be specifically replaced to render them highly immunogenic and protection-inducing. Such changes have a tremendous impact on these peptides' steric-electronic effects, such as modifications to peptide length peptide bonds and electronic orbitals' disposition, to allow a better fit into immune system MHCII molecules and better interaction with the TCR which might account for the final immunological outcome.

  16. Steric parameters and excess properties of hydroxamic acids

    International Nuclear Information System (INIS)

    Patre, Sandhya; Thakur, Piyush; Pande, Rama

    2012-01-01

    Graphical abstract: Plot of excess molar volume, V E , vs X 2 of (A) PBHA in DMF, (B) PMNHA in DMF, and (C) PNHA in DMF, at (■), 298.15 K; (▪), 303.15 K; (▪), 308.15 K; and (▪), 313.15 K. Highlights: ► Apparent molar volume indicates greater solute–solvent interactions. ► Excess properties show higher dispersion force in solution than pure solvent. ► Excess parameters suggest strong solute–solvent and solute–solute interactions. ► Limiting apparent molar expansibilities instigate highly hydrophobic characters. ► Hepler’s constant suggest the structure promoter nature of hydroxamic acids. - Abstract: Steric parameters of N-phenylbenzo-, N-phenyl-4-methyl-3-nitrobenzo-, and N-phenyl-4-nitrobenzo-, hydroxamic acids were measured in N,N-dimethylformamide (DMF) as a function of their concentrations at T = (298.15, 303.15, 308.15, and 313.15) K. The apparent molar volume (V φ ), limiting apparent molar volume (V φ 0 ) at infinite dilution and the slope (S V ∗ ) are calculated from the experimental values of density (ρ) by applying the Masson’s equation. The apparent molar expansibility at infinite dilution (φ E 0 ), molar volume (V) and the excess molar volume (V E ) are also computed. The refractive indices (n) have been used to calculate the steric parameters, viz. molar refraction (R M ), polarizability (α) and excess molar refraction (R) of these molecules. The results show the strong solute–solvent interactions present in the system and thus, help to explore the molecular structure.

  17. Novel 6FDA-based polyimides derived from sterically hindered Tröger's base diamines: Synthesis and gas permeation properties

    KAUST Repository

    Ghanem, Bader

    2016-04-30

    Two novel Tröger\\'s base-based di-o-substituted diamine monomers were synthesized and used to prepare two intrinsically microporous 6FDA-based polyimides (PIM-PI-TB-1 and PIM-PI-TB-2) with high molecular weight, high thermal stability and excellent solubility in common organic solvents. Compared to previously reported methods for preparing TB-based diamines, which are based on reduction of dimerized nitro-substituted anilines or condensation of phenylenediamine derivatives with dianhydrides, the novel protocol can be used to prepare different functionalized TB-based diamine monomers from a wide variety of aniline derivatives. PIM-PI-TB-1 (made from 6FDA and dibromo-tetramethyl-substituted TB diamine) and PIM-PI-TB-2 (made from 6FDA and tetramethyl-substituted TB diamine) are intrinsically microporous polymers with high BET surface areas of 440 m2/g and 580 m2/g, respectively. Pure-gas permeability coefficients of He, H2, N2, O2, CH4, and CO2 were measured at 35 °C and 2 bar for fresh and 180 days aged films. Both TB-based polyimides exhibited high gas permeability with moderate selectivity. The gas permeability dropped significantly coupled with a moderate increase in selectivity after long-term physical aging of 180 days.

  18. Novel 6FDA-based polyimides derived from sterically hindered Tröger's base diamines: Synthesis and gas permeation properties

    KAUST Repository

    Ghanem, Bader; Alaslai, Nasser Y.; Miao, Xiaohe; Pinnau, Ingo

    2016-01-01

    Two novel Tröger's base-based di-o-substituted diamine monomers were synthesized and used to prepare two intrinsically microporous 6FDA-based polyimides (PIM-PI-TB-1 and PIM-PI-TB-2) with high molecular weight, high thermal stability and excellent solubility in common organic solvents. Compared to previously reported methods for preparing TB-based diamines, which are based on reduction of dimerized nitro-substituted anilines or condensation of phenylenediamine derivatives with dianhydrides, the novel protocol can be used to prepare different functionalized TB-based diamine monomers from a wide variety of aniline derivatives. PIM-PI-TB-1 (made from 6FDA and dibromo-tetramethyl-substituted TB diamine) and PIM-PI-TB-2 (made from 6FDA and tetramethyl-substituted TB diamine) are intrinsically microporous polymers with high BET surface areas of 440 m2/g and 580 m2/g, respectively. Pure-gas permeability coefficients of He, H2, N2, O2, CH4, and CO2 were measured at 35 °C and 2 bar for fresh and 180 days aged films. Both TB-based polyimides exhibited high gas permeability with moderate selectivity. The gas permeability dropped significantly coupled with a moderate increase in selectivity after long-term physical aging of 180 days.

  19. Zirconium bisamidinate complexes with sterically demanding ligands : structure, solution dynamics, and reactivity

    NARCIS (Netherlands)

    Otten, Edwin; Dijkstra, Peter; Visser, Cindy; Meetsma, Auke; Hessen, Bart

    2005-01-01

    Bisamidinate zirconium dichloride and dimethyl complexes with the sterically demanding amidinate ligands [PhC(NAr)(2))](-) (A) and [PhC(NAr)(NAr')](-) (B) (Ar = 2,6-(Pr2C6H3)-Pr-i; Ar' = 2,6-Me2C6H3) were prepared. The steric demand of ligand A induces the unusual trans geometry in

  20. Steric and electrostatic interactions govern nanofiltration of amino acids.

    Science.gov (United States)

    Shim, Yongki; Chellam, Shankararaman

    2007-10-01

    Crossflow nanofiltration experiments were performed to investigate the factors influencing the removal of amino acids by a commercially available polymeric thin-film composite membrane. The removals of five monoprotic (Ala, Val, Leu, Gly, and Thr), one diprotic (Asp), and one dibasic (Arg) amino acids in a range of permeate fluxes, feed pH values, and ionic strengths were analyzed using a phenomenological model of membrane transport. At any given pH and ionic strength, reflection coefficients (rejection at asymptotically infinite flux) of monoprotic amino acids increased with molar radius demonstrating the role of steric interactions on their removal. Additionally, consistent with Donnan exclusion, higher reflection coefficients were obtained when the membrane and the amino acids both carried the same nature of charge (positive or negative). In other words, both co-ion repulsion and molecular size determined amino acids removal. Importantly, the removal of effectively neutral amino acids were significantly higher than neutral sugars and alcohols of similar size demonstrating that even near their isoelectric point, zwitterionic characteristics preclude them from being considered as strictly neutral. (c) 2007 Wiley Periodicals, Inc.

  1. Synthesis and characterization of copolymers from hindered amines and vinyl monomers

    Directory of Open Access Journals (Sweden)

    Marcelo Aparecido Chinelatto

    2014-01-01

    Full Text Available New copolymers from hindered amines and vinyl monomers were synthesized by radical chain polymerization. To obtain polymeric HALS, acrylamide-(1ATP and acrylate-(4ATP monomers, derivatives from 2,2,6,6-tetramethylpiperidine and 2,2,6,6-tetramethyl-4-piperidinol were synthesized. The radical chain polymerization of 1ATP with styrene (Sty using 1-butanethiol (BTN resulted in a copolymer with 95 units of Sty and 15 units of 1ATP. The radical chain polymerization of 1ATP and vinyl acetate (VAc has produced only 1ATP homopolymer. In the chain polymerization of 4ATP with Sty or VAc, the hydrogen atom bonded to the nitrogen of 4ATP is labile enough to originate another radical at this site. The steric hindrance imposed by methyl groups on this bonding site hampers its reaction with other propagating species and the formation of a copolymer or network structure will be dependent on the size of the pendent group in the vinyl monomer.

  2. Uncertainties in Steric Sea Level Change Estimation During the Satellite Altimeter Era: Concepts and Practices

    Science.gov (United States)

    MacIntosh, C. R.; Merchant, C. J.; von Schuckmann, K.

    2017-01-01

    This article presents a review of current practice in estimating steric sea level change, focussed on the treatment of uncertainty. Steric sea level change is the contribution to the change in sea level arising from the dependence of density on temperature and salinity. It is a significant component of sea level rise and a reflection of changing ocean heat content. However, tracking these steric changes still remains a significant challenge for the scientific community. We review the importance of understanding the uncertainty in estimates of steric sea level change. Relevant concepts of uncertainty are discussed and illustrated with the example of observational uncertainty propagation from a single profile of temperature and salinity measurements to steric height. We summarise and discuss the recent literature on methodologies and techniques used to estimate steric sea level in the context of the treatment of uncertainty. Our conclusions are that progress in quantifying steric sea level uncertainty will benefit from: greater clarity and transparency in published discussions of uncertainty, including exploitation of international standards for quantifying and expressing uncertainty in measurement; and the development of community "recipes" for quantifying the error covariances in observations and from sparse sampling and for estimating and propagating uncertainty across spatio-temporal scales.

  3. Poisson-Nernst-Planck equations with steric effects - non-convexity and multiple stationary solutions

    Science.gov (United States)

    Gavish, Nir

    2018-04-01

    We study the existence and stability of stationary solutions of Poisson-Nernst-Planck equations with steric effects (PNP-steric equations) with two counter-charged species. We show that within a range of parameters, steric effects give rise to multiple solutions of the corresponding stationary equation that are smooth. The PNP-steric equation, however, is found to be ill-posed at the parameter regime where multiple solutions arise. Following these findings, we introduce a novel PNP-Cahn-Hilliard model, show that it is well-posed and that it admits multiple stationary solutions that are smooth and stable. The various branches of stationary solutions and their stability are mapped utilizing bifurcation analysis and numerical continuation methods.

  4. Exploring electronic and steric effects on the insertion and polymerization reactivity of phosphinesulfonato pdii catalysts

    KAUST Repository

    Neuwald, Boris; Falivene, Laura; Caporaso, Lucia; Cavallo, Luigi; Mecking, Stefan

    2013-01-01

    incorporation at low MA concentrations in the copolymerization; and 3) steric shielding leads to a pronounced increase in polymer molecular weight in the copolymerization. The catalyst properties induced by a given P-aryl (alkyl) moiety were combined effectively

  5. Tuning and Quantifying Steric and Electronic Effects of N-Heterocyclic Carbenes

    KAUST Repository

    Falivene, Laura

    2014-07-12

    This chapter states that the main handles for tuning steric and electronic effects are the substituents on N atoms, the nature of the C4-C5 bridge (either saturated or unsaturated), and the substituents on the C4 and C5 atoms. The initial intuition that steric properties of N-heterocyclic carbenes (NHCs) could be modulated and could impact catalytic behavior stimulated the development of steric descriptors to quantify the steric requirement of different NHCs and, possibly, to compare them with tertiary phosphines. NHCs can be classified as typically strong σ-basic/π-acid ligands, although they have been also shown to exhibit reasonable π-basic properties. This electronic modularity allows NHC ligands to adapt flexibly to different chemical environments represented by a transition metal and the other ligands. © 2014 Wiley-VCH Verlag GmbH & Co. KGaA. All rights reserved.

  6. Antibody-Hapten Recognition at the Surface of Functionalized Liposomes Studied by SPR: Steric Hindrance of Pegylated Phospholipids in Stealth Liposomes Prepared for Targeted Radionuclide Delivery

    Directory of Open Access Journals (Sweden)

    Eliot. P. Botosoa

    2011-01-01

    Full Text Available Targeted PEGylated liposomes could increase the amount of drugs or radionuclides delivered to tumor cells. They show favorable stability and pharmacokinetics, but steric hindrance of the PEG chains can block the binding of the targeting moiety. Here, specific interactions between an antihapten antibody (clone 734, specific for the DTPA-indium complex and DTPA-indium-tagged liposomes were characterized by surface plasmon resonance (SPR. Non-PEGylated liposomes fused on CM5 chips whereas PEGylated liposomes did not. By contrast, both PEGylated and non-PEGylated liposomes attached to L1 chips without fusion. SPR binding kinetics showed that, in the absence of PEG, the antibody binds the hapten at the surface of lipid bilayers with the affinity of the soluble hapten. The incorporation of PEGylated lipids hinders antibody binding to extents depending on PEGylated lipid fraction and PEG molecular weight. SPR on immobilized liposomes thus appears as a useful technique to optimize formulations of liposomes for targeted therapy.

  7. Facilitating or hindering social cohesion? The impact of the ...

    African Journals Online (AJOL)

    However, we show in this article that that the impact of the CWP is not always positive and that the CWP may in some cases result in tensions and contradictions that hinder social cohesion and even cause violence. If not implemented in a consultative participatory manner, the CWP may be a source of conflict rather than of ...

  8. Challenges hindering female participation in politics as expressed ...

    African Journals Online (AJOL)

    The study challenges hindering female participation in politics as expressed by female politicians in the federal capital territory, Abuja, Nigeria. The research design adopted for this study was descriptive survey. The respondents were 210 female politicians selected from six Area Councils of the FCT using a proportionate ...

  9. Multiple solutions of steady-state Poisson–Nernst–Planck equations with steric effects

    International Nuclear Information System (INIS)

    Lin, Tai-Chia; Eisenberg, Bob

    2015-01-01

    Experiments measuring currents through single protein channels show unstable currents. Channels switch between ‘open’ or ‘closed’ states in a spontaneous stochastic process called gating. Currents are either (nearly) zero or at a definite level, characteristic of each type of protein, independent of time, once the channel is open. The steady state Poisson–Nernst–Planck equations with steric effects (PNP-steric equations) describe steady current through the open channel quite well, in a wide variety of conditions. Here we study the existence of multiple solutions of steady state PNP-steric equations to see if they themselves, without modification or augmentation, can describe two levels of current. We prove that there are two steady state solutions of PNP-steric equations for (a) three types of ion species (two types of cations and one type of anion) with a positive constant permanent charge, and (b) four types of ion species (two types of cations and their counter-ions) with a constant permanent charge but no sign condition. The excess currents (due to steric effects) associated with these two steady state solutions are derived and expressed as two distinct formulas. Our results indicate that PNP-steric equations may become a useful model to study spontaneous gating of ion channels. Spontaneous gating is thought to involve small structural changes in the channel protein that perhaps produce large changes in the profiles of free energy that determine ion flow. Gating is known to be modulated by external structures. Both can be included in future extensions of our present analysis. (paper)

  10. Reversible Redox-Induced Modulation of Sterics in an α-Diimine Ligand Coordinated to Gallium

    Energy Technology Data Exchange (ETDEWEB)

    Zarkesh, Ryan A. [Sandia National Lab. (SNL-CA), Livermore, CA (United States); Foster, Michael E. [Sandia National Lab. (SNL-CA), Livermore, CA (United States); Ichimura, Andrew S. [San Francisco State Univ., CA (United States); Anstey, Mitchell R. [Davidson College, Davidson, NC (United States)

    2017-07-01

    The ability to tune the steric envelope through redox events post-synthetically or in tandem with other chemical processes is a powerful tool that could assist in enabling new catalytic methodologies and understanding potential pitfalls in ligand design. The α-diimine ligand, dmp-BIAN, exhibits the peculiar and previously unreported feature of varying steric profiles depending on oxidation state when paired with a main group element. A study of the factors that give rise to this behaviour as well as its impact on the incorporation of other ligands is performed.

  11. Hindered bacterial mobility in porous media flow enhances dispersion

    Science.gov (United States)

    Dehkharghani, Amin; Waisbord, Nicolas; Dunkel, Jörn; Guasto, Jeffrey

    2017-11-01

    Swimming bacteria live in porous environments characterized by dynamic fluid flows, where they play a crucial role in processes ranging from the bioremediation to the spread of infections. We study bacterial transport in a quasi-two-dimensional porous microfluidic device, which is complemented by Langevin simulations. The cell trajectories reveal filamentous patterns of high cell concentration, which result from the accumulation of bacteria in the high-shear regions of the flow and their subsequent advection. Moreover, the effective diffusion coefficient of the motile bacteria is severely hindered in the transverse direction to the flow due to decorrelation of the cells' persistent random walk by shear-induced rotation. The hindered lateral diffusion has the surprising consequence of strongly enhancing the longitudinal bacterial transport through a dispersion effect. These results demonstrate the significant role of the flow and geometry in bacterial transport through porous media with potential implications for understanding ecosystem dynamics and engineering bioreactors. NSF CBET-1511340, NSF CAREER-1554095.

  12. Synthesis and Properties of New Polymer Having Hindered Phenol Antioxidants

    International Nuclear Information System (INIS)

    Kim, Taek Hyeon; Song, Yi Rang; Kim, Jae Nyoung

    2003-01-01

    Polymeric antioxidants was successfully prepared by the copolymerization of monomeric maleimide with MMA. The copolymers possess some stabilizing effect against thermal oxidation with oven aging in air at 120 .deg. C for 5 days and also have the some resistance to water extraction. It is well known that the addition of antioxidants is the most convenient and effective way to block the thermal oxidation of polyolefins. Hindered phenol antioxidants, which contain the 2,6-di-tert-butylphenol functional group, are very effective primary antioxidants. However, low molecular weight (MW) antioxidants are easily lost from the polymers by the physical loss such as migration, evaporation, and extraction by liquid. The effectiveness of low MW antioxidants is limited. Therefore a new trend for antioxidant development is to prepare antioxidant with higher MW. The copolymerization or homopolymerization of the functional monomer bearing hindered phenol antioxidants is a conventional method for preparing polymeric antioxidants

  13. Teamwork in a coronary care unit: facilitating and hindering aspects

    Directory of Open Access Journals (Sweden)

    Bethania Ferreira Goulart

    2016-06-01

    Full Text Available Abstract OBJECTIVE To identify, within a multidisciplinary team, the facilitating and hindering aspects for teamwork in a coronary care unit. METHOD A descriptive study, with qualitative and quantitative data, was carried out in the coronary care unit of a public hospital. The study population consisted of professionals working in the unit for at least one year. Those who were on leave or who were not located were excluded. The critical incident technique was used for data collection, by means of semi-structured interviews. For data analysis, content analysis and the critical incident technique were applied. RESULTS Participants were 45 professionals: 29 nursing professionals; 11 physicians; 4 physical therapists; and 1 psychologist. A total of 49 situations (77.6% with negative references; 385 behaviors (54.2% with positive references; and 182 consequences emerged (71.9% with negative references. Positive references facilitate teamwork, whereas negative references hinder it. A collaborative/communicative interprofessional relationship was evidenced as a facilitator; whereas poor collaboration among agents/inadequate management was a hindering aspect. CONCLUSION Despite the prevalence of negative situations and consequences, the emphasis on positive behaviors reveals the efforts the agents make in order to overcome obstacles and carry out teamwork.

  14. Factors Motivating and Hindering Information and Communication Technologies Action Competence

    Directory of Open Access Journals (Sweden)

    Adile Aşkım Kurt

    2013-01-01

    Full Text Available Information and Communication Technologies Action Competence (ICTAC can be defined as “individuals’ motivation and capacity to voluntarily employ their ICT skills for initiating or taking part in civic actions”. Since academic staff and teachers in ICT related fields have crucial roles in training action-competent individuals, this study aimed to determine the views of preservice teachers and instructors in Computer Education and Instructional Technology (CEIT departments about the motivating and hindering factors regarding ICTAC. Researchers used purposeful sampling technique and identified seven instructors and 16 students attending outlier CEIT departments from four different Turkish state universities. Since there is no contemporary framework on factors motivating or hindering ICTAC, the study was conducted with a qualitative approach and the data were collected through semi-structured interviews. Factors motivating and hindering ICTAC were identified through a content analysis. Findings of the study are believed to guide ICT and ICT education professionals in training students with higher levels of ICTAC and guide the course developers to focus on relevant social responsibility issues

  15. Hydrophilic luminescent silicon nanoparticles in steric colloidal solutions: their size, agglomeration and toxicity

    Czech Academy of Sciences Publication Activity Database

    Herynková, Kateřina; Šimáková, Petra; Cibulka, Ondřej; Fučíková, Anna; Kalbáčová, M.H.

    2017-01-01

    Roč. 14, č. 12 (2017), s. 1-4, č. článku 1700195. ISSN 1862-6351 Grant - others:AV ČR(CZ) DAAD-16-18 Program:Bilaterální spolupráce Institutional support: RVO:68378271 Keywords : silicon nanocrystals * colloidal solutions * steric stabilization * cytotoxicity Subject RIV: BO - Biophysics OBOR OECD: Biophysics

  16. Micro-flow synthesis and structural analysis of sterically crowded diimine ligands with five aryl rings

    Directory of Open Access Journals (Sweden)

    Shinichiro Fuse

    2013-11-01

    Full Text Available Sterically crowded diimine ligands with five aryl rings were prepared in one step in good yields using a micro-flow technique. X-ray crystallographic analysis revealed the detailed structure of the bulky ligands. The nickel complexes prepared from the ligands exerted high polymerization activity in the ethylene homopolymerization and copolymerization of ethylene with polar monomers.

  17. Tuning and Quantifying Steric and Electronic Effects of N-Heterocyclic Carbenes

    KAUST Repository

    Falivene, Laura; Poater, Albert; Cavallo, Luigi

    2014-01-01

    This chapter states that the main handles for tuning steric and electronic effects are the substituents on N atoms, the nature of the C4-C5 bridge (either saturated or unsaturated), and the substituents on the C4 and C5 atoms. The initial intuition

  18. Fisher information and steric effect: study of the internal rotation barrier of ethane.

    Science.gov (United States)

    Esquivel, Rodolfo O; Liu, Shubin; Angulo, Juan Carlos; Dehesa, Jesús S; Antolín, Juan; Molina-Espíritu, Moyocoyani

    2011-05-05

    On the basis of a density-based quantification of the steric effect [Liu, S. B. J. Chem. Phys.2007, 126, 244103], the origin of the internal rotation barrier between the eclipsed and staggered conformers of ethane is systematically investigated in this work from an information-theoretical point of view by using the Fisher information measure in conjugated spaces. Two kinds of computational approaches are considered in this work: adiabatic (with optimal structure) and vertical (with fixed geometry). The analyses are performed systematically by following, in each case, the conformeric path by changing the dihedral angle from 0 to 180° . This is calculated at the HF, MP2, B3LYP, and CCSD(T) levels of theory and with several basis sets. Selected descriptors of the densities are utilized to support the observations. Our results show that in the adiabatic case the eclipsed conformer possesses a larger steric repulsion than the staggered conformer, but in the vertical cases the staggered conformer retains a larger steric repulsion. Our results verify the plausibility for defining and computing the steric effect in the post-Hartree-Fock level of theory according to the scheme proposed by Liu.

  19. Steric effects on the primary isotope dependence of secondary kinetic isotope effects in hydride transfer reactions in solution: caused by the isotopically different tunneling ready state conformations?

    Science.gov (United States)

    Maharjan, Binita; Raghibi Boroujeni, Mahdi; Lefton, Jonathan; White, Ormacinda R; Razzaghi, Mortezaali; Hammann, Blake A; Derakhshani-Molayousefi, Mortaza; Eilers, James E; Lu, Yun

    2015-05-27

    The observed 1° isotope effect on 2° KIEs in H-transfer reactions has recently been explained on the basis of a H-tunneling mechanism that uses the concept that the tunneling of a heavier isotope requires a shorter donor-acceptor distance (DAD) than that of a lighter isotope. The shorter DAD in D-tunneling, as compared to H-tunneling, could bring about significant spatial crowding effect that stiffens the 2° H/D vibrations, thus decreasing the 2° KIE. This leads to a new physical organic research direction that examines how structure affects the 1° isotope dependence of 2° KIEs and how this dependence provides information about the structure of the tunneling ready states (TRSs). The hypothesis is that H- and D-tunneling have TRS structures which have different DADs, and pronounced 1° isotope effect on 2° KIEs should be observed in tunneling systems that are sterically hindered. This paper investigates the hypothesis by determining the 1° isotope effect on α- and β-2° KIEs for hydride transfer reactions from various hydride donors to different carbocationic hydride acceptors in solution. The systems were designed to include the interactions of the steric groups and the targeted 2° H/D's in the TRSs. The results substantiate our hypothesis, and they are not consistent with the traditional model of H-tunneling and 1°/2° H coupled motions that has been widely used to explain the 1° isotope dependence of 2° KIEs in the enzyme-catalyzed H-transfer reactions. The behaviors of the 1° isotope dependence of 2° KIEs in solution are compared to those with alcohol dehydrogenases, and sources of the observed "puzzling" 2° KIE behaviors in these enzymes are discussed using the concept of the isotopically different TRS conformations.

  20. Urban search mobile platform modeling in hindered access conditions

    Science.gov (United States)

    Barankova, I. I.; Mikhailova, U. V.; Kalugina, O. B.; Barankov, V. V.

    2018-05-01

    The article explores the control system simulation and the design of the experimental model of the rescue robot mobile platform. The functional interface, a structural functional diagram of the mobile platform control unit, and a functional control scheme for the mobile platform of secure robot were modeled. The task of design a mobile platform for urban searching in hindered access conditions is realized through the use of a mechanical basis with a chassis and crawler drive, a warning device, human heat sensors and a microcontroller based on Arduino platforms.

  1. Factors Hindering the Integration of CALL in a Tertiary Institution

    Directory of Open Access Journals (Sweden)

    Izaham Shah Ismail

    2008-12-01

    Full Text Available The field of Computer Assisted Language Learning (CALL is a field that is constantly evolving as it is very much dependent on the advancement of computer technologies. With new technologies being invented almost every day, experts in the field are looking for ways to apply these new technologies in the language classroom. Despite that, teachers are said to be slow at adopting technology in their classrooms and language teachers, whether at schools or tertiary institutions, are no exception. This study attempts to investigate the factors that hinder ESL instructors at an institution of higher learning from integrating CALL in their lessons. Interviews were conducted with five ESL instructors and results revealed that factors which hinder them from integrating CALL in their teaching are universal factors such as knowledge in technology and pedagogy, computer facilities and resources, absence of exemplary integration of CALL, personal beliefs on language teaching, views on the role of a computers as teacher, and evaluation of learning outcomes.

  2. SambVca 2. A Web Tool for Analyzing Catalytic Pockets with Topographic Steric Maps

    KAUST Repository

    Falivene, Laura; Credendino, Raffaele; Poater, Albert; Petta, Andrea; Serra, Luigi; Oliva, Romina; Scarano, Vittorio; Cavallo, Luigi

    2016-01-01

    Developing more efficient catalysts remains one of the primary targets of organometallic chemists. To accelerate reaching this goal, effective molecular descriptors and visualization tools can represent a remarkable aid. Here, we present a Web application for analyzing the catalytic pocket of metal complexes using topographic steric maps as a general and unbiased descriptor that is suitable for every class of catalysts. To show the broad applicability of our approach, we first compared the steric map of a series of transition metal complexes presenting popular mono-, di-, and tetracoordinated ligands and three classic zirconocenes. This comparative analysis highlighted similarities and differences between totally unrelated ligands. Then, we focused on a recently developed Fe(II) catalyst that is active in the asymmetric transfer hydrogenation of ketones and imines. Finally, we expand the scope of these tools to rationalize the inversion of enantioselectivity in enzymatic catalysis, achieved by point mutation of three amino acids of mononuclear p-hydroxymandelate synthase.

  3. Abstraction of iodine from aromatic iodides by alkyl radicals: steric and electronic effects.

    Science.gov (United States)

    Dolenc, Darko; Plesnicar, Bozo

    2006-10-13

    Abstraction of the iodine atom from aryl iodides by alkyl radicals takes place in some cases very efficiently despite the unfavorable difference in bond dissociation energies of C-I bonds in alkyl and aryl iodides. The abstraction is most efficient in iodobenzenes, ortho-substituted with bulky groups. The ease of abstraction can be explained by the release of steric strain during the elimination of the iodine atom. The rate of abstraction correlates fairly well with the strain energy, calculated by density functional theory (DFT) and Hartree-Fock (HF) methods as a difference in the total energy of ortho and para isomers. However, besides the steric bulk, the presence of some other functional groups in an ortho substituent also influences the rate. The stabilization of the transition state, resembling a 9-I-2 iodanyl radical, by electron-withdrawing groups seems to explain a positive sign of the Hammett rho value in the radical abstraction of halogen atoms.

  4. Steric and Stereochemical Modulation in Pyridyl- and Quinolyl-Containing Ligands

    Directory of Open Access Journals (Sweden)

    Zhaohua Dai

    2016-12-01

    Full Text Available Nitrogen-containing pyridine and quinoline are outstanding platforms on which excellent ionophores and sensors for metal ions can be built. Steric and stereochemical effects can be used to modulate the affinity and selectivity of such ligands toward different metal ions on the coordination chemistry front. On the signal transduction front, such effects can also be used to modulate optical responses of these ligands in metal sensing systems. In this review, steric modulation of achiral ligands and stereochemical modulation in chiral ligands, especially ionophores and sensors for zinc, copper, silver, and mercury, are examined using published structural and spectral data. Although it might be more challenging to construct chiral ligands than achiral ones, isotropic and anisotropic absorption signals from a single chiroptical fluorescent sensor provide not only detection but also differentiation of multiple analytes with high selectivity.

  5. SambVca 2. A Web Tool for Analyzing Catalytic Pockets with Topographic Steric Maps

    KAUST Repository

    Falivene, Laura

    2016-06-27

    Developing more efficient catalysts remains one of the primary targets of organometallic chemists. To accelerate reaching this goal, effective molecular descriptors and visualization tools can represent a remarkable aid. Here, we present a Web application for analyzing the catalytic pocket of metal complexes using topographic steric maps as a general and unbiased descriptor that is suitable for every class of catalysts. To show the broad applicability of our approach, we first compared the steric map of a series of transition metal complexes presenting popular mono-, di-, and tetracoordinated ligands and three classic zirconocenes. This comparative analysis highlighted similarities and differences between totally unrelated ligands. Then, we focused on a recently developed Fe(II) catalyst that is active in the asymmetric transfer hydrogenation of ketones and imines. Finally, we expand the scope of these tools to rationalize the inversion of enantioselectivity in enzymatic catalysis, achieved by point mutation of three amino acids of mononuclear p-hydroxymandelate synthase.

  6. Parameterization of phosphine ligands demonstrates enhancement of nickel catalysis via remote steric effects

    Science.gov (United States)

    Wu, Kevin; Doyle, Abigail G.

    2017-08-01

    The field of Ni-catalysed cross-coupling has seen rapid recent growth because of the low cost of Ni, its earth abundance, and its ability to promote unique cross-coupling reactions. Whereas advances in the related field of Pd-catalysed cross-coupling have been driven by ligand design, the development of ligands specifically for Ni has received minimal attention. Here, we disclose a class of phosphines that enable the Ni-catalysed Csp3 Suzuki coupling of acetals with boronic acids to generate benzylic ethers, a reaction that failed with known ligands for Ni and designer phosphines for Pd. Using parameters to quantify phosphine steric and electronic properties together with regression statistical analysis, we identify a model for ligand success. The study suggests that effective phosphines feature remote steric hindrance, a concept that could guide future ligand design tailored to Ni. Our analysis also reveals that two classic descriptors for ligand steric environment—cone angle and % buried volume—are not equivalent, despite their treatment in the literature.

  7. Estimating the magnitude of steric effects in rigid systems by NMR

    International Nuclear Information System (INIS)

    Yoneda, Julliane Diniz; Seidl, Peter Rudolf; Leal, Katia Zaccur

    2008-01-01

    The rapid advance of supramolecular chemistry has led to a better understanding of the forces and interactions that are responsible for many different phenomena. Among these, steric effects play an important role in determining the constraints to association between the species involved. Although the role of steric effects has been recognized for a long time, quantitative information has been mainly related to the comparison of these effects on a chemical reaction or conformational equilibrium rather than the properties of the group of atoms that is responsible for their manifestation. This situation has been changing with the increase in power of computational methods and the accumulation of data on model compounds that can be used for the purpose of comparison. Here we present a short review of our recent work on NMR of rigid carbocyclic systems and apply this type of approach to di- and triamantane systems. Our results show how NMR can be used to locate the segment of a molecule that is subjected to steric effects and evaluate the degree to which these effects will distort its geometry. (author)

  8. Peptide Probes Reveal a Hydrophobic Steric Ratchet in the Anthrax Toxin Protective Antigen Translocase.

    Science.gov (United States)

    Colby, Jennifer M; Krantz, Bryan A

    2015-11-06

    Anthrax toxin is a tripartite virulence factor produced by Bacillus anthracis during infection. Under acidic endosomal pH conditions, the toxin's protective antigen (PA) component forms a transmembrane channel in host cells. The PA channel then translocates its two enzyme components, lethal factor and edema factor, into the host cytosol under the proton motive force. Protein translocation under a proton motive force is catalyzed by a series of nonspecific polypeptide binding sites, called clamps. A 10-residue guest/host peptide model system, KKKKKXXSXX, was used to functionally probe polypeptide-clamp interactions within wild-type PA channels. The guest residues were Thr, Ala, Leu, Phe, Tyr, and Trp. In steady-state translocation experiments, the channel blocked most tightly with peptides that had increasing amounts of nonpolar surface area. Cooperative peptide binding was observed in the Trp-containing peptide sequence but not the other tested sequences. Trp substitutions into a flexible, uncharged linker between the lethal factor amino-terminal domain and diphtheria toxin A chain expedited translocation. Therefore, peptide-clamp sites in translocase channels can sense large steric features (like tryptophan) in peptides, and while these steric interactions may make a peptide translocate poorly, in the context of folded domains, they can make the protein translocate more rapidly presumably via a hydrophobic steric ratchet mechanism. Copyright © 2015 The Authors. Published by Elsevier Ltd.. All rights reserved.

  9. Estimating the magnitude of steric effects in rigid systems by NMR

    Energy Technology Data Exchange (ETDEWEB)

    Yoneda, Julliane Diniz [Universidade Federal Fluminense (UFF), Niteroi, RJ (Brazil). Programa Pos-Graduacao em Quimica Organica; Seidl, Peter Rudolf [Universidade Federal do Rio de Janeiro (UFRJ), RJ (Brazil). Escola de Quimica; Leal, Katia Zaccur, E-mail: pseidl@eq.ufrj.br [Universidade Federal Fluminense (UFF), Niteroi, RJ (Brazil). Dept. de Fisico-Quimica. Programa de Pos-Graduacao em Quimica Organica

    2008-07-01

    The rapid advance of supramolecular chemistry has led to a better understanding of the forces and interactions that are responsible for many different phenomena. Among these, steric effects play an important role in determining the constraints to association between the species involved. Although the role of steric effects has been recognized for a long time, quantitative information has been mainly related to the comparison of these effects on a chemical reaction or conformational equilibrium rather than the properties of the group of atoms that is responsible for their manifestation. This situation has been changing with the increase in power of computational methods and the accumulation of data on model compounds that can be used for the purpose of comparison. Here we present a short review of our recent work on NMR of rigid carbocyclic systems and apply this type of approach to di- and triamantane systems. Our results show how NMR can be used to locate the segment of a molecule that is subjected to steric effects and evaluate the degree to which these effects will distort its geometry. (author)

  10. Social prejudice hindering proper use of car safety seats.

    Science.gov (United States)

    Kanburoglu, Mehmet Kenan; Cizmeci, Mehmet Nevzat; Akelma, Ahmet Zulfikar; Orun, Emel; Yesilyurt, Kubra; Tatli, Mustafa Mansur

    2013-12-01

    The compliance of parents with child passenger safety (CPS) has been mainly explained by their level of knowledge. Social, ethnic and cultural factors have not been investigated in detail. This study investigated the rate of compliance of parents with CPS guidelines, as well as the factors hindering it. Parents of infants aged 2-10 days were enrolled. The proportions of families obtaining a car safety seat (CSS; 57%) and complying with CPS recommendations (2%) were very low. Most of the parents thought CSS were harmful for infants (mother, 57%; father, 63%), despite having already purchased one. Parents believed their children to be too small to use CSS and cannot sit in CSS because they should lie flat on their backs at all times. These prejudices may be due to the social and cultural circumstances specific to Turkey, or corresponding findings may be found in countries with similar socioeconomic status. © 2013 The Authors. Pediatrics International © 2013 Japan Pediatric Society.

  11. Endangered river fish: factors hindering conservation and restoration

    Science.gov (United States)

    Cooke, Steven J.; Paukert, Craig P.; Hogan, Zeb

    2012-01-01

    Globally, riverine fish face many anthropogenic threats including riparian and flood plain habitat degradation, altered hydrology, migration barriers, fisheries exploitation, environmental (climate) change, and introduction of invasive species. Collectively, these threats have made riverine fishes some of the most threatened taxa on the planet. Although much effort has been devoted to identifying the threats faced by river fish, there has been less effort devoted to identifying the factors that may hinder our ability to conserve and restore river fish populations and their watersheds. Therefore, we focus our efforts on identifying and discussing 10 general factors (can also be viewed as research and implementation needs) that constrain or hinder effective conservation action for endangered river fish: (1) limited basic natural history information; (2) limited appreciation for the scale/extent of migrations and the level of connectivity needed to sustain populations; (3) limited understanding of fish/river-flow relationships; (4) limited understanding of the seasonal aspects of river fish biology, particularly during winter and/or wet seasons; (5) challenges in predicting the response of river fish and river ecosystems to both environmental change and various restoration or management actions; (6) limited understanding of the ecosystem services provided by river fish; (7) the inherent difficulty in studying river fish; (8) limited understanding of the human dimension of river fish conservation and management; (9) limitations of single species approaches that often fail to address the broader-scale problems; and (10) limited effectiveness of governance structures that address endangered river fish populations and rivers that cross multiple jurisdictions. We suggest that these issues may need to be addressed to help protect, restore, or conserve river fish globally, particularly those that are endangered.

  12. A novel steric effect-regulated isothermal exponential amplification technology for the one-step homogeneous sensing of proteins.

    Science.gov (United States)

    Wu, Wanghua; Pan, Wufan; Yu, Dongdong; Yuan, Zhen; Qin, Yazhou; Lu, Yuxiang; Zhang, Tao; Zhou, Jianguang

    2018-02-12

    A simple and homogeneous technology, the steric effect-regulated isothermal exponential amplification reaction (SER-EXPAR), was developed to sense proteins. By using a small molecule linked DNA nanostructure, termed enzyme-binding hairpin (EBH), the protein-small molecule binding events could be readily sensed by utilizing the steric effect generated between the protein and enzyme. It set free the enzyme to be active again, thus regulating the amplification rate of EXPAR.

  13. Does Teaching Grammar Really Hinder Students' Speaking Abilities?

    Institute of Scientific and Technical Information of China (English)

    Kazumi Araki

    2015-01-01

    In the history of formal English education in Japan, grammar used to be the mainstream. In the secondary education system, teachers used to spend many hours teaching grammar to the students. However, it has been replaced by the aural/oral method of teaching a foreign language. There was even a remark that teaching grammar hinders students from communicating fluently. Literally, there was a time when grammar was set aside in formal English education. However, the author noticed that in grammar classes, the students speak English more loudly and confidently without much hesitation than in other types of English classes. One of the reasons is that they are not worried about the contents of the speeches. They are simply concentrating on the forms. They are not afraid of making major mistakes, and the errors they make are minor so they do not feel embarrassed in public. The atmosphere of the grammar classes is very positive and the students enjoy speaking English. In this paper, the author shows how grammar classes can contribute to the acquisition of the students' speaking abilities and manners. "Learning grammar was a precious experience", one student reported after the course.

  14. Is Urban Planning in Australia Hindered by Poor Metropolitan Governance?

    Directory of Open Access Journals (Sweden)

    Paul Burton

    2017-11-01

    Full Text Available There are many calls for urban planning in Australia to be reformed, although often in contradictory ways. For example, some argue it should be capable of delivering greater certainty to developers while others call for more flexibility in processes of urban development regulation; some would like to roll back its regulatory impact while others argue for a renewal of planning’s commitment to promoting social and spatial justice. The Australian planning system is also held to be hindered by a comparative lack of planning at and for the metropolitan scale. This is connected to the absence of well-developed structures of metropolitan governance in what is a three-tier federal system, with most power over planning concentrated at the State and Territory government scale. The paper explores this putative hindrance by considering three important issues in Australian urban policy debates about the efficacy of contemporary multi-level governance arrangements: spatial scale; identity and legitimacy; and efficiency and effectiveness. It includes some analysis of the case made for a more explicit and rigorous national urban policy and how this might relate to lower level planning regimes. The paper focuses on recent urban policy and planning initiatives in South East Queensland, one of Australia’s fastest growing metropolitan regions, and concludes that while incremental but nonetheless significant improvements in planning policy and practice are possible, these are unlikely to satisfy those calling for more radical changes to improve the Australian planning system.

  15. Steric sea level variability (1993-2010) in an ensemble of ocean reanalyses and objective analyses

    Science.gov (United States)

    Storto, Andrea; Masina, Simona; Balmaseda, Magdalena; Guinehut, Stéphanie; Xue, Yan; Szekely, Tanguy; Fukumori, Ichiro; Forget, Gael; Chang, You-Soon; Good, Simon A.; Köhl, Armin; Vernieres, Guillaume; Ferry, Nicolas; Peterson, K. Andrew; Behringer, David; Ishii, Masayoshi; Masuda, Shuhei; Fujii, Yosuke; Toyoda, Takahiro; Yin, Yonghong; Valdivieso, Maria; Barnier, Bernard; Boyer, Tim; Lee, Tony; Gourrion, Jérome; Wang, Ou; Heimback, Patrick; Rosati, Anthony; Kovach, Robin; Hernandez, Fabrice; Martin, Matthew J.; Kamachi, Masafumi; Kuragano, Tsurane; Mogensen, Kristian; Alves, Oscar; Haines, Keith; Wang, Xiaochun

    2017-08-01

    Quantifying the effect of the seawater density changes on sea level variability is of crucial importance for climate change studies, as the sea level cumulative rise can be regarded as both an important climate change indicator and a possible danger for human activities in coastal areas. In this work, as part of the Ocean Reanalysis Intercomparison Project, the global and regional steric sea level changes are estimated and compared from an ensemble of 16 ocean reanalyses and 4 objective analyses. These estimates are initially compared with a satellite-derived (altimetry minus gravimetry) dataset for a short period (2003-2010). The ensemble mean exhibits a significant high correlation at both global and regional scale, and the ensemble of ocean reanalyses outperforms that of objective analyses, in particular in the Southern Ocean. The reanalysis ensemble mean thus represents a valuable tool for further analyses, although large uncertainties remain for the inter-annual trends. Within the extended intercomparison period that spans the altimetry era (1993-2010), we find that the ensemble of reanalyses and objective analyses are in good agreement, and both detect a trend of the global steric sea level of 1.0 and 1.1 ± 0.05 mm/year, respectively. However, the spread among the products of the halosteric component trend exceeds the mean trend itself, questioning the reliability of its estimate. This is related to the scarcity of salinity observations before the Argo era. Furthermore, the impact of deep ocean layers is non-negligible on the steric sea level variability (22 and 12 % for the layers below 700 and 1500 m of depth, respectively), although the small deep ocean trends are not significant with respect to the products spread.

  16. Brownian dynamics simulations of an order-disorder transition in sheared sterically stabilized colloidal suspensions

    International Nuclear Information System (INIS)

    Rigos, A.A.; Wilemski, G.

    1992-01-01

    The shear thinning behavior of a sterically stabilized nonaqueous colloidal suspension was investigated using nonequilibrium Brownian dynamics simulations of systems with 108 and 256 particles. At a volume fraction of 0.4, the suspension is thixotropic: it has a reversible shear thinning transition from a disordered state to an ordered, lamellar state with triangularly packed strings of particles. The time scale for the transition is set by the free particle diffusion constant. For the smaller system, the transition occurs gradually with increasing shear rate. For the larger system, the transition is sharp and discontinuous shear thinning is found. 34 refs., 9 figs., 1 tab

  17. Steric Pressure among Membrane-Bound Polymers Opposes Lipid Phase Separation.

    Science.gov (United States)

    Imam, Zachary I; Kenyon, Laura E; Carrillo, Adelita; Espinoza, Isai; Nagib, Fatema; Stachowiak, Jeanne C

    2016-04-19

    Lipid rafts are thought to be key organizers of membrane-protein complexes in cells. Many proteins that interact with rafts have bulky polymeric components such as intrinsically disordered protein domains and polysaccharide chains. Therefore, understanding the interaction between membrane domains and membrane-bound polymers provides insights into the roles rafts play in cells. Multiple studies have demonstrated that high concentrations of membrane-bound polymeric domains create significant lateral steric pressure at membrane surfaces. Furthermore, our recent work has shown that lateral steric pressure at membrane surfaces opposes the assembly of membrane domains. Building on these findings, here we report that membrane-bound polymers are potent suppressors of membrane phase separation, which can destabilize lipid domains with substantially greater efficiency than globular domains such as membrane-bound proteins. Specifically, we created giant vesicles with a ternary lipid composition, which separated into coexisting liquid ordered and disordered phases. Lipids with saturated tails and poly(ethylene glycol) (PEG) chains conjugated to their head groups were included at increasing molar concentrations. When these lipids were sparse on the membrane surface they partitioned to the liquid ordered phase. However, as they became more concentrated, the fraction of GUVs that were phase-separated decreased dramatically, ultimately yielding a population of homogeneous membrane vesicles. Experiments and physical modeling using compositions of increasing PEG molecular weight and lipid miscibility phase transition temperature demonstrate that longer polymers are the most efficient suppressors of membrane phase separation when the energetic barrier to lipid mixing is low. In contrast, as the miscibility transition temperature increases, longer polymers are more readily driven out of domains by the increased steric pressure. Therefore, the concentration of shorter polymers required

  18. The cyclin-dependent kinase 8 module sterically blocks Mediator interactions with RNA polymerase II

    DEFF Research Database (Denmark)

    Elmlund, Hans; Baraznenok, Vera; Lindahl, Martin

    2006-01-01

    CDK8 (cyclin-dependent kinase 8), along with CycC, Med12, and Med13, form a repressive module (the Cdk8 module) that prevents RNA polymerase II (pol II) interactions with Mediator. Here, we report that the ability of the Cdk8 module to prevent pol II interactions is independent of the Cdk8......-dependent kinase activity. We use electron microscopy and single-particle reconstruction to demonstrate that the Cdk8 module forms a distinct structural entity that binds to the head and middle region of Mediator, thereby sterically blocking interactions with pol II....

  19. SNARE zippering is hindered by polyphenols in the neuron

    Energy Technology Data Exchange (ETDEWEB)

    Yang, Yoosoo [Department of Genetic Engineering and Center for Human Interface Nanotechnology, Sungkyunkwan University, Suwon 440-746 (Korea, Republic of); Biomedical Research Institute, Korea Institute of Science and Technology, Seoul 136-791 (Korea, Republic of); Kim, Se-Hyun; Heo, Paul; Kong, Byoungjae; Shin, Jonghyeok; Jung, Young-Hun; Yoon, Keejung; Chung, Woo-Jae [Department of Genetic Engineering and Center for Human Interface Nanotechnology, Sungkyunkwan University, Suwon 440-746 (Korea, Republic of); Shin, Yeon-Kyun [Biomedical Research Institute, Korea Institute of Science and Technology, Seoul 136-791 (Korea, Republic of); Department of Biochemistry, Biophysics, and Molecular Biology, Iowa State University, Ames, IA 50011 (United States); Kweon, Dae-Hyuk, E-mail: dhkweon@skku.edu [Department of Genetic Engineering and Center for Human Interface Nanotechnology, Sungkyunkwan University, Suwon 440-746 (Korea, Republic of)

    2014-07-18

    Highlights: • Membrane fusion driven by SNARE complex is hindered by several polyphenols. • Distinctive inhibitory effect of each polyphenol on SNARE zippering in neuron was examined. • FRET between fluorescence protein-tagged SNAREs probed well SNARE zippering in PC12 cells. • Delphinidin and cyanidin inhibit N-terminal SNARE nucleation in Ca{sup 2+}-independent manner. • Myricetin inhibits Ca{sup 2+}-dependent transmembrane association of SNARE complex. - Abstract: Fusion of synaptic vesicles with the presynaptic plasma membrane in the neuron is mediated by soluble N-ethylmaleimide-sensitive fusion protein-attachment protein receptor (SNARE) proteins. SNARE complex formation is a zippering-like process which initiates at the N-terminus and proceeds to the C-terminal membrane-proximal region. Previously, we showed that this zippering-like process is regulated by several polyphenols, leading to the arrest of membrane fusion and the inhibition of neuroexocytosis. In vitro studies using purified SNARE proteins reconstituted in liposomes revealed that each polyphenol uniquely regulates SNARE zippering. However, the unique regulatory effect of each polyphenol in cells has not yet been examined. In the present study, we observed SNARE zippering in neuronal PC12 cells by measuring the fluorescence resonance energy transfer (FRET) changes of a cyan fluorescence protein (CFP) and a yellow fluorescence protein (YFP) fused to the N-termini or C-termini of SNARE proteins. We show that delphinidin and cyanidin inhibit the initial N-terminal nucleation of SNARE complex formation in a Ca{sup 2+}-independent manner, while myricetin inhibits Ca{sup 2+}-dependent transmembrane domain association of the SNARE complex in the cell. This result explains how polyphenols exhibit botulinum neurotoxin-like activity in vivo.

  20. Steric Stabilization of “Charge-Free” Cellulose Nanowhiskers by Grafting of Poly(ethylene glycol

    Directory of Open Access Journals (Sweden)

    Jun Araki

    2014-12-01

    Full Text Available A sterically stabilized aqueous suspension of “charge-free” cellulose nanowhiskers was prepared by hydrochloric acid hydrolysis of cotton powders and subsequent surface grafting of monomethoxy poly(ethylene glycol (mPEG. The preparation scheme included carboxylation of the terminal hydroxyl groups in mPEG via oxidation with silica gel particles carrying 2,2,6,6-tetramethyl-1-pyperidinyloxyl (TEMPO moieties and subsequent esterification between terminal carboxyls in mPEG and surface hydroxyl groups of cellulose nanowhiskers, mediated by 1,1'-carbonyldiimidazole (CDI in dimethyl sulfoxide or dimethylacetamide. Some of the prepared PEG-grafted samples showed remarkable flow birefringence and enhanced stability after 24 h, even in 0.1 M NaCl, suggesting successful steric stabilization by efficient mPEG grafting. Actual PEG grafting via ester linkages was confirmed by attenuated total reflectance-Fourier transform infrared spectrometry. In a typical example, the amount of grafted mPEG was estimated as ca. 0.3 g/g cellulose by two measurements, i.e., weight increase after grafting and weight loss after alkali cleavage of ester linkages. Transmission electron microscopy indicated unchanged nanowhisker morphology after mPEG grafting.

  1. Unfavorable regions in the ramachandran plot: Is it really steric hindrance? The interacting quantum atoms perspective.

    Science.gov (United States)

    Maxwell, Peter I; Popelier, Paul L A

    2017-11-05

    Accurate description of the intrinsic preferences of amino acids is important to consider when developing a biomolecular force field. In this study, we use a modern energy partitioning approach called Interacting Quantum Atoms to inspect the cause of the φ and ψ torsional preferences of three dipeptides (Gly, Val, and Ile). Repeating energy trends at each of the molecular, functional group, and atomic levels are observed across both (1) the three amino acids and (2) the φ/ψ scans in Ramachandran plots. At the molecular level, it is surprisingly electrostatic destabilization that causes the high-energy regions in the Ramachandran plot, not molecular steric hindrance (related to the intra-atomic energy). At the functional group and atomic levels, the importance of key peptide atoms (O i -1 , C i , N i , N i +1 ) and some sidechain hydrogen atoms (H γ ) are identified as responsible for the destabilization seen in the energetically disfavored Ramachandran regions. Consistently, the O i -1 atoms are particularly important for the explanation of dipeptide intrinsic behavior, where electrostatic and steric destabilization unusually complement one another. The findings suggest that, at least for these dipeptides, it is the peptide group atoms that dominate the intrinsic behavior, more so than the sidechain atoms. © 2017 The Authors. Journal of Computational Chemistry Published by Wiley Periodicals, Inc. © 2017 The Authors. Journal of Computational Chemistry Published by Wiley Periodicals, Inc.

  2. Abaxial growth and steric constraints guide leaf folding and shape in Acer pseudoplatanus.

    Science.gov (United States)

    Couturier, Etienne; Brunel, Nicole; Douady, Stéphane; Nakayama, Naomi

    2012-08-01

    How leaf shape is regulated is a long-standing question in botany. For diverse groups of dicotyledon species, lamina folding along the veins and geometry of the space available for the primordia can explain the palmate leaf morphology. Dubbed the kirigami theory, this hypothesis of fold-dependent leaf shape regulation has remained largely theoretical. Using Acer pseudoplatanus, we investigated the mechanisms behind the two key processes of kirigami leaf development. Cytological examination and quantitative analyses were used to examine the course of the vein-dependent lamina folding. Surgical ablation and tissue culturing were employed to test the effects of physical constraints on primordia growth. The final morphology of leaves growing without steric constraints were predicted mathematically. The cytological examination showed that the lamina's abaxial side along the veins grows substantially more than the adaxial side. The abaxial hypergrowth along the veins and the lamina extension correlated with the lamina folding. When a primordium was released from the physical constraints imposed by the other primordia, it rapidly grew into the newly available space, while maintaining the curvature inward. The morphology of such a leaf was predicted to lack symmetry in the lobe shapes. The enhanced growth on the abaxial side of the lamina along the veins is likely to drive lamina folding. The surgical ablation provided clear support for the space-filling nature of leaf growth; thus, steric constraints play a role in determination of the shapes of folded leaves and probably also of the final leaf morphology.

  3. Role of Steric Hindrance in the Crystal Packing of Z′ = 4 Superstructure of Trimethyltin Hydroxide

    KAUST Repository

    Dey, S.

    2018-01-22

    The roomerature crystal structure of trimethyltin hydroxide, (CH)SnOH, has been described by Anderson et al. [Cryst. Growth Des. 2011, 11, 820-826] as a 2a × 2b × 8c, 32-fold superstructure. We report a a × b × 8c, eight-fold superstructure with orthorhombic P2cn symmetry and Z′ = 4. Structured diffuse scattering observed at the positions of presumed superlattice reflections along a∗ and b∗ might have appeared as Bragg reflections in the experiment by Anderson et al. Alternatively, Anderson et al. and the present work might have studied different polymorphs of (CH)SnOH. Crystalline (CH)SnOH constitutes polymeric chains arranged parallel to c. In the eight-fold superstructure at 220 K, the polymeric chains possess a distorted zigzag arrangement of linked linear O-Sn-O units with bent angle at oxygen of ∼139.2°. This structure is essentially different from the 8-helical arrangement in the published 32-fold superstructure model. The origin of the distorted zigzag structure is explained by steric hindrance between hydrogen atoms of adjacent hydroxy groups and (CH)Sn groups. Frustration in the packing of the chains is determined by steric hindrance between methyl groups of neighboring chains, which prevents the formation of interchain C-H···O hydrogen bonds.

  4. Remote Steric Effect as a Facile Strategy for Improving the Efficiency of Exciplex-Based OLEDs.

    Science.gov (United States)

    Hung, Wen-Yi; Wang, Ting-Chih; Chiang, Pin-Yi; Peng, Bo-Ji; Wong, Ken-Tsung

    2017-03-01

    This work reports a new strategy of introducing remote steric effect onto the electron donor for giving the better performance of the exciplex-based organic light-emitting device (OLED). The bulky triphenylsilyl group (SiPh 3 ) was introduced onto the fluorene bridge of 4,4'-(9H-fluorene-9,9-diyl)bis(N,N-di-p-tolylaniline) (DTAF) to create remote steric interactions for increasing the possibility of effective contacts between electron-donating chromophores and acceptor molecules, rendering the resulting exciplex to have a higher photoluminescence quantum yield (PLQY). The green exciplex device based on DSDTAF:3N-T2T (1:1) as an emitting layer exhibits a low turn-on voltage of 2.0 V, high maximum efficiencies (13.2%, 42.9 cd A -1 , 45.5 lm W -1 ), which are higher than the device employed DTAF (without SiPh 3 groups) (11.6%, 35.3 cd A -1 , 41.3 lm W -1 ) as donor under the same device structure. This strategy was further examined for blue exciplex, where the EQE was enhanced from 9.5% to 12.5% as the electron acceptor PO-T2T mixed with a tert-butyl group substituted carbazole-based donor (CPTBF) as the emitting exciplex in device. This strategy is simple and useful for developing high performance exciplex OLEDs.

  5. Steric hindrances create a discrete linear Dy4 complex exhibiting SMM behaviour.

    Science.gov (United States)

    Lin, Shuang-Yan; Zhao, Lang; Ke, Hongshan; Guo, Yun-Nan; Tang, Jinkui; Guo, Yang; Dou, Jianmin

    2012-03-21

    Two linear tetranuclear lanthanide complexes of general formula [Ln(4)(L)(2)(C(6)H(5)COO)(12)(MeOH)(4)], where HL = 2,6-bis((furan-2-ylmethylimino)methyl)-4-methylphenol, () and Ln(III) = Dy(III) (1) and Gd(III) (2), have been synthesized and characterized. The crystal structural analysis demonstrates that two Schiff-base ligands inhibit the growth of benzoate bridged 1D chains, leading to the isolation of discrete tetranuclear complexes due to their steric hindrances. Every Ln(III) ion is coordinated by eight donor atoms in a distorted bicapped trigonal-prismatic arrangement. Alternating current (ac) susceptibility measurements of complex 1 reveal a frequency- and temperature-dependent out-of-phase signal under zero dc field, typical of single-molecule magnet (SMM) behaviour with an anisotropic barrier Δ(eff) = 17.2 K.

  6. Multifaceted catalytic hydrogenation of amides via diverse activation of a sterically confined bipyridine-ruthenium framework.

    Science.gov (United States)

    Miura, Takashi; Naruto, Masayuki; Toda, Katsuaki; Shimomura, Taiki; Saito, Susumu

    2017-05-16

    Amides are ubiquitous and abundant in nature and our society, but are very stable and reluctant to salt-free, catalytic chemical transformations. Through the activation of a "sterically confined bipyridine-ruthenium (Ru) framework (molecularly well-designed site to confine adsorbed H 2 in)" of a precatalyst, catalytic hydrogenation of formamides through polyamide is achieved under a wide range of reaction conditions. Both C=O bond and C-N bond cleavage of a lactam became also possible using a single precatalyst. That is, catalyst diversity is induced by activation and stepwise multiple hydrogenation of a single precatalyst when the conditions are varied. The versatile catalysts have different structures and different resting states for multifaceted amide hydrogenation, but the common structure produced upon reaction with H 2 , which catalyzes hydrogenation, seems to be "H-Ru-N-H."

  7. Comparative study of PBI Cross Linked Utilizing Agents of Varying Steric Configurations

    DEFF Research Database (Denmark)

    Kirkebcek, Andreas; Aili, David; Li, Qingfeng

    2016-01-01

    ionic or covalent cross linking. When considering such, little attention is devoted to explore the effect of the sterical configuration of the cross linking agent. In this contribution three different cross linking agents are utilized to evaluate how these affects final membrane properties.......The high thermal and chemical stability of poly[2,2'-(m-phenylene)-5,5' bibenzimidazole] (PBI) accounts for its wise spread use in high temperature polymer electrolyte membrane fuel cells (HT- PEMFC). By doping the membrane with phosphoric acid (PA) ionic conductivity is obtained. Thus conductivity...... is dependent on the amount of PA present within the membrane. However mechanical properties are reduced are significantly reduced due to the plasticizing effect shown by PA [1]. This effect is due to PBI chain displacement. This effect can be lessened by use of cross linking [2-4]. This can be obtained using...

  8. Steric and mass-induced Mediterranean sea level trends from 14 years of altimetry data

    Science.gov (United States)

    Criado-Aldeanueva, Francisco; Del Río Vera, Jorge; García-Lafuente, Jesús

    2008-02-01

    Long-term series of almost 14 years of altimetry data (1992-2005) have been analysed along with Sea Surface Temperature (SST) and temperature and salinity profiles to investigate sea level trends over the Mediterranean Sea. Although sea level variations are mainly driven by the steric contribution, the mass-induced component plays some role in modulating its oscillation. A spatially averaged positive trend of 2.1 ± 0.6 mm/year has been observed, but a change in sign in 2001 seems to appear. Steric effects (mainly on thermal origin) account for ˜ 55% of sea level trend. Although Mediterranean Sea is a semi-enclosed basin, this value is comparable to that reported for the global ocean. Sea level rise is particularly important in the Levantine basin south of Crete with values up to 10 ± 1 mm/year. Other areas of sea level rise are localised throughout the Levantine basin and in the Adriatic and Alboran Seas, with more moderate values. Sea level drop areas are localised in the Algerian basin, between the Balearic Islands and the African coasts and, particularly, in the Ionian basin. In this area, negative trends as high as - 10 ± 0.8 mm/year are detected mainly due to the mass-induced contribution, which suggests decadal changes of surface circulation. The inferred sea level trends have been correlated with North Atlantic Oscillation (NAO) indices and a low but significant correlation has been detected between sea level in the Levantine and Balearic basins and NAO index.

  9. Targeted Sterically Stabilized Phospholipid siRNA Nanomedicine for Hepatic and Renal Fibrosis

    Directory of Open Access Journals (Sweden)

    Fatima Khaja

    2016-01-01

    Full Text Available Since its discovery, small interfering RNA (siRNA has been considered a potent tool for modulating gene expression. It has the ability to specifically target proteins via selective degradation of messenger RNA (mRNA not easily accessed by conventional drugs. Hence, RNA interference (RNAi therapeutics have great potential in the treatment of many diseases caused by faulty protein expression such as fibrosis and cancer. However, for clinical application siRNA faces a number of obstacles, such as poor in vivo stability, and off-target effects. Here we developed a unique targeted nanomedicine to tackle current siRNA delivery issues by formulating a biocompatible, biodegradable and relatively inexpensive nanocarrier of sterically stabilized phospholipid nanoparticles (SSLNPs. This nanocarrier is capable of incorporating siRNA in its core through self-association with a novel cationic lipid composed of naturally occuring phospholipids and amino acids. This overall assembly protects and delivers sufficient amounts of siRNA to knockdown over-expressed protein in target cells. The siRNA used in this study, targets connective tissue growth factor (CTGF, an important regulator of fibrosis in both hepatic and renal cells. Furthermore, asialoglycoprotein receptors are targeted by attaching the galactosamine ligand to the nanocarries which enhances the uptake of nanoparticles by hepatocytes and renal tubular epithelial cells, the major producers of CTGF in fibrosis. On animals this innovative nanoconstruct, small interfering RNA in sterically stabilized phospholipid nanoparticles (siRNA-SSLNP, showed favorable pharmacokinetic properties and accumulated mostly in hepatic and renal tissues making siRNA-SSLNP a suitable system for targeting liver and kidney fibrotic diseases.

  10. Steric restrictions of RISC in RNA interference identified with size-expanded RNA nucleobases.

    Science.gov (United States)

    Hernández, Armando R; Peterson, Larryn W; Kool, Eric T

    2012-08-17

    Understanding the interactions between small interfering RNAs (siRNAs) and the RNA-induced silencing complex (RISC), the key protein complex of RNA interference (RNAi), is of great importance to the development of siRNAs with improved biological and potentially therapeutic function. Although various chemically modified siRNAs have been reported, relatively few studies with modified nucleobases exist. Here we describe the synthesis and hybridization properties of siRNAs bearing size-expanded RNA (xRNA) nucleobases and their use as a novel and systematic set of steric probes in RNAi. xRNA nucleobases are expanded by 2.4 Å using benzo-homologation and retain canonical Watson-Crick base-pairing groups. Our data show that the modified siRNA duplexes display small changes in melting temperature (+1.4 to -5.0 °C); substitutions near the center are somewhat destabilizing to the RNA duplex, while substitutions near the ends are stabilizing. RNAi studies in a dual-reporter luciferase assay in HeLa cells revealed that xRNA nucleobases in the antisense strand reduce activity at some central positions near the seed region but are generally well tolerated near the ends. Most importantly, we observed that xRNA substitutions near the 3'-end increased activity over that of wild-type siRNAs. The data are analyzed in terms of site-dependent steric effects in RISC. Circular dichroism experiments show that single xRNA substitutions do not significantly distort the native A-form helical structure of the siRNA duplex, and serum stability studies demonstrated that xRNA substitutions protect siRNAs against nuclease degradation.

  11. Sterically demanding diphosphonite ligands - synthesis and application in nickel-catalyzed isomerization of 2-methyl-3-butenenitrile

    NARCIS (Netherlands)

    Vlugt, van der J.I.; Hewat, A.C.; Neto, S.; Sablong, R.J.; Mills, A.M.; Lutz, M.; Spek, A.L.; Müller, C.; Vogt, D.

    2004-01-01

    The synthesis of a novel class of sterically demanding diphosphonites 1-8, based on rigid backbones, is described. The starting materials are all commercially available and the methodology allows for a modular approach. All ligands have been fully characterized, including an X-ray crystal structure

  12. Exploring electronic and steric effects on the insertion and polymerization reactivity of phosphinesulfonato pdii catalysts

    KAUST Repository

    Neuwald, Boris

    2013-11-21

    Thirteen different symmetric and asymmetric phosphinesulfonato palladium complexes ([{(X1-Cl)-μ-M}n], M=Na, Li, 1= X(P^O)PdMe) were prepared (see Figure 1). The solid-state structures of the corresponding pyridine or lutidine complexes were determined for (MeO)21-py, (iPrO)21-lut, (MeO,Me2)1-lut, (MeO)31-lut, CF31-lut, and Ph1-lut. The reactivities of the catalysts X1, obtained after chloride abstraction with AgBF4, toward methyl acrylate (MA) were quantified through determination of the rate constants for the first and the consecutive MA insertion and the analysis of β-H and other decomposition products through NMR spectroscopy. Differences in the homo- and copolymerization of ethylene and MA regarding catalyst activity and stability over time, polymer molecular weight, and polar co-monomer incorporation were investigated. DFT calculations were performed on the main insertion steps for both monomers to rationalize the effect of the ligand substitution patterns on the polymerization behaviors of the complexes. Full analysis of the data revealed that: 1) electron-deficient catalysts polymerize with higher activity, but fast deactivation is also observed; 2) the double ortho-substituted catalysts (MeO)21 and (MeO)31 allow very high degrees of MA incorporation at low MA concentrations in the copolymerization; and 3) steric shielding leads to a pronounced increase in polymer molecular weight in the copolymerization. The catalyst properties induced by a given P-aryl (alkyl) moiety were combined effectively in catalysts with two different non-chelating aryl moieties, such as cHexO/(MeO)21, which led to copolymers with significantly increased molecular weights compared to the prototypical MeO1. Catalyst control: The influence of steric and electronic effects on the reactivity of phosphinesulfonato PdII catalysts in polymerization and copolymerization is explored through experimental and DFT methods. A comparison of thirteen different X(P O)PdMe catalysts ((P O)= κ2-P

  13. Steric control of the donor/acceptor interface: Implications in organic photovoltaic charge generation

    KAUST Repository

    Holcombe, Thomas W.; Norton, Joseph E.; Rivnay, Jonathan; Woo, Claire; Goris, Ludwig J.; Piliego, Claudia; Griffini, Gianmarco; Sellinger, Alan; Bré das, Jean Luc; Salleo, Alberto; Frechet, Jean

    2011-01-01

    The performance of organic photovoltaic (OPV) devices is currently limited by modest short-circuit current densities. Approaches toward improving this output parameter may provide new avenues to advance OPV technologies and the basic science of charge transfer in organic semiconductors. This work highlights how steric control of the charge separation interface can be effectively tuned in OPV devices. By introducing an octylphenyl substituent onto the investigated polymer backbones, the thermally relaxed charge-transfer state, and potentially excited charge-transfer states, can be raised in energy. This decreases the barrier to charge separation and results in increased photocurrent generation. This finding is of particular significance for nonfullerene OPVs, which have many potential advantages such as tunable energy levels and spectral breadth, but are prone to poor exciton separation efficiencies. Computational, spectroscopic, and synthetic methods were combined to develop a structure-property relationship that correlates polymer substituents with charge-transfer state energies and, ultimately, device efficiencies. © 2011 American Chemical Society.

  14. Steric exclusion and protein conformation determine the localization of plasma membrane transporters.

    Science.gov (United States)

    Bianchi, Frans; Syga, Łukasz; Moiset, Gemma; Spakman, Dian; Schavemaker, Paul E; Punter, Christiaan M; Seinen, Anne-Bart; van Oijen, Antoine M; Robinson, Andrew; Poolman, Bert

    2018-02-05

    The plasma membrane (PM) of Saccharomyces cerevisiae contains membrane compartments, MCC/eisosomes and MCPs, named after the protein residents Can1 and Pma1, respectively. Using high-resolution fluorescence microscopy techniques we show that Can1 and the homologous transporter Lyp1 are able to diffuse into the MCC/eisosomes, where a limited number of proteins are conditionally trapped at the (outer) edge of the compartment. Upon addition of substrate, the immobilized proteins diffuse away from the MCC/eisosomes, presumably after taking a different conformation in the substrate-bound state. Our data indicate that the mobile fraction of all integral plasma membrane proteins tested shows extremely slow Brownian diffusion through most of the PM. We also show that proteins with large cytoplasmic domains, such as Pma1 and synthetic chimera of Can1 and Lyp1, are excluded from the MCC/eisosomes. We hypothesize that the distinct localization patterns found for these integral membrane proteins in S. cerevisiae arises from a combination of slow lateral diffusion, steric exclusion, and conditional trapping in membrane compartments.

  15. The role of atomic level steric effects and attractive forces in protein folding.

    Science.gov (United States)

    Lammert, Heiko; Wolynes, Peter G; Onuchic, José N

    2012-02-01

    Protein folding into tertiary structures is controlled by an interplay of attractive contact interactions and steric effects. We investigate the balance between these contributions using structure-based models using an all-atom representation of the structure combined with a coarse-grained contact potential. Tertiary contact interactions between atoms are collected into a single broad attractive well between the C(β) atoms between each residue pair in a native contact. Through the width of these contact potentials we control their tolerance for deviations from the ideal structure and the spatial range of attractive interactions. In the compact native state dominant packing constraints limit the effects of a coarse-grained contact potential. During folding, however, the broad attractive potentials allow an early collapse that starts before the native local structure is completely adopted. As a consequence the folding transition is broadened and the free energy barrier is decreased. Eventually two-state folding behavior is lost completely for systems with very broad attractive potentials. The stabilization of native-like residue interactions in non-perfect geometries early in the folding process frequently leads to structural traps. Global mirror images are a notable example. These traps are penalized by the details of the repulsive interactions only after further collapse. Successful folding to the native state requires simultaneous guidance from both attractive and repulsive interactions. Copyright © 2011 Wiley Periodicals, Inc.

  16. Gauche effect in 1,2-difluoroethane. Hyperconjugation, bent bonds, steric repulsion.

    Science.gov (United States)

    Goodman, Lionel; Gu, Hongbing; Pophristic, Vojislava

    2005-02-17

    Natural bond orbital deletion calculations show that whereas the gauche preference arises from vicinal hyperconjugative interaction between anti C-H bonds and C-F* antibonds, the cis C-H/C-F* interactions are substantial (approximately 25% of the anti interaction). The established significantly >60 degrees FCCF dihedral angle for the equilibrium conformer can then be rationalized in terms of the hyperconjugation model alone by taking into account both anti interactions that maximize near 60 degrees and the smaller cis interactions that maximize at a much larger dihedral angle. This explanation does not invoke repulsive forces to rationalize the 72 degrees equilibrium conformer angle. The relative minimum energy for the trans conformer is the consequence of a balance between decreasing hyperconjugative stabilization and decreasing steric destabilization as the FCCF torsional angle approaches 180 degrees . The torsional coordinate is predicted to be strongly contaminated by CCF bending, with the result that approximately half of the trans --> gauche stabilization energy stems from mode coupling.

  17. Steric control of the donor/acceptor interface: Implications in organic photovoltaic charge generation

    KAUST Repository

    Holcombe, Thomas W.

    2011-08-10

    The performance of organic photovoltaic (OPV) devices is currently limited by modest short-circuit current densities. Approaches toward improving this output parameter may provide new avenues to advance OPV technologies and the basic science of charge transfer in organic semiconductors. This work highlights how steric control of the charge separation interface can be effectively tuned in OPV devices. By introducing an octylphenyl substituent onto the investigated polymer backbones, the thermally relaxed charge-transfer state, and potentially excited charge-transfer states, can be raised in energy. This decreases the barrier to charge separation and results in increased photocurrent generation. This finding is of particular significance for nonfullerene OPVs, which have many potential advantages such as tunable energy levels and spectral breadth, but are prone to poor exciton separation efficiencies. Computational, spectroscopic, and synthetic methods were combined to develop a structure-property relationship that correlates polymer substituents with charge-transfer state energies and, ultimately, device efficiencies. © 2011 American Chemical Society.

  18. Feeling hindered by health problems and functional capacity at 60 years and above.

    Science.gov (United States)

    Fagerström, Cecilia; Holst, Göran; Hallberg, Ingalill R

    2007-01-01

    It is common to use activities of daily living (ADL) rating scales to identify the impact of health problems such as diseases, impaired eyesight or hearing on daily life. However, for various reasons people with health problems might feel hindered in daily life before limitations in ability to perform ADL have occurred. In addition, there is sparse knowledge of what makes people feel hindered by health problems in relation to their ADL capacity. The aim was to investigate feeling hindered by health problems among 1297 people aged 60-89 living at home in relation to ADL capacity, health problems, life satisfaction, self-esteem, and social and financial resources, using a self-reported questionnaire, including questions from Older Americans' Resources and Services schedule (OARS), Rosenberg's self-esteem and Life Satisfaction Index Z (LSIZ). People feeling greatly hindered by health problems rarely had anyone who could help when they needed support, had lower life satisfaction and self-esteem than those not feeling hindered. Feeling hindered by health problems appeared to take on a different meaning depending on ADL capacity, knowledge that seems essential to include when accomplishing health promotion and rehabilitation interventions, especially at the early stages of reduced ADL capacity.

  19. Steric Interference of Adhesion Supports In-Vitro Chondrogenesis of Mesenchymal Stem Cells on Hydrogels for Cartilage Repair

    OpenAIRE

    Goldshmid, Revital; Cohen, Shlomit; Shachaf, Yonatan; Kupershmit, Ilana; Sarig-Nadir, Offra; Seliktar, Dror; Wechsler, Roni

    2015-01-01

    Recent studies suggest the presence of cell adhesion motifs found in structural proteins can inhibit chondrogenesis. In this context, the current study aims to determine if a polyethylene glycol (PEG)-modified fibrinogen matrix could support better chondrogenesis of human bone marrow mesenchymal stem cells (BM-MSC) based on steric interference of adhesion, when compared to a natural fibrin matrix. Hydrogels used as substrates for two-dimensional (2D) BM-MSC cultures under chondrogenic conditi...

  20. A Steric-inhibition model for regulation of nucleotide exchange via the Dock180 family of GEFs.

    Science.gov (United States)

    Lu, Mingjian; Kinchen, Jason M; Rossman, Kent L; Grimsley, Cynthia; Hall, Matthew; Sondek, John; Hengartner, Michael O; Yajnik, Vijay; Ravichandran, Kodi S

    2005-02-22

    CDM (CED-5, Dock180, Myoblast city) family members have been recently identified as novel, evolutionarily conserved guanine nucleotide exchange factors (GEFs) for Rho-family GTPases . They regulate multiple processes, including embryonic development, cell migration, apoptotic-cell engulfment, tumor invasion, and HIV-1 infection, in diverse model systems . However, the mechanism(s) of regulation of CDM proteins has not been well understood. Here, our studies on the prototype member Dock180 reveal a steric-inhibition model for regulating the Dock180 family of GEFs. At basal state, the N-terminal SH3 domain of Dock180 binds to the distant catalytic Docker domain and negatively regulates the function of Dock180. Further studies revealed that the SH3:Docker interaction sterically blocks Rac access to the Docker domain. Interestingly, ELMO binding to the SH3 domain of Dock180 disrupted the SH3:Docker interaction, facilitated Rac access to the Docker domain, and contributed to the GEF activity of the Dock180/ELMO complex. Additional genetic rescue studies in C. elegans suggested that the regulation of the Docker-domain-mediated GEF activity by the SH3 domain and its adjoining region is evolutionarily conserved. This steric-inhibition model may be a general mechanism for regulating multiple SH3-domain-containing Dock180 family members and may have implications for a variety of biological processes.

  1. Revealing climate modes in steric sea levels: lessons learned from satellite geodesy, objective analyses and ocean reanalyses

    Science.gov (United States)

    Pfeffer, J.; Tregoning, P.; Purcell, A. P.

    2017-12-01

    Due to increased greenhouse gases emissions, the oceans are accumulating heat. In response to the ocean circulation and atmospheric forcing, the heat is irregularly redistributed within the oceans, causing sea level to rise at variable rates in space and time. These rates of steric expansion are extremely difficult to assess because of the sparsity of in-situ hydrographic observations available within the course of the 20th century. We compare here three methods to reconstruct the steric sea levels over the past 13, 25 and 58 years based on satellite geodesy, objective analyses and ocean reanalyses. The interannual to decadal variability of each dataset is explored with a model merging six climate indices representative of the natural variability of the ocean and climate system. Consistent regional patterns are identified for the Pacific Decadal Oscillation (PDO) and El Niño Southern Oscillation (ENSO) in all datasets at all timescales. Despite the short time coverage (13 years), the combination of satellite geodetic data (altimetry and GRACE) also reveals significant steric responses to the North Pacific Gyre Oscillation (NPGO), Indian Dipole (IOD) and Indian ocean basinwide (IOBM) mode. The richer information content in the ocean reanalyses allows us to recover the regional fingerprints of the PDO, ENSO, NPGO, IOD and IOBM, but also of the Atlantic Multidecadal Oscillation (AMO) acting over longer time scales (40 to 60 years). Therefore, ocean reanalyses, coupled with climate mode analyses, constitute innovative and promising tools to investigate the mechanisms triggering the variability of sea level rise over the past decades.

  2. Volumetric and steric properties of hydroxamic acids in ethanol at different temperatures

    International Nuclear Information System (INIS)

    Yadav, Sushama Singh; Pande, Rama; Khare, Deepesh; Tripathi, Manorama

    2012-01-01

    Highlights: ► Density, ρ and refractive index, n of PBHA and o-TBHA are measured in ethanol at different temperatures. ► From the experimental value of ρ and n, V φ , V φ 0 , S V ∗ , φ E 0 , V, R M , R S and α are calculated. ► Excess properties such as V E , R M E , n E are also computed. ► The behaviour of these parameters suggests that PBHA and o-TBHA act as structure maker in ethanol. - Abstract: Physical properties, such as density, ρ and refractive index, n of two hydroxamic acids (N-Phenylbenzo, C 6 H 5 NOH·C 6 H 5 C=O and N-o-tolylbenzo, o-CH 3 ·C 6 H 4 NOH·C 6 H 5 C=O) have been measured in ethanol as a function of concentration at T = (298.15, 303.15, and 308.15) K. The apparent molar volume, V φ , apparent molar volume at infinite dilution, V φ 0 and the slope, S V ∗ are calculated from the experimental value of density, ρ by applying the Masson’s equation. The apparent molar expansibility at infinite dilution, φ E 0 , molar volume, V and the excess molar volume, V E are also computed. The refractive index, n, data have been used to calculate the steric parameters viz. molar refraction, R M , excess refractive index, n E , excess molar refraction, R M E and polarizability, α of these molecules. The results obtained have been qualitatively used to interpret the solute–solute and solute–solvent interactions between hydroxamic acids and ethanol.

  3. Mass-induced sea level variations in the Red Sea from GRACE, steric-corrected altimetry, in situ bottom pressure records, and hydrographic observations

    Science.gov (United States)

    Feng, W.; Lemoine, J.-M.; Zhong, M.; Hsu, H. T.

    2014-08-01

    An annual amplitude of ∼18 cm mass-induced sea level variations (SLV) in the Red Sea is detected from the Gravity Recovery and Climate Experiment (GRACE) satellites and steric-corrected altimetry from 2003 to 2011. The annual mass variations in the region dominate the mean SLV, and generally reach maximum in late January/early February. The annual steric component of the mean SLV is relatively small (mass-induced SLV. In situ bottom pressure records at the eastern coast of the Red Sea validate the high mass variability observed by steric-corrected altimetry and GRACE. In addition, the horizontal water mass flux of the Red Sea estimated from GRACE and steric-corrected altimetry is validated by hydrographic observations.

  4. Mass-induced sea level variations in the Red Sea from steric-corrected altimetry, GRACE, in-situ bottom pressure records, and hydrographic observations

    Science.gov (United States)

    Feng, Wei; Lemoine, Jean-Michel; Zhong, Min; Xu, Houze

    2014-05-01

    An annual amplitude of ~18 cm mass-induced sea level variations (SLV) in the Red Sea is detected from steric-corrected altimetry and the Gravity Recovery and Climate Experiment (GRACE) satellites from 2003 to 2011, which dominates the mean sea level in the region. Seawater mass variations here generally reach maximum in late January/early February. The steric component of SLV calculated from oceanographic temperature and salinity data is relatively small and peaks about seven months later than mass variations. The phase difference between the steric SLV and the mass-induced SLV indicates that when the Red Sea gains the mass from inflow water in winter, the steric SLV fall, and vice versa in summer. In-situ bottom pressure records in the eastern coast of the Red Sea validate the high mass variability observed by steric-corrected altimetry and GRACE. Furthermore, we compare the horizontal water mass flux in the Red Sea from steric-corrected altimetry and GRACE with that estimated from hydrographic observations.

  5. Electronic and steric influences of pendant amine groups on the protonation of molybdenum bis (dinitrogen) complexes

    Energy Technology Data Exchange (ETDEWEB)

    Labios, Liezel A. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Heiden, Zachariah M. [Washington State Univ., Pullman, WA (United States); Mock, Michael T. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States)

    2015-05-04

    The synthesis of a series of PEtPNRR' (PEtPNRR' = Et₂PCH₂CH₂P(CH₂NRR')₂, R = H, R' = Ph or 2,4-difluorophenyl; R = R' = Ph or iPr) diphosphine ligands containing mono- and disubstituted pendant amine groups, and the preparation of their corresponding molybdenum bis(dinitrogen) complexes trans-Mo(N₂)₂(PMePh₂)₂(PEtPNRR') is described. In situ IR and multinuclear NMR spectroscopic studies monitoring the stepwise addition of (HOTf) to trans-Mo(N₂)₂(PMePh₂)₂(PEtPNRR') complexes in THF at -40 °C show that the electronic and steric properties of the R and R' groups of the pendant amines influence whether the complexes are protonated at Mo, a pendant amine, a coordinated N2 ligand, or a combination of these sites. For example, complexes containing mono-aryl substituted pendant amines are protonated at Mo and pendant amine to generate mono- and dicationic Mo–H species. Protonation of the complex containing less basic diphenyl-substituted pendant amines exclusively generates a monocationic hydrazido (Mo(NNH₂)) product, indicating preferential protonation of an N₂ ligand. Addition of HOTf to the complex featuring more basic diisopropyl amines primarily produces a monocationic product protonated at a pendant amine site, as well as a trace amount of dicationic Mo(NNH₂) product that contain protonated pendant amines. In addition, trans-Mo(N₂)₂(PMePh₂)₂(depe) (depe = Et₂PCH₂CH₂PEt₂) without a pendant amine was synthesized and treated with HOTf, generating a monocationic Mo(NNH₂) product. Protonolysis experiments conducted on select complexes in the series afforded trace amounts of NH₄⁺. Computational analysis of the series of trans-Mo(N₂)₂(PMePh₂)₂(PEtPNRR') complexes provides further insight into the proton affinity values of the metal center, N

  6. Helpful and Hindering Multicultural Events in Group Supervision: Climate and Multicultural Competence

    Science.gov (United States)

    Kaduvettoor, Anju; O'Shaughnessy, Tiffany; Mori, Yoko; Beverly, Clyde, III; Weatherford, Ryan D.; Ladany, Nicholas

    2009-01-01

    This study examines the relationship between multicultural events in group supervision, group climate, and supervisee multicultural competence using a mixed qualitative/quantitative design. The discovery-oriented approach yielded 196 helpful and hindering multicultural events among 136 participants. The most common events included multicultural…

  7. On the hindered settling of suspensions of mud and mud-sand mixtures

    NARCIS (Netherlands)

    Dankers, P.J.T.

    2006-01-01

    Highly concentrated suspensions are present in many natural environments. When the concentration becomes large enough, particles start to interfere with each other and their settling velocity reduces. This is called hindered settling. As a result of the reduced settling velocity, particles remain in

  8. The Experience of Unemployment for Fishery Workers in Newfoundland: What Helps and Hinders.

    Science.gov (United States)

    Borgen, William A.; Amundson, Norman E.; McVicar, Jonathan

    2002-01-01

    Explores the unemployment experience of people involved in the fishery and living in the outports of Newfoundland and Labrador. Fifty-three critical incident interviews were conducted by community outreach workers. These interviews yielded important information about the factors that facilitated or hindered the unemployment experience. (Contains…

  9. Factors that Promote or Hinder Young Disabled People in Work Participation: A Systematic Review

    NARCIS (Netherlands)

    Achterberg, T. J.; Wind, H.; de Boer, A. G. E. M.; Frings-Dresen, M. H. W.

    2009-01-01

    Introduction The aim of this systematic review was to study factors which promote or hinder young disabled people entering the labor market. Methods We systematically searched PubMed (by means of MESH and text words), EMBASE, PsycINFO, Web of Science and CINAHL for studies regarding (1) disabled

  10. Direct access to highly crystalline mesoporous nano TiO2 using sterically bulky organic acid templates

    Science.gov (United States)

    Bakre, Pratibha V.; Tilve, S. G.

    2018-05-01

    Sterically bulky monocarboxylic acid templates pivalic acid and phenoxyacetic acid are reported for the first time as organic templates in the sol-gel synthesis of TiO2. Mesoporous nanoparticulates of pure anatase phase and of well defined size were synthesized. The characterization of the materials prepared was done by various methods such as XRD, SEM, TEM, FTIR, UV-DRS, BET, etc. The prepared TiO2 samples were evaluated for the day light photodegradation of methylene blue by comparing with Degussa P25 and templates free synthesized TiO2 and were found to be more efficient.

  11. Steric modulation of coordination number and reactivity in the synthesis of lanthanoid(III) formamidinates.

    Science.gov (United States)

    Cole, Marcus L; Deacon, Glen B; Forsyth, Craig M; Junk, Peter C; Konstas, Kristina; Wang, Jun

    2007-01-01

    Reactions of a range of the readily prepared and sterically tunable N,N'-bis(aryl)formamidines with lanthanoid metals and bis(pentafluorophenyl)mercury (Hg(C6F5)2) in THF have given an extensive series of tris(formamidinato)lanthanoid(III) complexes, [Ln(Form)3(thf)n], namely [La(o-TolForm)3(thf)2], [Er(o-TolForm)3(thf)], [La(XylForm)3(thf)], [Sm(XylForm)3], [Ln(MesForm)3] (Ln=La, Nd, Sm and Yb), [Ln(EtForm)3] (Ln=La, Nd, Sm, Ho and Yb), and [Ln(o-PhPhForm)3] (Ln=La, Nd, Sm and Er). [For an explanation of the N,N'-bis(aryl)formamidinate abbreviations used see Scheme 1.] Analogous attempts to prepare [Yb(o-TolForm)3] by this method invariably yielded [{Yb(o-TolForm)2(mu-OH)(thf)}2], but [Yb(o-TolForm)3] was isolated from a metathesis synthesis. X-ray crystal structures show exclusively N,N'-chelation of the Form ligands and a gradation in coordination number with Ln3+ size and with Form ligand bulk. The largest ligands, MesForm, EtForm and o-PhPhForm give solely homoleptic complexes, the first two being six-coordinate, the last having an eta1-pi-Ar--Ln interaction. Reaction of lanthanoid elements and Hg(C6F5)2 with the still bulkier DippFormH in THF resulted in C--F activation and formation of [Ln(DippForm)2F(thf)] (Ln=La, Ce, Nd, Sm and Tm) complexes, and o-HC6F4O(CH2)4DippForm in which the formamidine is functionalised by a ring-opened THF that has trapped tetrafluorobenzyne. Analogous reactions between Ln metals, Hg(o-HC6F4)2 and DippFormH yielded [Ln(DippForm)2F(thf)] (Ln=La, Sm and Nd) and 3,4,5-F3C6H2O(CH2)4DippForm. X-ray crystal structures of the heteroleptic fluorides show six-coordinate monomers with two chelating DippForm ligands and cisoid fluoride and THF ligands in a trigonal prismatic array. The organometallic species [Ln(DippForm)2(C[triple chemical bond]CPh)(thf)] (Ln=Nd or Sm) are obtained from reaction of Nd metal, bis(phenylethynyl)mercury (Hg(C[triple chemical bond]CPh)2) and DippFormH, and the oxidation of [Sm(DippForm)2(thf)2] with Hg

  12. Steric effects in the dynamics of electrolytes at large applied voltages. II. Modified Poisson-Nernst-Planck equations.

    Science.gov (United States)

    Kilic, Mustafa Sabri; Bazant, Martin Z; Ajdari, Armand

    2007-02-01

    In situations involving large potentials or surface charges, the Poisson-Boltzman (PB) equation has shortcomings because it neglects ion-ion interactions and steric effects. This has been widely recognized by the electrochemistry community, leading to the development of various alternative models resulting in different sets "modified PB equations," which have had at least qualitative success in predicting equilibrium ion distributions. On the other hand, the literature is scarce in terms of descriptions of concentration dynamics in these regimes. Here, adapting strategies developed to modify the PB equation, we propose a simple modification of the widely used Poisson-Nernst-Planck (PNP) equations for ionic transport, which at least qualitatively accounts for steric effects. We analyze numerical solutions of these modified PNP equations on the model problem of the charging of a simple electrolyte cell, and compare the outcome to that of the standard PNP equations. Finally, we repeat the asymptotic analysis of Bazant, Thornton, and Ajdari [Phys. Rev. E 70, 021506 (2004)] for this new system of equations to further document the interest and limits of validity of the simpler equivalent electrical circuit models introduced in Part I [Kilic, Bazant, and Ajdari, Phys. Rev. E 75, 021502 (2007)] for such problems.

  13. Different Steric-Twist-Induced Ternary Memory Characteristics in Nonconjugated Copolymers with Pendant Naphthalene and 1,8-Naphthalimide Moieties.

    Science.gov (United States)

    Wang, Ming; Li, Zhuang; Li, Hua; He, Jinghui; Li, Najun; Xu, Qingfeng; Lu, Jianmei

    2017-10-18

    Herein, novel random copolymers PMNN and PMNB were designed and synthesized, and the memory devices Al/PMNN and PMNB/ITO both exhibited ternary memory performance. The switching voltages of the OFF-ON1 and ON1-ON2 transitions for both memory devices are around -2.0 and -3.5 V, respectively, and the ON1/OFF, ON2/ON1 current ratios are both up to 10 3 . The observed tristable electrical conductivity switching could be attributed to field-induced conformational ordering of the naphthalene rings in the side chains, and subsequent charge trapping by 1,8-naphthalimide moieties. More interestingly, by adjusting the connection sites of 1,8-naphthalimide moieties to tune the steric-twist effect, different memory properties were achieved (PMNN showed nonvolatile write once, read many (WORM) memory behavior, whereas PMNB showed volatile static RAM (SRAM) memory behavior). This result will offer a guideline for the design of different high-performance multilevel memory devices by tuning the steric effects of the chemical moieties. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Competences for enhancing interprofessional collaboration in a paediatrics setting: Enabling and hindering factors.

    Science.gov (United States)

    Solevåg, Anne Lee; Karlgren, Klas

    2016-01-01

    In 2011 an interprofessional educational programme called "Pediatric systematic assessment and communication for preventing emergencies" designed to increase clinical staff's competence in treating sick children was introduced in one paediatrics department in Norway. To elicit an in-depth understanding of the perceptions of clinical staff about the programme and enact adjustments according to identified enabling and hindering factors for learning, nurses and paediatricians were invited to participate in focus group interviews. The interviews were analysed by content analysis. Enabling factors for learning included improved interprofessional collaboration and positive feedback on performance. Hindering factors included perceptions that the programme was redundant and the fact that collaborating departments, such as the surgical departments, were not familiar with the programme. Peer learning, more interprofessional learning activities, and the fostering of a learning organization were suggestions for sustained learning. Based on the results of the study we have now included collaborating departments in the programme.

  15. Fusion hindrance in reactions with very heavy ions: Border between normal and hindered fusion

    International Nuclear Information System (INIS)

    Shen Caiwan; Li Qingfeng; Boilley, David; Shen Junjie; Abe, Yasuhisa

    2011-01-01

    The fusion hindrance in heavy-ion collisions is studied in the framework of the two-center liquid drop model. It appears that the neck and the radial degrees of freedom might both be hampered by an inner potential barrier on their path between the contact configuration to the compound nucleus. Heavy-ion reactions with and without the two kinds of fusion hindrance are classified through systematic calculations. It is found that the number of reactions without radial fusion hindrance is much smaller than that without neck fusion hindrance, and for both kinds of fusion hindrance the number of reactions without fusion hindrance at small mass-asymmetry parameter α is smaller than that at large α. In the formation of a given compound nucleus, if a reaction with α c is not hindered, then other reactions with α>α c are also not hindered, as is well known experimentally.

  16. Help or hinder? : Journalists affecting the future of female genital mutilation in a patriarchal society

    OpenAIRE

    Hallonsten, Sofia

    2016-01-01

    Is it possible to cover an issue as a journalist to the extent that you are practically a human rights activist, and still contribute to its continuation by unconsciously upholding the values causing the issue? This study asks the question if journalists help or hinder the elimination of female genital mutilation (FGM), and puts forth the thesis that journalists as a collective in fact are affecting the development more negatively through their attitudes than positively through their actions....

  17. Helpful and Hindering Factors in Psychodrama Field Training: A Longitudinal Mixed Methods Study of Student Development

    Directory of Open Access Journals (Sweden)

    Bracha Azoulay

    2018-02-01

    Full Text Available Although the literature indicates that students in mental health professions start to form their professional identity and competence in graduate school, there are few studies on the in-training experience of creative arts therapies students. This mixed methods study examined how five first-year students in a psychodrama master’s degree program in Israel experienced their field training, with the aim of identifying the factors likely to promote or hinder the development of their professional identity and sense of professional ability. Longitudinal data were collected weekly throughout the 20-week field training experience. The students reported qualitatively on helpful and hindering factors and were assessed quantitatively on questionnaires measuring professional identity, perceived demands-abilities fit, client involvement, and therapy session evaluations. A thematic analysis of the students’ reports indicated that a clear and defined setting and structure, observing the instructor as a role model, actively leading parts of the session, and observing fellow students were all helpful factors. The hindering factors included role confusion, issues related to coping with client resistance and disciplinary problems, as well as school end-of-year activities that disrupted the continuity of therapy. The quantitative results indicated that students’ professional identity did not significantly change over the year, whereas a U-shaped curve trajectory characterized the changes in demands-abilities fit and other measures. Students began their field training with an overstated sense of ability that soon declined and later increased. These findings provide indications of which helping and hindering factors should be maximized and minimized, to enhance students’ field training.

  18. Helpful and Hindering Factors in Psychodrama Field Training: A Longitudinal Mixed Methods Study of Student Development.

    Science.gov (United States)

    Azoulay, Bracha; Orkibi, Hod

    2018-01-01

    Although the literature indicates that students in mental health professions start to form their professional identity and competence in graduate school, there are few studies on the in-training experience of creative arts therapies students. This mixed methods study examined how five first-year students in a psychodrama master's degree program in Israel experienced their field training, with the aim of identifying the factors likely to promote or hinder the development of their professional identity and sense of professional ability. Longitudinal data were collected weekly throughout the 20-week field training experience. The students reported qualitatively on helpful and hindering factors and were assessed quantitatively on questionnaires measuring professional identity, perceived demands-abilities fit, client involvement, and therapy session evaluations. A thematic analysis of the students' reports indicated that a clear and defined setting and structure, observing the instructor as a role model, actively leading parts of the session, and observing fellow students were all helpful factors. The hindering factors included role confusion, issues related to coping with client resistance and disciplinary problems, as well as school end-of-year activities that disrupted the continuity of therapy. The quantitative results indicated that students' professional identity did not significantly change over the year, whereas a U-shaped curve trajectory characterized the changes in demands-abilities fit and other measures. Students began their field training with an overstated sense of ability that soon declined and later increased. These findings provide indications of which helping and hindering factors should be maximized and minimized, to enhance students' field training.

  19. Statin Use and Self-Reported Hindering Muscle Complaints in Older Persons: A Population Based Study.

    Directory of Open Access Journals (Sweden)

    Milly A van der Ploeg

    Full Text Available Statins are widely used by older persons in primary and secondary prevention of cardiovascular disease. Although serious adverse events are rare, many statin users report mild muscle pain and/or muscle weakness. It's unclear what impact statins exert on a patient's daily life. Research on statin related side effects in older persons is relatively scarce. We therefore investigated the relation between statin use and self-reported hindering muscle complaints in older persons in the general population.The present research was performed within the Integrated Systematic Care for Older Persons (ISCOPE study in the Netherlands (Netherlands trial register, NTR1946. All registered adults aged ≥ 75 years from 59 participating practices (n = 12,066 were targeted. Information about the medical history and statin use at baseline and after 9 months was available for 4355 participants from the Electronic Patient Records of the general practitioners. In the screening questionnaire at baseline we asked participants: 'At the moment, which health complaints limit you the most in your day-to-day life?' Answers indicating muscle or musculoskeletal complaints were coded as such. No specific questions about muscle complaints were asked.The participants had a median age of 80.3 (IQR 77.6-84.4 years, 60.8% were female and 28.5% had a history of CVD. At baseline 29% used a statin. At follow-up, no difference was found in the prevalence of self-reported hindering muscle complaints in statin users compared to non-statin users (3.3% vs. 2.5%, OR 1.39, 95% CI 0.94-2.05; P = 0.98. Discontinuation of statin use during follow-up was independent of self-reported hindering muscle complaints.Based on the present findings, prevalent statin use in this community-dwelling older population is not associated with self-reported hindering muscle complaints; however, the results might be different for incident users.

  20. Statin Use and Self-Reported Hindering Muscle Complaints in Older Persons: A Population Based Study.

    Science.gov (United States)

    van der Ploeg, Milly A; Poortvliet, Rosalinde K E; van Blijswijk, Sophie C E; den Elzen, Wendy P J; van Peet, Petra G; de Ruijter, Wouter; Blom, Jeanet W; Gussekloo, Jacobijn

    2016-01-01

    Statins are widely used by older persons in primary and secondary prevention of cardiovascular disease. Although serious adverse events are rare, many statin users report mild muscle pain and/or muscle weakness. It's unclear what impact statins exert on a patient's daily life. Research on statin related side effects in older persons is relatively scarce. We therefore investigated the relation between statin use and self-reported hindering muscle complaints in older persons in the general population. The present research was performed within the Integrated Systematic Care for Older Persons (ISCOPE) study in the Netherlands (Netherlands trial register, NTR1946). All registered adults aged ≥ 75 years from 59 participating practices (n = 12,066) were targeted. Information about the medical history and statin use at baseline and after 9 months was available for 4355 participants from the Electronic Patient Records of the general practitioners. In the screening questionnaire at baseline we asked participants: 'At the moment, which health complaints limit you the most in your day-to-day life?' Answers indicating muscle or musculoskeletal complaints were coded as such. No specific questions about muscle complaints were asked. The participants had a median age of 80.3 (IQR 77.6-84.4) years, 60.8% were female and 28.5% had a history of CVD. At baseline 29% used a statin. At follow-up, no difference was found in the prevalence of self-reported hindering muscle complaints in statin users compared to non-statin users (3.3% vs. 2.5%, OR 1.39, 95% CI 0.94-2.05; P = 0.98). Discontinuation of statin use during follow-up was independent of self-reported hindering muscle complaints. Based on the present findings, prevalent statin use in this community-dwelling older population is not associated with self-reported hindering muscle complaints; however, the results might be different for incident users.

  1. Heat-conserving postures hinder escape: a thermoregulation–predation trade-off in wintering birds

    OpenAIRE

    Jennie M. Carr; Steven L. Lima

    2012-01-01

    Wintering birds may conserve body heat by adopting postures with minimal leg exposure or significant ptiloerection. However, maximally heat-conserving postures may hinder a bird's ability to escape attack, leading to a trade-off between predation risk and thermoregulation. Such a trade-off implies that birds should use the most heat-conserving postures only at very cold temperatures. Feeding in a relatively low-risk environment should also facilitate the use of such heat-conserving postures. ...

  2. What hinders implementation of the WHO FCTC Article 5.3? - The case of South Korea.

    Science.gov (United States)

    Lee, Sungkyu

    2016-10-01

    The aims of this study are to identify what hinders implementation of the WHO Framework Convention on Tobacco Control (FCTC) Article 5.3 in Korea, and to provide suggestions for the implementation of Article 5.3. Official governmental documents on tobacco control were reviewed. We also searched news articles for data triangulation. There were three factors that hindered the implementation of Article 5.3 in Korea. Firstly, there has been legal conflict between two tobacco-related laws, one of which is designed to promote the tobacco industry. The other is designed to promote public health. Secondly, the government has had economic interests in the tobacco industry, and its lack of action to effectively regulate the tobacco industry's corporate social responsibility (CSR) practices has hindered the implementation of Article 5.3. Thirdly, the tobacco industry's lobby and active interference in the policy-making process has been a barrier. To fully implement Article 5.3, this study suggests: defusing legal conflict between tobacco-related laws; not considering tobacco industry as a stakeholder; regulating tobacco industry's CSR activities; raising awareness of tobacco industry interference; securing transparency between the government and tobacco industry; and establishing a core group or a committee under the government to implement Article 5.3.

  3. Factors that promote or hinder young disabled people in work participation: a systematic review.

    Science.gov (United States)

    Achterberg, T J; Wind, H; de Boer, A G E M; Frings-Dresen, M H W

    2009-06-01

    The aim of this systematic review was to study factors which promote or hinder young disabled people entering the labor market. We systematically searched PubMed (by means of MESH and text words), EMBASE, PsycINFO, Web of Science and CINAHL for studies regarding (1) disabled patients diagnosed before the age of 18 years and (2) factors of work participation. Out of 1,268 retrieved studies and 28 extended studies from references and four from experts, ten articles were included. Promoting factors are male gender, high educational level, age at survey, low depression scores, high dispositional optimism and high psychosocial functioning. Female and low educational level gives high odds of unemployment just like low IQ, inpatient treatment during follow up, epilepsy, motor impairment, wheelchair dependency, functional limitations, co-morbidity, physical disability and chronic health conditions combined with mental retardation. High dose cranial radiotherapy, type of cancer, and age of diagnosis also interfered with employment. Of the promoting factors, education appeared to be important, and several physical obstructions were found to be hindering factors. The last mentioned factors can be influenced in contrast to for instance age and gender. However, to optimize work participation of this group of young disabled it is important to know the promoting or hindering influence for employment.

  4. Steric effects in release of amides from linkers in solid-phase synthesis. Molecular mechanics modeling of key step in peptide and combinatorial chemistry

    DEFF Research Database (Denmark)

    Norrby, Per-Ola; Jensen, Knud Jørgen

    2006-01-01

    Acidolytic release of an amide from a solid support by C-N bond cleavage is all ubiquitous and crucial step in many solid-phase syntheses. We have used molecular modeling of a pseudo-equilibrium to explore substituent and steric effects in the release of peptides. The high acid-lability of the ba......Acidolytic release of an amide from a solid support by C-N bond cleavage is all ubiquitous and crucial step in many solid-phase syntheses. We have used molecular modeling of a pseudo-equilibrium to explore substituent and steric effects in the release of peptides. The high acid......-lability of the backbone amide linkage (BAL), which releases sec. amides, compared to C-terminal amide anchoring, which releases primary amides, was rationalized by steric relief upon cleavage. Thus, the relative stability of the carbenium ion formed from the linker in the acidolytic release is an insufficient measure...

  5. Effects of the steric hindrance of micropores in the hyper-cross-linked polymeric adsorbent on the adsorption of p-nitroaniline in aqueous solution

    International Nuclear Information System (INIS)

    Xiao, Guqing; Wen, Ruimin; Wei, Dongmei; Wu, Dan

    2014-01-01

    Graphical abstract: The hyper-cross-linked polymeric adsorbents (GQ-05 and GQ-03) with different steric hindrance of micropores were designed. The adsorption capacity and adsorption rate of PNA onto the two adsorbents followed the order GQ-05 > GQ-03. The steric hindrance of micropores was a crucial factor for the adsorption capacity and adsorption rate order. - Highlights: • Two adsorbents with different steric hindrance of micropores were designed. • The adsorption capacity and adsorption rate followed the order GQ-05 > GQ-03. • The steric hindrance of micropores was a crucial factor for the order. - Abstract: A hyper-cross-linked polymeric adsorbent with “-CH 2 -phenol-CH 2 -” as the cross-linked bridge (denoted GQ-05), and another hyper-cross-linked polymeric adsorbent with “-CH 2 -p-cresol-CH 2 -” as the cross-linked bridge (denoted GQ-03) were synthesized to reveal the effect of the steric hindrance of micropores in the hyper-cross-linked polymeric adsorbent on adsorption capacity and adsorption rate of p-nitroaniline (PNA) from aqueous solution. The results of adsorption kinetics indicated the order of the adsorption rate GQ-05 > GQ-03. The pseudo-first-order rate equation could describe the entire adsorption process of PNA onto GQ-05 while the equation characterized the adsorption process of GQ-03 in two stages. The order of the adsorption capacity GQ-05 > GQ-03 was demonstrated by thermodynamic analysis and dynamic adsorption. The steric hindrance of micropores in the hyper-cross-linked polymeric adsorbent was a crucial factor for the order of the adsorption capacity and adsorption rate

  6. The role of PEG conformation in mixed layers: from protein corona substrate to steric stabilization avoiding protein adsorption

    Directory of Open Access Journals (Sweden)

    Joan Comenge

    2015-03-01

    Full Text Available Although nanoparticles (NPs have been traditionally modified with a single ligand layer, mixture of ligands might help to combine different functionalities and to further engineer the NP surface. A detailed study of the competition between an alkanethiol (11-mercaptoundecanoic acid and SH-PEG for the surface of AuNPs and the resultant behaviors of this model nanoconjugate is presented here. As a result, the physicochemical properties of these conjugates can be progressively tuned by controlling the composition and especially the conformation of the mixed monolayer. This has implications in the physiological stability. The controlled changes on the SH-PEG conformation rather than its concentration induce a change in the stabilization mechanism from electrostatic repulsion to steric hindrance, which changes the biological fate of NPs. Importantly, the adsorption of proteins on the conjugates can be tailored by tuning the composition and conformation of the mixed layer.

  7. The effects of conformational constraints and steric bulk in the amino acid moiety of philanthotoxins on AMPAR antagonism

    DEFF Research Database (Denmark)

    Jørgensen, Malene; Olsen, Christian A; Mellor, Ian R

    2005-01-01

    , establishing general protocols for philanthotoxin solution- and solid-phase synthesis (39-90% and 42-54% overall yields, respectively). The analogues were tested for their ability to antagonize kainate-induced currents of 2-amino-3-(3-hydroxy-5-methyl-4-isoxazoyl)propanoic acid receptors (AMPAR) expressed...... in Xenopus oocytes from rat brain mRNA. This showed that steric bulk in the amino acid moiety is well tolerated and suggests that binding to AMPAR does not involve the alpha-NHCO group as a donor in hydrogen bonding.......Philanthotoxin-343 (PhTX-343), a synthetic analogue of wasp toxin PhTX-433, is a noncompetitive antagonist at ionotropic receptors (e.g., AChR or iGluR). To determine possible effects of variations of the amino acid side chain, a library consisting of seventeen PhTX-343 analogues was prepared. Thus...

  8. Steric and electronic effects of 1,3-disubstituted cyclopentadienyl ligands on metallocene derivatives of Cerium, Titanium, Manganese, and Iron

    Energy Technology Data Exchange (ETDEWEB)

    Sofield, Chadwick Dean [Univ. of California, Berkeley, CA (United States)

    2000-05-01

    Sterically demanding 1,3-disubstituted cyclopentadienyl ligands were used to modify the physical properties of the corresponding metallocenes. Sterically demanding ligands provided kinetic stabilization for trivalent cerium compounds. Tris(di-t-butylcyclopentadienyl)cerium was prepared and anion competition between halides and cyclopentadienyl groups which had complicated synthesis of the tris(cyclopentadienyl)compound was qualitatively examined. Bis(di-t-butylcyclopentadienyl)cerium methyl was prepared and its rate of decomposition, by ligand redistribution, to tris(di-t-butylcyclopentadienyl)cerium was shown to be slower than the corresponding rate for less sterically demanding ligands. Asymmetrically substituted ligands provided a symmetry label for examination of chemical exchange processes. Tris[trimethylsilyl(t-butyl)cyclopentadienyl]cerium was prepared and the rate of interconversion between the C1 and C3 isomers was examined. The enthalpy difference between the two distereomers is 7.0 kJ/mol. The sterically demanding cyclopentadienyl ligands ansa-di-t-butylcyclopentadiene (Me2Si[(Me3C)2C5H3]2), ansa-bis(trimethylsilyl)cyclopentadiene (Me2Si[(Me3Si)2C5H3]2) and tetra-t-butylfulvalene and metallocene derivatives of the ligands were prepared and their structures were examined by single crystal X-ray crystallography. The effect that substituents on the cyclopentadienyl ring have on the pi-electron system of the ligand was examined through interaction between ligand and metal orbitals. A series of 1,3-disubstituted manganocenes was prepared and their electronic states were determined by solid-state magnetic susceptibility, electron paramagnetic resonance, X-ray crystallography, and variable temperature UV-vis spectroscopy. Spin-equilibria in [(Me3C)2C5H3]2Mn and [(Me3

  9. Analysis of 3D models of octopus estrogen receptor with estradiol: evidence for steric clashes that prevent estrogen binding.

    Science.gov (United States)

    Baker, Michael E; Chandsawangbhuwana, Charlie

    2007-09-28

    Relatives of the vertebrate estrogen receptor (ER) are found in Aplysia californica, Octopus vulgaris, Thais clavigera, and Marisa cornuarietis. Unlike vertebrate ERs, invertebrate ERs are constitutively active and do not bind estradiol. To investigate the molecular basis of the absence of estrogen binding, we constructed a 3D model of the putative steroid-binding domain on octopus ER. Our 3D model indicates that binding of estradiol to octopus ER is prevented by steric clashes between estradiol and amino acids in the steroid-binding pocket. In this respect, octopus ER resembles vertebrate estrogen-related receptors (ERR), which have a ligand-binding pocket that cannot accommodate estradiol. Like ERR, octopus ER also may have the activation function 2 domain (AF2) in a configuration that can bind to coactivators in the absence of estrogens, which would explain constitutive activity of octopus ER.

  10. Synthesis of zinc phthalocyanine with large steric hindrance and its photovoltaic performance for dye-sensitized solar cells.

    Science.gov (United States)

    Lin, Li; Peng, Bosi; Shi, Wenye; Guo, Yingying; Li, Renjie

    2015-03-28

    A zinc phthalocyanine (ZnPc) derivative (Zn-tri-PcNc-8) containing tri-benzonaphtho-condensed porphyrazine with one carboxylic and six diphenylphenoxy peripheral substitutions was designed and synthesized as a sensitizer for dye-sensitized solar cells (DSSCs). For the purpose of extending the absorption spectra while minimizing the formation of ZnPc molecular aggregates, bulky 2,6-diphenylphenoxy groups were used as electron donor moieties, and the carboxylic group as an anchoring group to graft the sensitizer onto the semiconductor. It was found that a TiO2-based solar cell sensitized by Zn-tri-PcNc-8 shows a maximum incident photon-to-current conversion efficiency in the red/near-IR light range (650-750 nm), and a solar cell sensitized at near room temperature (30 °C) for 48 h exhibits the best efficiency (3.01%). The efficiency was much higher than that (1.96%) for a solar cell sensitized by its analogue (Zn-tri-PcNc-2) having one carboxyl and three tert-butyl groups without chenodeoxycholic acid (CDCA), indicating that the introduction of six bulky diphenylphenoxy substitutions with large steric hindrance in the ZnPc macrocycle can effectively suppress the molecular aggregates, thus resulting in an improved conversion efficiency. The present results shed light on an effective solution to adjust the ZnPc property via chemical modification such as changing the "push-pull" effect and adding large steric hindrance substituents to further improve the efficiency of the phthalocyanine-sensitized solar cell.

  11. Exploring bikeability in a metropolitan setting: stimulating and hindering factors in commuting route environments

    Directory of Open Access Journals (Sweden)

    Wahlgren Lina

    2012-03-01

    Full Text Available Abstract Background Route environments may influence people's active commuting positively and thereby contribute to public health. Assessments of route environments are, however, needed in order to better understand the possible relationship between active commuting and the route environment. The aim of this study was, therefore, to assess the potential associations between perceptions of whether the route environment on the whole hinders or stimulates bicycle commuting and perceptions of environmental factors. Methods The Active Commuting Route Environment Scale (ACRES was used for the assessment of bicycle commuters' perceptions of their route environments in the inner urban parts of Greater Stockholm, Sweden. Bicycle commuters (n = 827 were recruited by advertisements in newspapers. Simultaneous multiple regression analyses were used to assess the relation between predictor variables (such as levels of exhaust fumes, noise, traffic speed, traffic congestion and greenery and the outcome variable (hindering - stimulating route environments. Two models were run, (Model 1 without and (Model 2 with the item traffic: unsafe or safe included as a predictor. Results Overall, about 40% of the variance of hindering - stimulating route environments was explained by the environmental predictors in our models (Model 1, R2 = 0.415, and Model 2, R 2= 0.435. The regression equation for Model 1 was: y = 8.53 + 0.33 ugly or beautiful + 0.14 greenery + (-0.14 course of the route + (-0.13 exhaust fumes + (-0.09 congestion: all types of vehicles (p ≤ 0.019. The regression equation for Model 2 was y = 6.55 + 0.31 ugly or beautiful + 0.16 traffic: unsafe or safe + (-0.13 exhaust fumes + 0.12 greenery + (-0.12 course of the route (p ≤ 0.001. Conclusions The main results indicate that beautiful, green and safe route environments seem to be, independently of each other, stimulating factors for bicycle commuting in inner urban areas. On the other hand, exhaust

  12. 13C nuclear magnetic resonance data of lanosterol derivatives—Profiling the steric topology of the steroid skeleton via substituent effects on its 13C NMR

    Science.gov (United States)

    Dias, Jerry Ray; Gao, Hongwu

    2009-12-01

    The 13C NMR spectra of over 24 tetracyclic triterpenoid derivatives have been structurally analyzed. The 13C NMR chemical shifts allow one to probe the steric topology of the rigid steroid skeleton and inductive effects of its substituents. Use of deuterium labeling in chemical shift assignment and B-ring aromatic terpenoids are also featured.

  13. Quinoidal Oligo(9,10-anthryl)s with Chain-Length-Dependent Ground States: A Balance between Aromatic Stabilization and Steric Strain Release

    KAUST Repository

    Lim, Zhenglong; Zheng, Bin; Huang, Kuo-Wei; Liu, Ye; Wu, Jishan

    2015-01-01

    : the large steric repulsion between the anthryl/phenyl units in the closed-shell quinoidal form that drives the molecule to a flexible open-shell diradical structure, and aromatic stabilisation due to the gain of more aromatic sextet rings in the closed

  14. Influence of steric hindrance on enantioseparation of Dns-amino acids and pesticides on terguride based chiral selectors in capillary electrophoresis

    Czech Academy of Sciences Publication Activity Database

    Honzátko, Aleš; Cvak, Jan; Vaingátová, Silvie; Flieger, Miroslav

    2005-01-01

    Roč. 28, - (2005), s. 673-677 ISSN 1615-9306 R&D Projects: GA ČR GA203/02/0933 Institutional research plan: CEZ:AV0Z50200510 Keywords : steric hindrance * capillary electrophoresis * pesticides Subject RIV: EE - Microbiology, Virology Impact factor: 1.829, year: 2005

  15. Data versus Spock: lay theories about whether emotion helps or hinders.

    Science.gov (United States)

    Karnaze, Melissa M; Levine, Linda J

    2018-05-01

    The android Data from Star Trek admired human emotion whereas Spock viewed emotion as irrational and maladaptive. The theory that emotions fulfil adaptive functions is widely accepted in academic psychology but little is known about laypeople's theories. The present study assessed the extent to which laypeople share Data's view of emotion as helpful or Spock's view of emotion as a hindrance. We also assessed how help and hinder theory endorsement were related to reasoning, emotion regulation, and well-being. Undergraduates (N = 630) completed a stressful timed reasoning task and questionnaires that assessed their theories of emotion, emotion regulation strategies, happiness, and social support. Overall, participants viewed emotion more as a help than a hindrance. The more they endorsed the view that emotion helps, the better their reasoning scores. Endorsing a help theory also predicted the use of reappraisal which, in turn, predicted greater happiness and social support. In contrast, endorsing the view that emotion hinders was associated with emotion suppression and less social support. Thus, people's theories about the functionality of emotion may have important implications for their reasoning and emotional well-being.

  16. Factors hindering clinical training of students in selected nursing educational institutions in Southeastern Nigeria.

    Science.gov (United States)

    Anarado, Agnes N; Agu, Grace U; Nwonu, Eunice I

    2016-05-01

    Clinical training is an integral part of professional nursing education as it equips students with the required knowledge, skills, attitudes, and values needed for optimal practice in real-life situations. Inappropriate professional attributes have been observed among nursing graduates, while challenges to acquisition of clinical skills have been understudied in Nigeria. This study investigated system factors related to the provision of infrastructure/equipment, training/supervisory activities, and students' factors that may hinder clinical training of nursing students in two selected institutions in Southeastern Nigeria. This cross-sectional descriptive study purposively enlisted 283 students from a diploma and a degree nursing education program. Data were collected with researchers' developed questionnaire and analyzed in percentages, and means, with a mean decision criterion of valueprogram students had significantly less opportunity for return demonstration under supervision and independent practice in the laboratory; the diploma program students had significantly fewer teachers in their school and patients in their clinical area, clinical nurses as role models were not following the standard procedures in practice and students were not evaluated by supervisors at the end of each clinical experience. Identified factors in these training environments could hinder learners' interest and acquisition of professional attributes. Rectifying these situations could enhance the acquisition and display of appropriate professional performance behavior in practice by nursing graduates. Copyright © 2016 Elsevier Ltd. All rights reserved.

  17. Fragmentation approach to the point-island model with hindered aggregation: Accessing the barrier energy

    Science.gov (United States)

    González, Diego Luis; Pimpinelli, Alberto; Einstein, T. L.

    2017-07-01

    We study the effect of hindered aggregation on the island formation process in a one- (1D) and two-dimensional (2D) point-island model for epitaxial growth with arbitrary critical nucleus size i . In our model, the attachment of monomers to preexisting islands is hindered by an additional attachment barrier, characterized by length la. For la=0 the islands behave as perfect sinks while for la→∞ they behave as reflecting boundaries. For intermediate values of la, the system exhibits a crossover between two different kinds of processes, diffusion-limited aggregation and attachment-limited aggregation. We calculate the growth exponents of the density of islands and monomers for the low coverage and aggregation regimes. The capture-zone (CZ) distributions are also calculated for different values of i and la. In order to obtain a good spatial description of the nucleation process, we propose a fragmentation model, which is based on an approximate description of nucleation inside of the gaps for 1D and the CZs for 2D. In both cases, the nucleation is described by using two different physically rooted probabilities, which are related with the microscopic parameters of the model (i and la). We test our analytical model with extensive numerical simulations and previously established results. The proposed model describes excellently the statistical behavior of the system for arbitrary values of la and i =1 , 2, and 3.

  18. Multi-layer foil web hindering radiation, particularly radioactive radiation. Strahlung, insbesondere radioaktive Strahlung hemmende mehrschichtige Folienbahn

    Energy Technology Data Exchange (ETDEWEB)

    Anon,

    1987-02-19

    The invention concerns surfaces hindering radiation, which contain lead or other heavy material, which have a layer containing heavy material particles, particularly lead particles, for use as protective clothing.

  19. Nitroxyl free radicals formed from hindered amine light stabilizers under 60Co γ-ray irradiation

    International Nuclear Information System (INIS)

    Wang Huiliang; Chen Wenxiu

    2006-01-01

    Nitroxyl free radicals formed from several low molecular weight (LMW) hindered amine light stabilizers (HALS) under 60 Co γ-ray irradiation was studied with electron spin resonance (ESR) spectroscopy. All the HALSs irradiated in air formed nitroxyl free radicals under irradiation in air. For most of the HALSs, concentration of the nitroxyl free radicals increased linearly and quickly with absorbed dose in 0-10 kGy range, but increased slowly, or even kept constant, with doses of greater than 10 kGy. Concentration of nitroxyl free radicals formed from LMW HALS was usually higher than high molecular weight HALS. Tetramethyl HALS was easier to form nitroxyl free radicals than pentamethyl HLAS. Concentration of nitroxyl free radicals formed from the samples irradiated in oxygen was about two times higher than that the samples irradiated in air. Mechanisms of the nitroxyl free radical formation from the γ-ray irradiated HALSs were was discussed. (authors)

  20. What Hinders the Implementation of the Supply Chain Risk Management Process Into Practice Organizations?

    DEFF Research Database (Denmark)

    Gredal, Pauline; Panyi, Zsófia; Kinra, Aseem

    2017-01-01

    Supply chain risk management process (SCRMP) is being advanced as a systematic and structured approach for identifying, assessing, mitigating, and monitoring all risks arising from complex supply chains. However, while the literature deems it necessary to implement such a process as the solution ...... indicate that the unavailability of information and lack of proper data management hinders the implementation of SCRMP in the context global supply chains.......Supply chain risk management process (SCRMP) is being advanced as a systematic and structured approach for identifying, assessing, mitigating, and monitoring all risks arising from complex supply chains. However, while the literature deems it necessary to implement such a process as the solution...... to the increasing vulnerability companies face, there is a lack of empirical evidence on whether the process model can be implemented. This paper shows possible hindrances in the implementation of SCRMP for companies with global supply chains based on the findings of an in-depth case study. Our empirical findings...

  1. Steric Interference of Adhesion Supports In-Vitro Chondrogenesis of Mesenchymal Stem Cells on Hydrogels for Cartilage Repair.

    Science.gov (United States)

    Goldshmid, Revital; Cohen, Shlomit; Shachaf, Yonatan; Kupershmit, Ilana; Sarig-Nadir, Offra; Seliktar, Dror; Wechsler, Roni

    2015-09-28

    Recent studies suggest the presence of cell adhesion motifs found in structural proteins can inhibit chondrogenesis. In this context, the current study aims to determine if a polyethylene glycol (PEG)-modified fibrinogen matrix could support better chondrogenesis of human bone marrow mesenchymal stem cells (BM-MSC) based on steric interference of adhesion, when compared to a natural fibrin matrix. Hydrogels used as substrates for two-dimensional (2D) BM-MSC cultures under chondrogenic conditions were made from cross-linked PEG-fibrinogen (PF) and compared to thrombin-activated fibrin. Cell morphology, protein expression, DNA and sulfated proteoglycan (GAG) content were correlated to substrate properties such as stiffness and adhesiveness. Cell aggregation and chondrogenic markers, including collagen II and aggrecan, were observed on all PF substrates but not on fibrin. Shielding fibrinogen's adhesion domains and increasing stiffness of the material are likely contributing factors that cause the BM-MSCs to display a more chondrogenic phenotype. One composition of PF corresponding to GelrinC™--a product cleared in the EU for cartilage repair--was found to be optimal for supporting chondrogenic differentiation of BM-MSC while minimizing hypertrophy (collagen X). These findings suggest that semi-synthetic biomaterials based on ECM proteins can be designed to favourably affect BM-MSC towards repair processes involving chondrogenesis.

  2. A highly sensitive and selective fluorescent sensor for detection of sulfide anion based on the steric hindrance effect

    Science.gov (United States)

    Chen, Guanfan; Tang, Mengzhuo; Fu, Xiufang; Cheng, Fenmin; Zou, Xianghua; Wang, Jingpei; Zeng, Rongjin

    2018-01-01

    Sulfide anions are not only generated as a byproduct from industrial processes but also as a crucial kind of element in biological systems. Therefore, fluorescent probes for detecting sulfide anion with sensitive and selective characters are highly popular. In this study, we report a highly sensitive and selective fluorescent sensor M1 for detection of sulfide anion based on the steric hindrance effect, where the recognition unit, dinitrobenzenesulfonate ester group is linked to aromatic ortho-position in the porphyrin, and correspondingly the fluorescence of fluorescein is efficiently quenched. Compared with the sensors with recognition unit linked to the other aromatic positions, the fluorescent sensor M1 has a lower fluorescence background. Furthermore, the corresponding fluorescence responses (F/F0) of M1 for mercapto amino-acid GSH, Hcy and Cys, were all far lower than the relative fluorescence ratio F/F0 values for S2-. It means that M1 is sensitive and selective to detection of S2-, and has an anti-disturbance ability to the biologically-relevant thiols, GSH, Hcy and Cys, and has the prospect of application in the exact detection of sulfide anions in living organisms. This approach offers some useful insights for realizing sensitive and selective fluorescent turn-on sensing in the detection assays for other analytes.

  3. Study of the role of bran water binding and the steric hindrance by bran in straight dough bread making.

    Science.gov (United States)

    Hemdane, S; Langenaeken, N A; Jacobs, P J; Verspreet, J; Delcour, J A; Courtin, C M

    2018-07-01

    This study investigates the effect of the physical presence and water binding of wheat bran during bread making, and the possible mechanisms behind this effect. Regular bran, pericarp-enriched bran and synthetic bran-like particles with different water binding capacities and particle sizes were used. Incorporation of regular and pericarp-enriched bran in dough (15% dm) led to a lower oven rise than the control dough. Bread volumes decreased with 11% and 30%, respectively. Dough with synthetic bran, having a low water binding capacity, displayed a near to normal leavening and oven rise and resulted in a bread volume decrease of only 5% compared to the control. Particle size reduction of regular bran and synthetic bran to an average size of 200 µm did not affect final bread quality. Results indicate that water binding by bran affects bread quality the most, whereas steric hindrance by physical presence of bran particles is less determinative. Copyright © 2018 Elsevier Ltd. All rights reserved.

  4. Synthesis, autoxidation and photooxidation of hindered pyrrole derivatives. Hindered pyrrolic nitroxide radicals; Synthese, autoxydation et photoxidation de pyrroles encombres radicaux nitroxydes pyrroliques encombres

    Energy Technology Data Exchange (ETDEWEB)

    Ramasseul, R [Commissariat a l' Energie Atomique, Grenoble (France). Centre d' Etudes Nucleaires

    1969-07-01

    2,5-di-t-butyl and 2,3,5-tri-t-butyl pyrrole are prepared from pinacoline and their structure is confirmed by comparison with 2,5-di-t-butyl furan and thiophene (I.R., U.V. and N.M.R. {sup 13}C satellites observation giving J{sub 13{sub C-H}} and J{sub H{sub 3}-H{sub 4}}). The sensitized photooxidation of these hindered pyrroles gives corresponding hydroperoxides which most likely structure is determined using physical and chemical methods. Oxidation of 2,5-di-t-butyl and 2,3,5-tri-t-butyl pyrrole by hydrogen peroxide in presence of inorganic per-acid of by p-nitro-perbenzoic acid does not give the pyrrolic nitroxides in contrast with secondary amines. Some N-hydroxypyrroles are then prepared from pinacoline and ethyl pivaloyl-acetate. Their oxidation by lead dioxide gives the corresponding pyrrolic nitroxides. 2,5-di-t-butyl 3,4-di-ethoxycarbonyl pyrryl 1-oxy is isolated and studied spectroscopically (visible and U.V., E.P.R.). In marked contrast with ordinary nitroxides it does not show solvent effect. It can be compared with 2,4-di-t-butyl cyclopentadienone, a carbon analog. For both, the long wave length transition does not show the usual n - {pi}* behaviour; that is confirmed by E.P.R. Using Huckel method for pyrrolic nitroxide skeleton, it is possible to have a good interpretation of experimental data. (author) [French] Les di-t-butyl 2,5 et tri-t-butyl-2,3,5 pyrrole sont synthetises a partir de la pinacoline et leur structure confirmee par comparaison avec les di-t-butyl-2,5 furanne et thiophene (I.R., U.V. et R.M.N.: observation des satellites {sup 13}C conduisant a la mesure des J{sub 13{sub C-H}} et J{sub H{sub 3}{sub -H{sub 4}}). La photoxydation sensibilisee de ces pyrroles encombres conduit aux hydroperoxydes correspondants dont la structure la plus probable est determinee par les methodes physicochimiques. L'oxydation des di-t-butyl-2,5 et tri-t-butyl-2,3,5 pyrrole par l'eau oxygenee en presence de peracide mineral ou par l'acide p

  5. Sterics level the rates of proton transfer to [Ni(XPh){PhP(CH₂CH₂PPh₂)₂}]⁺ (X = O, S or Se).

    Science.gov (United States)

    Alwaaly, Ahmed; Henderson, Richard A

    2014-09-04

    Rates of proton transfers between lutH(+) (lut = 2,6-dimethylpyridine) and [Ni(XPh)(PhP{CH2CH2PPh2}2)](+) (X = O, S or Se) are slow and show little variation (k(O) : k(S) : k(Se) = 1 : 12 : 9). This unusual behaviour is a consequence of sterics affecting the optimal interaction between the reactants prior to proton transfer.

  6. Re-evaluating the role of sterics and electronic coupling in determining the open-circuit voltage of organic solar cells

    KAUST Repository

    Graham, Kenneth; Erwin, Patrick; Nordlund, Dennis; Vandewal, Koen; Li, Ruipeng; Ngongang Ndjawa, Guy Olivier; Hoke, Eric T.; Salleo, Alberto; Thompson, Mark E.; McGehee, Michael D.; Amassian, Aram

    2013-01-01

    The effects of sterics and molecular orientation on the open-circuit voltage and absorbance properties of charge-transfer states are explored in model bilayer organic photovoltaics. It is shown that the open-circuit voltage correlates linearly with the charge-transfer state energy and is not significantly influenced by electronic coupling. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Re-evaluating the role of sterics and electronic coupling in determining the open-circuit voltage of organic solar cells

    KAUST Repository

    Graham, Kenneth

    2013-07-30

    The effects of sterics and molecular orientation on the open-circuit voltage and absorbance properties of charge-transfer states are explored in model bilayer organic photovoltaics. It is shown that the open-circuit voltage correlates linearly with the charge-transfer state energy and is not significantly influenced by electronic coupling. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Preschoolers' social and moral judgments of third-party helpers and hinderers align with infants' social evaluations.

    Science.gov (United States)

    Van de Vondervoort, Julia W; Hamlin, J Kiley

    2017-12-01

    Two experiments explored preschoolers' social preferences and moral judgments of prosocial and antisocial others. In Experiment 1, 3- to 5-year-olds (N=74) observed helping and hindering scenarios previously used to explore sociomoral evaluation in preverbal infants. Whereas 3-year-olds in Experiment 1 did not reliably distinguish between the helper and hinderer when reporting social preferences or moral judgments, both 4- and 5-year-olds preferred the helper, judged the helper to be "nicer" than the hinderer, selectively allocated punishment to the hinderer, and were able to justify their punishment allocations. A simplified procedure and the addition of comprehension questions in Experiment 2 (N=24) improved 3-year-olds' performance, suggestive that their performance in Experiment 1 was likely due to processing or memory difficulties rather than an inability to engage in explicit social and moral evaluation. These studies reveal that young children readily interpret helping and hindering scenarios as socially and morally relevant. Copyright © 2017 Elsevier Inc. All rights reserved.

  9. Modeling back-relaxation in ionic polymer metal composites: The role of steric effects and composite layers

    Science.gov (United States)

    Porfiri, Maurizio; Sharghi, Hesam; Zhang, Peng

    2018-01-01

    Ionic polymer metal composites (IPMCs) are a new class of active materials that are gaining traction as soft actuators in medical and industrial applications. IPMCs can undergo large deformations under modest voltage inputs, in dry and wet environments. Past studies have demonstrated that physical and geometric properties of all the IPMC constituents (ionomer, electrodes, and counterions) may all influence the time scales of the transient response and severity of the back-relaxation. In this study, we present a detailed mathematical model to investigate how the finite size of the counterions and the presence of metal particles in the vicinity of the electrodes modulate IPMC actuation. We build on previous work by our group on thermodynamically consistent modeling of IPMC mechanics and electrochemistry, which attributes IPMC actuation to the interplay between Maxwell stress and osmotic forces. To gain insight into the role of physical and geometric parameters, the resulting nonlinear partial differential equations are solved semianalytically using the method of matched asymptotic expansions, for the initial transient and the steady-state. A numerical solution in COMSOL Multiphysics® is developed to verify semianalytical findings and further explore IPMC actuation. Our model can successfully predict the entire response of IPMCs, from the initial bending toward the anode to the steady-state toward the cathode. We find that the steric effect can abolish the back-relaxation of IPMCs by restraining the counterions' concentration near the electrodes. We also find that increasing the thickness of the ionomer-metal composite layers may enhance IPMC actuation through increased osmotic forces and Maxwell stress.

  10. Steric congestion at, and proximity to, a ferrous center leads to hydration of α-nitrile substituents forming coordinated carboxamides.

    Science.gov (United States)

    Thallaj, Nasser K; Orain, Pierre-Yves; Thibon, Aurore; Sandroni, Martina; Welter, Richard; Mandon, Dominique

    2014-08-04

    The question of the conversion of nitrile groups into amides (nitrile hydration) by action of water in mild and eco-compatible conditions and in the presence of iron is addressed in this article. We come back to the only known example of hydration of a nitrile function into carboxamide by a ferrous [Fe(II)] center in particularly mild conditions and very efficiently and demonstrate that these unusual conditions result from the occurrence of steric stress at the reaction site and formation of a more stable end product. Two bis(cyano-substituted) (tris 2-pyridyl methyl amine) ligands have been prepared, and the structures of the corresponding FeCl2 complexes are reported, both in the solid state and in solution. These two ligands only differ by the position of the nitrile group on the tripod in the α and β position, respectively, with respect to the pyridine nitrogen. In any case, intramolecular coordination is impossible. Upon action of water, the nitrile groups are hydrated however only if they are located in the α position. The fact that the β-substituted β-(NC)2TPAFeCl2 complex is not water sensitive suggests that the reaction proceeds in an intramolecular way at the vicinity of the metal center. In the bis α-substituted α-(NC)2TPAFeCl2 complex, both functions are converted in a very clean fashion, pointing out that this complex exhibits ligand flexibility and is not deactivated after the first hydration. At a preparative scale, this reaction allows the one-pot conversion of the bis(cyano-substituted) tripod into a bis(amido-substituted) one in particularly mild conditions with a very good yield. Additionally, the XRD structure of a ferric compound in which the two carboxamido ligands are bound to the metal in a seven-coordinate environment is reported.

  11. Phospholipids chiral at phosphorus. Steric course of the reactions catalyzed by phosphatidylserine synthase from Escherichia coli and yeast

    International Nuclear Information System (INIS)

    Raetz, C.R.H.; Carman, G.M.; Dowhan, W.; Jiang, R.T.; Waszkuc, W.; Loffredo, W.; Tsai, M.D.

    1987-01-01

    The steric courses of the reactions catalyzed by phosphatidylserine (PS) synthase from Escherichia coli and yeast were elucidated by the following procedure. R/sub P/ and S/sub P/ isomers of 1,2-dipalmitoyl-sn-glycero-3-[ 17 O, 18 O]phosphoethanolamine ([ 17 O, 18 O]DPPE) were synthesized and converted to (R/sub P/)- and (S/sub P/)-1,2-dipalmitoyl-sn-glycero-3-[ 16 O, 17 O, 18 O]DPPA), respectively, by incubating with phospholipase D. Condensation of [ 16 O, 17 O, 18 O]DPPA with cytidine 5'-monophosphomorpholidate in pyridine gave the desired substrate for PS synthase, [ 17 O, 18 O]cytidine 5'-diphospho-1,2-dipalmitoyl-sn-glycerol ([ 17 O, 18 O]CDP-DPG), as a mixture of several isotopic and configurational isomers. Incubation of [ 17 O, 18 O]CDP-DPG), as a mixture of several isotopic and configurational isomers. Incubation of [ 17 O, 18 O] CDP-DPG with a mixture of L-serine, PS synthase and PS decarboxylase gave [ 17 O, 18 O]DPPE. The configuration and isotopic enrichments of the starting [ 17 O, 18 O]DPPE and the product were analyzed by 31 P NMR following trimethylsilylation of the DPPE. The results indicate that the reaction of E. coli PS synthase proceeds with retention of configuration at phosphorus, which suggests a two-step mechanism involving a phosphatidyl-enzyme intermediate, while the yeast PS synthase catalyzes the reaction with inversion of configuration, which suggests a single-displacement mechanism. Such results lend strong support to the ping-pong mechanism proposed for the E. coli enzyme and the sequential Bi-Bi mechanism proposed for the yeast enzyme, both based on previous isotopic exchange experiments

  12. Hinder för utomhusundervisning med fokus på årskurs 4-6

    OpenAIRE

    Petersson, Essi; Carstensen, Linnea

    2018-01-01

    I den här studien har vi tagit fram de hinder som begränsar möjligheterna för utomhusundervisning för elever i grundskolan, med fokus på årskurs 4-6 och middle school. Syftet med studien var att synliggöra vilka hinder som kan stå i vägen för utomhusundervisning samt visa på behov av vidare forskning i området. Forskningsfrågan som vi har försökt svara på är: Vad utgör hinder för utomhusundervisning med elever i grundskolan, med fokus på årskurs 4-6 och middle school? Studien bygger på den pr...

  13. Anomalous diffusion due to hindering by mobile obstacles undergoing Brownian motion or Orstein-Ulhenbeck processes.

    Science.gov (United States)

    Berry, Hugues; Chaté, Hugues

    2014-02-01

    In vivo measurements of the passive movements of biomolecules or vesicles in cells consistently report "anomalous diffusion," where mean-squared displacements scale as a power law of time with exponent αmovement hindrance by obstacles is often invoked. However, our understanding of how hindered diffusion leads to subdiffusion is based on diffusion amidst randomly located immobile obstacles. Here, we have used Monte Carlo simulations to investigate transient subdiffusion due to mobile obstacles with various modes of mobility. Our simulations confirm that the anomalous regimes rapidly disappear when the obstacles move by Brownian motion. By contrast, mobile obstacles with more confined displacements, e.g., Orstein-Ulhenbeck motion, are shown to preserve subdiffusive regimes. The mean-squared displacement of tracked protein displays convincing power laws with anomalous exponent α that varies with the density of Orstein-Ulhenbeck (OU) obstacles or the relaxation time scale of the OU process. In particular, some of the values we observed are significantly below the universal value predicted for immobile obstacles in two dimensions. Therefore, our results show that subdiffusion due to mobile obstacles with OU type of motion may account for the large variation range exhibited by experimental measurements in living cells and may explain that some experimental estimates are below the universal value predicted for immobile obstacles.

  14. Natural rubber/nitrile butadiene rubber/hindered phenol composites with high-damping properties

    Directory of Open Access Journals (Sweden)

    Xiuying Zhao

    2015-10-01

    Full Text Available New natural rubber (NR/nitrile butadiene rubber (NBR/hindered phenol (AO-80 composites with high-damping properties were prepared in this study. The morphological, structural, and mechanical properties were characterized by atomic force microscopy (AFM, polarized Fourier transform infrared spectrometer (FTIR, dynamic mechanical thermal analyzer (DMTA, and a tensile tester. Each composite consisted of two phases: the NR phase and the NBR/AO-80 phase. There was partial compatibility between the NR phase and the NBR/AO-80 phase, and the NR/NBR/AO-80 (50/50/20 composite exhibited a co-continuous morphology. Strain-induced crystallization occurred in the NR phase at strains higher than 200%, and strain-induced orientation appeared in the NBR/AO-80 phase with the increase of strain from 100% to 500%. The composites had a special stress–strain behavior and mechanical properties because of the simultaneous strain-induced orientation and strain-induced crystallization. In the working temperature range of a seismic isolation bearing, the composites (especially the NR/NBR/AO-80 (50/50/20 composite presented a high loss factor, high area of loss peak (TA, and high hysteresis energy. Therefore, the NR/NBR/AO-80 rubber composites are expected to have important application as a high-performance damping material for rubber bearing.

  15. Local characterization of hindered Brownian motion by using digital video microscopy and 3D particle tracking

    Energy Technology Data Exchange (ETDEWEB)

    Dettmer, Simon L.; Keyser, Ulrich F.; Pagliara, Stefano [Cavendish Laboratory, University of Cambridge, 19 J J Thomson Avenue, Cambridge CB3 0HE (United Kingdom)

    2014-02-15

    In this article we present methods for measuring hindered Brownian motion in the confinement of complex 3D geometries using digital video microscopy. Here we discuss essential features of automated 3D particle tracking as well as diffusion data analysis. By introducing local mean squared displacement-vs-time curves, we are able to simultaneously measure the spatial dependence of diffusion coefficients, tracking accuracies and drift velocities. Such local measurements allow a more detailed and appropriate description of strongly heterogeneous systems as opposed to global measurements. Finite size effects of the tracking region on measuring mean squared displacements are also discussed. The use of these methods was crucial for the measurement of the diffusive behavior of spherical polystyrene particles (505 nm diameter) in a microfluidic chip. The particles explored an array of parallel channels with different cross sections as well as the bulk reservoirs. For this experiment we present the measurement of local tracking accuracies in all three axial directions as well as the diffusivity parallel to the channel axis while we observed no significant flow but purely Brownian motion. Finally, the presented algorithm is suitable also for tracking of fluorescently labeled particles and particles driven by an external force, e.g., electrokinetic or dielectrophoretic forces.

  16. Water Sorption and Hindered Diffusion with Different Chain Stiffness of Superabsorbent Polymer

    Energy Technology Data Exchange (ETDEWEB)

    Chun, Myung-Suk; Lee, Dae-Young [Korea Institute of Science and Technology, Seoul (Korea, Republic of)

    2015-01-15

    Water sorption and diffusion are essential physicochemical properties of a high-performance superabsorbent polymer (SAP). We combine the Park model with the obstruction-scaling model and the water clustering in confined spaces of the polymer hydrogel. Special attention is focused on elucidating the effect of chain stiffness by considering the conformation of the polymer chain. Theoretical model parameters are determined from the best fits by simultaneous nonlinear regressions for both sorption and corrected diffusion data based on previous experiments with poly(acrylamide-co-sodium acrylate) hydrogel. Predictions show that the hindered water diffusivity leads to a sigmoid curve with relative humidity a{sub w}, where it increases monotonically up to aw{sub ≅} 0.6 due to the swelling but decreases at higher a{sub w} caused by water clustering. Water diffusion decreases with increasing chain stiffness, and the larger persistence length provides a smaller opening radius in void spaces regarding the weak elastic deformation of hydrogel under the applied stress.

  17. Observation/confirmation of hindered E2 strength in {sup 18}C/{sup 16}C

    Energy Technology Data Exchange (ETDEWEB)

    Ong, H.J. [Osaka University, RCNP, Ibaraki, Osaka (Japan); Imai, N. [KEK, Tsukuba, Ibaraki (Japan); Suzuki, D.; Iwasaki, H.; Onishi, T.K.; Suzuki, M.K.; Nakao, T.; Ichikawa, Y. [University of Tokyo, Department of Physics, Bunkyo,Tokyo (Japan); Sakurai, H.; Takeuchi, S.; Kondo, Y.; Aoi, N.; Baba, H.; Bishop, S.; Ishihara, M.; Kubo, T.; Motobayashi, T.; Yanagisawa, Y. [RIKEN, RIKEN Nishina Center, Wako, Saitama (Japan); Ota, S. [University of Tokyo, RIKEN Campus, CNS, Wako, Saitama (Japan); Togano, Y.; Kurita, K. [Rikkyo University, Department of Physics, Toshima, Tokyo (Japan); Nakamura, T.; Okumura, T. [Tokyo Institute of Technology, Department of Physics, Meguro, Tokyo (Japan)

    2009-12-15

    We have measured the lifetime of the first excited 2{sup +} state in {sup 18}C using an upgraded recoil shadow method to determine the electric quadrupole transition. The measured mean lifetime is 18.9{+-}0.9 (stat){+-}4.4 (syst) ps, corresponding to B(E2;2{sub 1} {sup +}{yields} 0{sup +} {sub gs}) = 4.3{+-}0.2{+-}1.0 e{sup 2}fm{sup 4}, or about 1.5 Weisskopf units. The mean lifetime of the first 2{sup +} state in {sup 16}C was remeasured to be 18.3{+-}1.4{+-}4.8 ps, about four times shorter than the value reported previously. The discrepancy is explained by incorporating the {gamma} -ray angular distribution obtained in this work into the previous measurement. The observed transition strengths in {sup 16,18}C are hindered compared to the empirical values, indicating that the anomalous E2 strength observed in {sup 16}C persists in {sup 18}C. (orig.)

  18. Doxorubicin hinders DNA condensation promoted by the protein bovine serum albumin (BSA).

    Science.gov (United States)

    Lima, C H M; de Paula, H M C; da Silva, L H M; Rocha, M S

    2017-12-01

    In this work, we have studied the interaction between the anticancer drug doxorubicin (doxo) and condensed DNA, using optical tweezers. To perform this task, we use the protein bovine serum albumin (BSA) in the working buffer to mimic two key conditions present in the real intracellular environment: the condensed state of the DNA and the abundant presence of charged macromolecules in the surrounding medium. In particular, we have found that, when doxo is previously intercalated in disperse DNA, the drug hinders the DNA condensation process upon the addition of BSA in the buffer. On the other hand, when bare DNA is firstly condensed by BSA, doxo is capable to intercalate and to unfold the DNA condensates at relatively high concentrations. In addition, a specific interaction between BSA and doxo was verified, which significantly changes the chemical equilibrium of the DNA-doxo interaction. Finally, the presence of BSA in the buffer stabilizes the double-helix structure of the DNA-doxo complexes, preventing partial DNA denaturation induced by the stretching forces. © 2017 Wiley Periodicals, Inc.

  19. The hyperturbid state of the water column in estuaries and rivers: the importance of hindered settling

    Science.gov (United States)

    Dijkstra, Yoeri M.; Schuttelaars, Henk M.; Winterwerp, Johan C.

    2018-03-01

    Over the last few decades, some estuaries have undergone a transition to a hyperturbid state, characterised by suspended sediment concentrations of several grammes per litre averaged over the water column. To improve our understanding of this transition and of naturally hyperturbid estuaries, we systematically identify the processes allowing for high suspended sediment concentrations using a water column (1DV) model. Under a range of realistic forcing conditions, the state of the water column can be characterised by one of two equilibrium states. The first is an erosion-limited state, in which there still is sediment available for erosion at the bed. We find that this state only occurs with relatively low concentrations. The second is a supply-limited state, in which all erodable sediment is in suspension. The concentration in this state depends entirely on the amount of sediment in the system and can potentially be very high. We identify the conditions under which the state of the water column can jump from a low to a high concentration and identify hysteresis in the transition between the two states. The mechanism responsible for this hysteresis is hindered settling. It thus follows that hyperturbidity is only possible in a supply-limited state. From this observation we derive a necessary condition for an estuarine system to make the transition from low turbidity to hyperturbidity in a 1DV context. This is an important step towards understanding why some estuaries are hyperturbid and assessing the risk that particular estuaries may become hyperturbid in the future.

  20. The Heisenberg-Weyl algebra on the circle and a related quantum mechanical model for hindered rotation.

    Science.gov (United States)

    Kouri, Donald J; Markovich, Thomas; Maxwell, Nicholas; Bodmann, Bernhard G

    2009-07-02

    We discuss a periodic variant of the Heisenberg-Weyl algebra, associated with the group of translations and modulations on the circle. Our study of uncertainty minimizers leads to a periodic version of canonical coherent states. Unlike the canonical, Cartesian case, there are states for which the uncertainty product associated with the generators of the algebra vanishes. Next, we explore the supersymmetric (SUSY) quantum mechanical setting for the uncertainty-minimizing states and interpret them as leading to a family of "hindered rotors". Finally, we present a standard quantum mechanical treatment of one of these hindered rotor systems, including numerically generated eigenstates and energies.

  1. NCEI ocean heat content, temperature anomalies, salinity anomalies, thermosteric sea level anomalies, halosteric sea level anomalies, and total steric sea level anomalies from 1955 to present calculated from in situ oceanographic subsurface profile data (NCEI Accession 0164586)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — This accession contains ocean heat content change, oceanic temperature and salinity changes, and steric sea level change (change in volume without change in mass),...

  2. Helping or hindering: the role of nurse managers in the transfer of practice development learning.

    Science.gov (United States)

    Currie, Kay; Tolson, Debbie; Booth, Jo

    2007-09-01

    This paper reports selected findings from a recent PhD study exploring how graduates from a BSc Specialist Nursing programme, with an NMC-approved Specialist Practitioner Qualification, engage in practice development during their subsequent careers. The UKCC (1998) defines specialist practice as requiring higher levels of judgement, discretion and decision-making, with leadership in clinical practice development forming a core dimension of this level of practice. However, there is little evidence in the published literature that describes or evaluates the practice development role of graduate specialist practitioners. This study applied a modified Glaserian approach to grounded theory methods. A preliminary descriptive survey questionnaire was posted to all graduates from the programme, response rate of 45% (n=102). From these respondents, theoretical sampling decisions directed the selection of 20 participants for interview, permitting data saturation. The grounded theory generated by this study discovered a basic social process labelled 'making a difference', whereby graduate specialist practitioners are increasingly able to impact in developing patient care at a strategic level by coming to own the identity of an expert practitioner (Currie, 2006). Contextual factors strongly influence the practitioner journey, with organizational position and other people presenting enabling or blocking conditions. The line manager plays a crucial role in helping or hindering graduate specialist practitioners to transfer their learning to the clinical setting and become active in practice development. Recommendations to enhance managerial support for the practice development role of graduate specialist practitioners are proposed. ADDING TO CURRENT KNOWLEDGE: This work adds to currently limited knowledge of the graduate specialist practitioners' role in the leadership of clinical practice development. In addition, the findings emphasize the potential influence of the workplace

  3. Decline of Phosphotransfer and Substrate Supply Metabolic Circuits Hinders ATP Cycling in Aging Myocardium.

    Directory of Open Access Journals (Sweden)

    Emirhan Nemutlu

    Full Text Available Integration of mitochondria with cytosolic ATP-consuming/ATP-sensing and substrate supply processes is critical for muscle bioenergetics and electrical activity. Whether age-dependent muscle weakness and increased electrical instability depends on perturbations in cellular energetic circuits is unknown. To define energetic remodeling of aged atrial myocardium we tracked dynamics of ATP synthesis-utilization, substrate supply, and phosphotransfer circuits through adenylate kinase (AK, creatine kinase (CK, and glycolytic/glycogenolytic pathways using 18O stable isotope-based phosphometabolomic technology. Samples of intact atrial myocardium from adult and aged rats were subjected to 18O-labeling procedure at resting basal state, and analyzed using the 18O-assisted HPLC-GC/MS technique. Characteristics for aging atria were lower inorganic phosphate Pi[18O], γ-ATP[18O], β-ADP[18O], and creatine phosphate CrP[18O] 18O-labeling rates indicating diminished ATP utilization-synthesis and AK and CK phosphotransfer fluxes. Shift in dynamics of glycolytic phosphotransfer was reflected in the diminished G6P[18O] turnover with relatively constant glycogenolytic flux or G1P[18O] 18O-labeling. Labeling of G3P[18O], an indicator of G3P-shuttle activity and substrate supply to mitochondria, was depressed in aged myocardium. Aged atrial myocardium displayed reduced incorporation of 18O into second (18O2, third (18O3, and fourth (18O4 positions of Pi[18O] and a lower Pi[18O]/γ-ATP[18 O]-labeling ratio, indicating delayed energetic communication and ATP cycling between mitochondria and cellular ATPases. Adrenergic stress alleviated diminished CK flux, AK catalyzed β-ATP turnover and energetic communication in aging atria. Thus, 18O-assisted phosphometabolomics uncovered simultaneous phosphotransfer through AK, CK, and glycolytic pathways and G3P substrate shuttle deficits hindering energetic communication and ATP cycling, which may underlie energetic

  4. Driving and hindering factors for rural electrification in developing countries: Lessons from Bangladesh

    International Nuclear Information System (INIS)

    Rahman, Md. Mizanur; Paatero, Jukka V.; Poudyal, Aditya; Lahdelma, Risto

    2013-01-01

    Rural electrification is essential for bringing about social and economic developments, but the progress is distressingly slow in most developing countries. The Bangladesh Rural Electrification Program (BREP) has been highlighted as a positive case among developing countries, but from 2006 onwards there have been doubts about the program's chances of success. In this paper, we examine the rural electrification practices in Bangladesh and evaluate the claim that, whereas they were successful up to 2005, they then began to decline in terms of their performance. This study determines the factors behind the initial success of the program as well as those that account for the recent downturn in BREP. We found that the BREP was a clear success in terms of its growth and progress; however, its performance has been declining since 2006. The key driving factors for the success of this program had to do with prioritizing system investment, community involvement, anti-corruption features, standardized practices and performance-based incentives while excluding political parties. The major issues accounting for the decline were the lack of organizational autonomy, a shortage of funding, unrealistic tariffs, and power supply shortages. Renewable-based, off-grid technologies have been successfully supplementing the on-grid program in remote areas. - Highlights: • Rural electrification is essential for bringing about socio-economic developments. • The pace of rural electrification in the developing countries has been very slow. • A multitude of issues plays behind in making the task a success or a failure. • Lack of policy reforms, unrealistic tariffs are the main hinderers. • Rural electrification cannot be successful by sticking to a rigid model

  5. What hinders the development of small businesses: the view of the Murmansk Oblast entrepreneurs

    Directory of Open Access Journals (Sweden)

    Tat’yana Igorevna Barasheva

    2014-07-01

    Full Text Available In recent years there has been a slowdown in the growth rate of Russia’s sector of small and medium entrepreneurship; this issue once again brings to the fore the search for new ways and mechanisms in the management of its subjects. A necessary condition for such a search consists in focusing on the problems that hinder the development of this sector and that can be revealed exclusively in the formation of valuable and accurate information – the collective views of its representatives. In this regard, the information base for the analysis was found in the results of several studies initiated by the all-Russian public organization “OPORA Rossii” (Moscow, its regional branch in Murmansk and the Northern Chamber of Commerce and Industry; the results were obtained in the course of the questionnaire survey, which was conducted among entrepreneurs with the purpose of revealing their assessment of the terms of doing business. The generalization of the research results and information obtained by the author in cooperation with representatives of small business and workers of the Prosecutor’s Office has identified the main problems, their causes and consequences of their impact on the activity of the Murmansk Oblast business sector. In the opinion of a significant part of businessmen, such factor as business climate plays a decisive role in the creation and development of the sector in the region. Despite the complexity of the situation, entrepreneurs do not lose hope of solving their problems and see the solution to the problem in efficient work of the regional and municipal authorities. The author’s conclusions may become a reference point for further reforms in the sphere of management of small enterprises in the Murmansk Oblast

  6. Rehydrated sterically stabilized phospholipid nanomicelles of budesonide for nebulization: physicochemical characterization and in vitro, in vivo evaluations

    Directory of Open Access Journals (Sweden)

    Sahib MN

    2011-10-01

    Full Text Available Mohanad Naji Sahib, Yusrida Darwis, Kok Khiang Peh, Shaymaa Abdalwahed Abdulameer, Yvonne Tze Fung TanSchool of Pharmaceutical Sciences, Universiti Sains Malaysia, Penang, MalaysiaBackground: Inhaled corticosteroids provide unique systems for local treatment of asthma or chronic obstructive pulmonary disease. However, the use of poorly soluble drugs for nebulization has been inadequate, and many patients rely on large doses to achieve optimal control of their disease. Theoretically, nanotechnology with a sustained-release formulation may provide a favorable therapeutic index. The aim of this study was to determine the feasibility of using sterically stabilized phospholipid nanomicelles of budesonide for pulmonary delivery via nebulization.Methods: PEG5000-DSPE polymeric micelles containing budesonide (BUD-SSMs were prepared by the coprecipitation and reconstitution method, and the physicochemical and pharmacodynamic characteristics of BUD-SSMs were investigated.Results: The optimal concentration of solubilized budesonide at 5 mM PEG5000-DSPE was 605.71 ± 6.38 µg/mL, with a single-sized peak population determined by photon correlation spectroscopy and a particle size distribution of 21.51 ± 1.5 nm. The zeta potential of BUD-SSMs was -28.43 ± 1.98 mV. The percent entrapment efficiency, percent yield, and percent drug loading of the lyophilized formulations were 100.13% ± 1.09%, 97.98% ± 1.95%, and 2.01% ± 0.02%, respectively. Budesonide was found to be amorphous by differential scanning calorimetry, and had no chemical interaction with PEGylated polymer according to Fourier transform infrared spectroscopy. Transmission electron microscopic images of BUD-SSMs revealed spherical nanoparticles. BUD-SSMs exhibited prolonged dissolution behavior compared with Pulmicort Respules® (P , 0.05. Aerodynamic characteristics indicated significantly higher deposition in the lungs compared with Pulmicort Respules®. The mass median aerodynamic, geometric

  7. Professionals' Perspectives on Organizational Factors that Support or Hinder the Successful Implementation of Family-Centered Practice

    Science.gov (United States)

    Wright, Alexandra; Hiebert-Murphy, Diane; Trute, Barry

    2010-01-01

    This article presents findings from an exploratory, qualitative study whose objective was to identify professionals' perceptions of organizational factors that support or hinder the implementation of family-centered practice (FCP). Two disability services organizations in Manitoba, Canada, were selected as the research sites. In 2002, all staff…

  8. How Perspective-Taking Helps and Hinders Group-Based Guilt as a Function of Group Identification

    NARCIS (Netherlands)

    Zebel, Sven; Doosje, Bertjan; Spears, Russell

    In two studies we hypothesized that outgroup perspective-taking promotes group-based guilt among weakly identified perpetrator group members, but hinders it among higher identifiers. In Study 1, native Dutch participants (N = 153) confronted their group's past mistreatment of outgroups, while

  9. Steric asymmetry and lambda-doublet propensities in state-to-state rotationally inelastic scattering of NO(2 π/2) with He

    International Nuclear Information System (INIS)

    Wiskerke, Arjan E.; de Lange, Marc J.L.; Stolte, Steven; Taatjes, Craig A.; van der Avoird, Ad; Klos, Jacek

    2004-01-01

    Relative integrated cross sections are measured for rotationally inelastic scattering of NO( 2 π 1/2 ), hexapole selected in the upper Λ-doublet level of the ground rotational state (j = 0.5), in collisions with He at a nominal energy of 514 cm -1 . Application of a static electric field E in the scattering region, directed parallel or antiparallel to the relative velocity vector v, allows the state-selected NO molecule to be oriented with either the N end or the O end towards the incoming He atom. Laser-induced fluorescence detection of the final state of the NO molecule is used to determine the experimental steric asymmetry, SA (triple b ond) (σ v ↑↓ E -σ v ↑↑ E )/(σ v ↑↓ E + σ v ↑↑ E ), which is equal to within a factor of (-1) to the molecular steric effect, S i # yields# f (triple b ond) (σ He # yields# NO - σ He # yields# ON )/(σ He # yields# NO + σ He # yields# ON ). The dependence of the integral inelastic cross section on the incoming λ-doublet component is also observed as a function of the final rotational (j(prime)), spin-orbit ((Omega)(prime)), and Λ-doublet (ε(prime)) state. The measured steric asymmetries are significantly larger than previously observed for NO-Ar scattering, supporting earlier proposals that the repulsive part of the interaction potential is responsible for the steric asymmetry. In contrast to the case of scattering with Ar, the steric asymmetry of NO-He collisions is not very sensitive to the value of (Omega)(prime) . However, the Λ-doublet propensities are very different for ((Omega) = 0.5(F 1 ) → (Omega)(prime) = 0.5(F 1 )) transitions. Spin-orbit manifold conserving collisions exhibit a propensity for parity conservation at low Δ j , but spin-orbit manifold changing collisions do not show this propensity. In conjunction with the experiments, state-to-state cross sections for scattering of oriented NO( 2 π) molecules with He atoms are predicted from close-coupling calculations on restricted

  10. On the nature of the electronic effect of multiple hydroxyl groups in the 6-membered ring - the effects are additive but steric hindrance plays a role too

    DEFF Research Database (Denmark)

    Pedersen, Christian Marcus; Bols, Mikael

    2017-01-01

    Research during the last two decades has shown a remarkable directional component of the substituent effects of hydroxy groups, which has a profound effect on the properties of hydroxylated compounds such as carbohydrates. While the epimerisation of a single hydroxyl function is well studied...... synthesized and their pKa and conformation were studied. The results show that the large difference in the electronic effect between the axial and equatorial hydroxyls is partially cancelled by counteracting steric hindrance from 1,3-diaxial interactions. Hydrogen bonding does not appear to play any role...

  11. Steric control of redox events in organo-uranium chemistry: synthesis and characterisation of U(V) oxo and nitrido complexes

    OpenAIRE

    Tsoureas, Nikolaos; Kilpatrick, Alexander; Inman, Christopher; Cloke, Frederick Geoffrey

    2016-01-01

    The synthesis and molecular structures of a U(V) neutral terminal oxo complex and a U(V) sodium uranium nitride contact ion pair are described. The synthesis of the former is achieved by the use of tBuNCO as a mild oxygen transfer reagent, whilst that of the latter is via the reduction of NaN3. Both mono-uranium complexes are stabilised by the presence of bulky silyl substituents on the ligand framework that facilitate a 2e- oxidation of a single U(III) centre. In contrast, when steric hindra...

  12. A numerical investigation of fine sediment resuspension in the wave boundary layer - effect of hindered settling and bedforms

    Science.gov (United States)

    Hsu, T. J.; Cheng, Z.; Yu, X.

    2016-02-01

    The wave bottom boundary layer is a major conduit delivering fine terrestrial sediments to the continental margin. Hence, studying the fine sediment resuspension in the wave boundary layer is crucial to the understanding of various components of the earth system, such as carbon cycle. By assuming the settling velocity to be a constant in each simulation, previous turbulence-resolving numerical simulations reveal the existence of three transport modes in the wave boundary layer associated with the sediment availability. As the sediment availability and hence the sediment-induced stable stratification increase, a sequence of transport modes, namely, (I) well-mixed transport, (II) formulation of lutocline resembling a two-layer system, and (III) completely laminarized transport are observed. In general, the settling velocity is a flow variable due to the floc dynamics and hindered settling. This study further investigate the effect of hindered settling. Particularly, for flocs with lower gelling concentrations, the hindered settling effect can play a key role in sustaining large amount of suspended sediment load and results in the laminarized transport (III). For the simulation with a very significant hindered settling effect due to a low gelling concentration, results also indicate the occurrence of gelling ignition, a state in which the erosion rate is always higher than the deposition rate. A condition for the occurrence of gelling ignition is proposed for a range of wave intensities as a function of sediment/floc properties and erodibility parameters. These aforementioned studies are limited to fine sediment transport over a flat bed. However, recent field and laboratory observation show that a small amount of sand fraction can lead to the formation of small bedforms, which can armor the bed while in the meantime enhance near bed turbulence. Preliminary investigation on the effect of bedforms on the resulting transport modes will also be presented.

  13. Diazo Reagents with Small Steric Footprints for Simultaneous Arming/SAR Studies of Alcohol-Containing Natural Products via O–H Insertion

    Science.gov (United States)

    Chamni, Supakarn; He, Qing-Li; Dang, Yongjun; Bhat, Shridhar; Liu, Jun O.; Romo, Daniel

    2011-01-01

    Natural products are essential tools for basic cellular studies leading to the identification of medically relevant protein targets and the discovery of potential therapeutic leads. The development of methods that enable mild and selective derivatization of natural products continues to be of significant interest for mining their information-rich content. Herein, we describe novel diazo reagents for simultaneous arming and structure-activity relationship (SAR) studies of alcohol-containing natural products with a small steric footprint, namely an α-trifluoroethyl (HTFB) substituted reagent. The Rh(II)-catalyzed O–H insertion reaction of several natural products, including the potent translation inhibitor lactimidomycin, was investigated and useful reactivity and both chemo- and site (chemosite) selectivities were observed. Differential binding to the known protein targets of both FK506 and fumagillol was demonstrated, validating the advantage of the smaller steric footprint of trifluoroethyl derivatives. A p-azidophenyl diazo reagent is also described that will prove useful for photoaffinity labeling of low affinity small molecule protein receptors. PMID:21894934

  14. Quinoidal Oligo(9,10-anthryl)s with Chain-Length-Dependent Ground States: A Balance between Aromatic Stabilization and Steric Strain Release

    KAUST Repository

    Lim, Zhenglong

    2015-11-12

    Quinoidal π-conjugated polycyclic hydrocarbons have attracted intensive research interest due to their unique optical/electronic properties and possible magnetic activity, which arises from a thermally excited triplet state. However, there is still lack of fundamental understanding on the factors that determine the electronic ground states. Herein, by using quinoidal oligo(9,10-anthryl)s, it is demonstrated that both aromatic stabilisation and steric strain release play balanced roles in determining the ground states. Oligomers with up to four anthryl units were synthesised and their ground states were investigated by electronic absorption and electron spin resonance (ESR) spectroscopy, assisted by density functional theory (DFT) calculations. The quinoidal 9,10-anthryl dimer 1 has a closed-shell ground state, whereas the tri- (2) and tetramers (3) both have an open-shell diradical ground state with a small singlet-triplet gap. Such a difference results from competition between two driving forces: the large steric repulsion between the anthryl/phenyl units in the closed-shell quinoidal form that drives the molecule to a flexible open-shell diradical structure, and aromatic stabilisation due to the gain of more aromatic sextet rings in the closed-shell form, which drives the molecule towards a contorted quinoidal structure. The ground states of these oligomers thus depend on the overall balance between these two driving forces and show chain-length dependence. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Sterically Bulky NHC Adducts of GaMe3 and InMe3 for H2 Activation and Lactide Polymerization

    Directory of Open Access Journals (Sweden)

    Anaëlle Bolley

    2018-01-01

    Full Text Available The sterically bulky Ga(III and In(III (IPr*MMe3 adducts (1 and 2 and (SItBuMMe3 adducts (3 and 4 (M = Ga, In; IPr* = 1,3-bis{2,6-bis(diphenylmethyl-4-methylphenyl}-1,3-dihydro- imidazol-2-ylidene; SItBu = 1,3-bis(1,1-dimethylethyl-imidazolidin-2-ylidene were prepared and structurally characterized, allowing an estimation of the steric hindrance of such Lewis pairs (yields in 1–4: 92%, 90%, 73%, and 42%, respectively. While the IPr* adducts 1 and 2 are robust species, the more severely congested SItBu adducts 3 and 4 are more reactive and exhibit a limited stability in solution. Adduct (SItBuGaMe3 (3 reacts quickly with H2 at room temperature to afford the corresponding aminal product, 1,3-di-tert-butylimidazolidine (5, along with free GaMe3. Such Frustrated Lewis Pair (FLP reactivity constitutes the first instance of a H2 activation involving a simple trialkyl GaR3 species. Adduct 3 also mediates the ring-opening polymerization (ROP of rac-lactide at room temperature to afford cyclic polylactide (PLA.

  16. Understanding the Steric Height Long Term Variability at the Bermuda Atlantic Time-Series Study (BATS) Site with a Neutral Density Approach

    Science.gov (United States)

    Goncalves Neto, A.; Johnson, R. J.; Bates, N. R.

    2016-02-01

    Rising sea level is one of the main concerns for human life in a scenario with global atmosphere and ocean warming, which is of particular concern for oceanic islands. Bermuda, located in the center of the Sargasso Sea, provides an ideal location to investigate sea level rise since it has a long term tide gauge (1933-present) and is in close proximity to deep ocean time-series sites, namely, Hydrostation `S' (1954-present) and the Bermuda Atlantic Time-Series Study site (1988-present). In this study, we use the monthly CTD deep casts at BATS to compute the contribution of steric height (SH) to the local sea surface height (SSH) for the past 24 years. To determine the relative contribution from the various water masses we first define 8 layers (Surface Layer, Upper Thermocline, Subtropical Mode-Water, Lower Thermocline, Antarctic Intermediate Water, Labrador Sea Water, Iceland-Scotland Overflow Water, Denmark Strait Overflow Water) based on neutral density criteria for which SH is computed. Additionally, we calculate the thermosteric and halosteric components for each of the defined neutral density layers. Surprisingly, the results show that, despite a 3.3mm/yr sea level rise observed at the Bermuda tide gauge, the steric contribution to the SSH at BATS has decreased at a rate of -1.1mm/yr during the same period. The thermal component is found to account for the negative trend in the steric height (-4.4mm/yr), whereas the halosteric component (3.3mm/yr) partially compensates the thermal signal and can be explained by an overall cooling and freshening at the BATS site. Although the surface layer and the upper thermocline waters are warming, all the subtropical and polar water masses, which represent most of the local water column, are cooling and therefore drive the overall SH contribution to the local SSH. Hence, it suggests that the mass contribution to the local SSH plays an important role in the sea level rise, for which we investigate with GRACE data.

  17. Atropisomerism about aryl-Csp(3) bonds: the electronic and steric influence of ortho-substituents on conformational exchange in cannabidiol and linderatin derivatives.

    Science.gov (United States)

    Berber, Hatice; Lameiras, Pedro; Denhez, Clément; Antheaume, Cyril; Clayden, Jonathan

    2014-07-03

    Terpenylation reactions of substituted phenols were used to prepare cannabidiol and linderatin derivatives, and their structure and conformational behavior in solution were investigated by NMR and, for some representative examples, by DFT. VT-NMR spectra and DFT calculations were used to determine the activation energies of the conformational change arising from restricted rotation about the aryl-Csp(3) bond that lead to two unequally populated rotameric epimers. The NBO calculation was applied to explain the electronic stabilization of one conformer over another by donor-acceptor charge transfer interactions. Conformational control arises from a combination of stereoelectronic and steric effects between substituents in close contact with each other on the two rings of the endocyclic epoxide atropisomers. This study represents the first exploration of the stereoelectronic origins of atropisomerism around C(sp(2))-C(sp(3)) single bonds through theoretical calculations.

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

    KAUST Repository

    Poater, Albert

    2013-07-01

    The reactivity of a new family of complexes with general formula [Ru IV(T)(R-D)(O)]2+ (T = trispyrazolylmethane (tpm); D = N-(1-hydroxy-3-methylbutan-(2S)-(-)-2-yl)-(4S)-(-)-4-isopropyl-4, 5-dihydrooxazole-2-carbimidate, R = Bz (1); iPr (2)) has been analyzed. There is a significant difference in regioselectivity between the two catalysts in the epoxidation of 4-vinylcyclohexene; 1 leads to the regioselective oxidation at the ring alkene position, whereas 2 leads to the oxidation at the terminal position. Although computational calculations indicate small energy differences, both the geometry through steric maps and the electronic parameters of the reactants via conceptual DFT, or charges via NPA, explain the reactivity differences found for the catalysts depending on the substituents of the oxazoline ligands. © 2013 Elsevier B.V. All rights reserved.

  19. Climate change under a scenario near 1.5 °C of global warming: monsoon intensification, ocean warming and steric sea level rise

    Directory of Open Access Journals (Sweden)

    J. Schewe

    2011-03-01

    Full Text Available We present climatic consequences of the Representative Concentration Pathways (RCPs using the coupled climate model CLIMBER-3α, which contains a statistical-dynamical atmosphere and a three-dimensional ocean model. We compare those with emulations of 19 state-of-the-art atmosphere-ocean general circulation models (AOGCM using MAGICC6. The RCPs are designed as standard scenarios for the forthcoming IPCC Fifth Assessment Report to span the full range of future greenhouse gas (GHG concentrations pathways currently discussed. The lowest of the RCP scenarios, RCP3-PD, is projected in CLIMBER-3α to imply a maximal warming by the middle of the 21st century slightly above 1.5 °C and a slow decline of temperatures thereafter, approaching today's level by 2500. We identify two mechanisms that slow down global cooling after GHG concentrations peak: The known inertia induced by mixing-related oceanic heat uptake; and a change in oceanic convection that enhances ocean heat loss in high latitudes, reducing the surface cooling rate by almost 50%. Steric sea level rise under the RCP3-PD scenario continues for 200 years after the peak in surface air temperatures, stabilizing around 2250 at 30 cm. This contrasts with around 1.3 m of steric sea level rise by 2250, and 2 m by 2500, under the highest scenario, RCP8.5. Maximum oceanic warming at intermediate depth (300–800 m is found to exceed that of the sea surface by the second half of the 21st century under RCP3-PD. This intermediate-depth warming persists for centuries even after surface temperatures have returned to present-day values, with potential consequences for marine ecosystems, oceanic methane hydrates, and ice-shelf stability. Due to an enhanced land-ocean temperature contrast, all scenarios yield an intensification of monsoon rainfall under global warming.

  20. Understanding what helps or hinders asthma action plan use: a systematic review and synthesis of the qualitative literature.

    Science.gov (United States)

    Ring, Nicola; Jepson, Ruth; Hoskins, Gaylor; Wilson, Caroline; Pinnock, Hilary; Sheikh, Aziz; Wyke, Sally

    2011-11-01

    To understand better what helps and/or hinders asthma action plan use from the professionals and patients/carers perspective. Systematic review and qualitative synthesis (using meta-ethnography). Nineteen studies (20 papers) were included in an analysis of patients/carers' and professionals' views. Seven main influences on action plan implementation were identified including perceived un-helpfulness and irrelevance of the plans. Translation and synthesis of the original authors' interpretations suggested that action plan promotion and use was influenced by professional and patient/carers' asthma beliefs and attitudes and patient/carer experiences of managing asthma. Action plan use is hindered because professionals and patients/carers have different explanatory models of asthma, its management and their respective roles in the management process. Patients/carers, based on their experiential knowledge of their condition, perceive themselves as capable, effective in managing their asthma, but health professionals do not always share this view. Professionally provided medically focused action plans that do not 'fit' with and incorporate the patients'/carers' views of asthma, and their management strategies, will continue to be under-utilised. Professionals need to develop a more patient-centred, partnership-based, approach to the joint development and review of action plans, recognising the experiential asthma knowledge of patients/carers. Copyright © 2011 Elsevier Ireland Ltd. All rights reserved.

  1. Factors that hinder community participation in developing and implementing comprehensive council health plans in Manyoni District, Tanzania

    Directory of Open Access Journals (Sweden)

    Emmanuel G. Kilewo

    2015-06-01

    Full Text Available Background: Decentralization of public health planning is proposed to facilitate public participation in health issues. Health Sector Reform in Tanzania places emphasis on the participation of lower level health facilities and community in health planning process. Despite availability of policies, guidelines, and community representative organs, actual implementation of decentralization strategies is poorly achieved. This study intended to find out factors that hinder community participation in developing and implementing Comprehensive Council Health Plan (CCHP. Materials and methods: A qualitative approach was conducted in this study with key informants from Health Facility Governing Committees (HFGC, Council Health Service Board (CHSB, and Council Health Management Team (CHMT. Data were collected using in-depth interviews. Data generated were analyzed for themes and patterns. Results: Factors that hindered community participation included lack of awareness on the CCHP among HFGC members, poor communication and information sharing between CHMT and HFGC, unstipulated roles and responsibilities of HFGC, lack of management capacity among HFGC members, and lack of financial resources for implementing HFGC activities. Conclusions: The identified challenges call for policy makers to revisit the decentralization by devolution policy by ensuring that local governance structures have adequate resources as well as autonomy to participate in planning and managing CCHP in general and health facility plans in particular.

  2. Hindering factors and suggestions related to organ donation decisions: perspective of the Taiwan Ali-Shan Tsou aboriginal tribe.

    Science.gov (United States)

    Chen, A N; Chen, K F; Chang, P C; Shih, F Jong; Chen, C R; Shih, F-Jin; Huang, C-Y

    2014-05-01

    Ali-San Tsou (AST) is one of leading aboriginal tribes in Taiwan with traditional godly beliefs related to life and death. Lacking related knowledge, health professionals (HPs) often failed to help them reach good dying or organ donation (OD). This study aimed to explore hindering factors and suggestions related to OD for good dying from Taiwan AST's own perspective. An explorative qualitative design was employed using a purposive sample of the AST tribes from Taiwan. Data were collected with AST residents by face-to-face interviews and analyzed by content analysis. Thirty AST residents (16 females and 14 males) with ages ranging from 28 to 78 (mean, 54.5) years completed interviews. Of them, 85% reported various diseases. In this study 73% were Catholics and Christians, 17% held traditional godly believes, and 10% had no religious affiliation. Eight hindering factors were reported: (1) limited information about organs and OD; (2) no qualified organs for donation; (3) worry about lack of forgiveness by ancestors; (4) tribe elders who might not accept concept of OD; (5) intact bodies were required at home during spirit-companion rituals; (6) earth burial with intact bodies was preferred; (7) bodies due to accidental and bad death were impermissible for OD; and (8) worry about possession by the donor's spirit. Seven suggestions were also reported for HPs to enhance AST's OD decisions: (1) starting with friendship and a caring relationship; (2) providing spiritual support from reverent religions; (3) stressing good deeds and honoring tribe folks by OD; (4) avoiding accidental/bad death; (5) providing relevant modern medical knowledge of human organs and OD; (6) introducing OD as part of a good-dying care plan; and (7) demonstrating a respectful discussion mindset about OD. Eight hindering factors and 7 types of suggestions for enhancing AST aboriginal people's OD decisions were first explored in this project. In the future, HPs are encouraged to invite AST to share

  3. Dependency links can hinder the evolution of cooperation in the prisoner's dilemma game on lattices and networks.

    Directory of Open Access Journals (Sweden)

    Xuwen Wang

    Full Text Available Networks with dependency links are more vulnerable when facing the attacks. Recent research also has demonstrated that the interdependent groups support the spreading of cooperation. We study the prisoner's dilemma games on spatial networks with dependency links, in which a fraction of individual pairs is selected to depend on each other. The dependency individuals can gain an extra payoff whose value is between the payoff of mutual cooperation and the value of temptation to defect. Thus, this mechanism reflects that the dependency relation is stronger than the relation of ordinary mutual cooperation, but it is not large enough to cause the defection of the dependency pair. We show that the dependence of individuals hinders, promotes and never affects the cooperation on regular ring networks, square lattice, random and scale-free networks, respectively. The results for the square lattice and regular ring networks are demonstrated by the pair approximation.

  4. What community characteristics help or hinder rural communities in becoming age-friendly? Perspectives from a Canadian prairie province.

    Science.gov (United States)

    Spina, John; Menec, Verena H

    2015-06-01

    Age-friendly initiatives are increasingly promoted as a policy solution to healthy aging, The primary objective of this article was to examine older adults' and key stakeholders' perceptions of the factors that either help or hinder a community from becoming age-friendly in the context of rural Manitoba, a Canadian prairie province. Twenty-four older adults and 17 key informants completed a qualitative interview. The findings show that contextual factors including size, location, demographic composition, ability to secure investments, and leadership influence rural communities' ability to become age-friendly. Government must consider the challenges these communities face in becoming more age-friendly and develop strategies to support communities. © The Author(s) 2013.

  5. Effect of montmorillonite on carboxylated styrene butadiene rubber/hindered phenol damping material with improved extraction resistance

    International Nuclear Information System (INIS)

    Gao, Yuan; Wang, Xiaoping; Liu, Meijun; Xi, Xue; Zhang, Xin; Jia, Demin

    2014-01-01

    Highlights: • MMT and XSBR display synergic effect on protecting HP1098 from being extracted. • A new hindered phenol HP1098 was used to prepare damping material. • Effects of three preparation methods on the material properties were studied. - Abstract: Three methods of blending, including direct blending, melt blending and latex blending, were introduced to disperse sodium based montmorillonite (Na-MMT) and N,N′-hexane-1,6-diylbis{3-(5-di-tert-butyl-4-hydroxyphenyl-propionamide)} (HP1098) into the carboxylated styrene butadiene (XSBR) matrix. Small angle X-ray Diffraction testing indicated that melting Na-MMT with HP1098 enlarged the d-spacing of Na-MMT, which was further enlarged by mechanical blending with XSBR, and this led to homogeneous dispersion of Na-MMT and HP1098, which was indicated by Transmission Electronic Microscopy; latex blending was found most advantageous in dispersing HP1098 which was essential for improved damping performance. Dynamic Mechanical Analysis was utilized to characterize damping properties, and enhanced static mechanical properties were presumably originated from molecule chains being intercalated into the enlarged galleries of Na-MMT by mechanical blending. Formation of hydrogen bonds was observed by Fourier Transformation Infrared Spectrum and was supposed to be responsible for exceptional damping performance at elevated temperature. Extraction measurement of XSBR/Na-MMT/HP1098 composite indicated that XSBR and Na-MMT showed synergic effect in protecting HP1098 molecules from being extracted, which is a promising method in preparing rubber/hindered phenol damping materials with improved extraction resistance, whereby increasing the performance stability and lifespan of the composite materials. Additional advantage of this type of materials is better processability and shortened vulcanization process

  6. When Trauma Hinders Learning

    Science.gov (United States)

    Barr, Donald A.

    2018-01-01

    Many kindergarten teachers have encountered children who enter school lacking the ability to control their behavior, but they may not understand the social and biological processes behind these children's disruptive behavior. The author reviews research into early childhood brain development to explain how trauma and chronic stress can make it…

  7. Mechanochemical Preparation of Stable Sub-100 nm γ-Cyclodextrin:Buckminsterfullerene (C60) Nanoparticles by Electrostatic or Steric Stabilization.

    Science.gov (United States)

    Van Guyse, Joachim F R; de la Rosa, Victor R; Hoogenboom, Richard

    2018-02-21

    Buckminster fullerene (C 60 )'s main hurdle to enter the field of biomedicine is its low bioavailability, which results from its extremely low water solubility. A well-known approach to increase the water solubility of C 60 is by complexation with γ-cyclodextrins. However, the formed complexes are not stable in time as they rapidly aggregate and eventually precipitate due to attractive intermolecular forces, a common problem in inclusion complexes of cyclodextrins. In this study we attempt to overcome the attractive intermolecular forces between the complexes by designing custom γ-cyclodextrin (γCD)-based supramolecular hosts for C 60 that inhibit the aggregation found in native γCD-C 60 complexes. The approach entails the introduction of either repulsive electrostatic forces or increased steric hindrance to prevent aggregation, thus enhancing the biomedical application potential of C 60 . These modifications have led to new sub-100 nm nanostructures that show long-term stability in solution. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Diffusion of ionic and non-ionic contrast agents in articular cartilage with increased cross-linking--contribution of steric and electrostatic effects.

    Science.gov (United States)

    Kulmala, K A M; Karjalainen, H M; Kokkonen, H T; Tiitu, V; Kovanen, V; Lammi, M J; Jurvelin, J S; Korhonen, R K; Töyräs, J

    2013-10-01

    To investigate the effect of threose-induced collagen cross-linking on diffusion of ionic and non-ionic contrast agents in articular cartilage. Osteochondral plugs (Ø=6mm) were prepared from bovine patellae and divided into two groups according to the contrast agent to be used in contrast enhanced computed tomography (CECT) imaging: (I) anionic ioxaglate and (II) non-ionic iodixanol. The groups I and II contained 7 and 6 sample pairs, respectively. One of the paired samples served as a reference while the other was treated with threose to induce collagen cross-linking. The equilibrium partitioning of the contrast agents was imaged after 24h of immersion. Fixed charge density (FCD), water content, contents of proteoglycans, total collagen, hydroxylysyl pyridinoline (HP), lysyl pyridinoline (LP) and pentosidine (Pent) cross-links were determined as a reference. The equilibrium partitioning of ioxaglate (group I) was significantly (p=0.018) lower (-23.4%) in threose-treated than control samples while the equilibrium partitioning of iodixanol (group II) was unaffected by the threose-treatment. FCD in the middle and deep zones of the cartilage (pionic iodixanol showed no changes in partition after cross-linking, in contrast to anionic ioxaglate, we conclude that the cross-linking induced changes in charge distribution have greater effect on diffusion compared to the cross-linking induced changes in steric hindrance. Copyright © 2013 IPEM. Published by Elsevier Ltd. All rights reserved.

  9. Autoregulation of transcription of the hupA gene in Escherichia coli: evidence for steric hindrance of the functional promoter domains induced by HU.

    Science.gov (United States)

    Kohno, K; Yasuzawa, K; Hirose, M; Kano, Y; Goshima, N; Tanaka, H; Imamoto, F

    1994-06-01

    The molecular mechanism of autoregulation of expression of the hupA gene in Escherichia coli was examined. The promoter of the gene contains a palindromic sequence with the potential to form a cruciform DNA structure in which the -35 sequence lies at the base of the stem and the -10 sequence forms a single-stranded loop. An artificial promoter lacking the palindrome, which was constructed by replacing a 10 nucleotide repeat for the predicted cruciform arm by a sequence in the opposite orientation, was not subject to HU-repression. DNA relaxation induced by deleting HU proteins and/or inhibiting DNA gyrase in cells results in increased expression from the hupA promoter. We propose that initiation of transcription of the hupA gene is negatively regulated by steric hindrance of the functional promoter domains for formation of the cruciform configuration, which is facilitated at least in part by negative supercoiling of the hupA promoter DNA region. The promoter region of the hupB gene also contains a palindromic sequence that can assume a cruciform configuration. Negative regulation of this gene by HU proteins may occur by a mechanism similar to that operating for the hupA gene.

  10. What factors hinder the decision-making process for women with cancer and contemplating fertility preservation treatment?

    Science.gov (United States)

    Jones, Georgina; Hughes, Jane; Mahmoodi, Neda; Smith, Emily; Skull, Jonathan; Ledger, William

    2017-07-01

    Although fertility preservation (FP) treatment options have increased, the existing evidence suggests that many women with cancer do not feel well supported in making these decisions, but find them stressful and complex and fail to take up fertility care at this crucial time. Whilst existing reviews have all made important contributions to our understanding of the FP decision-making process, none of them examine solely and specifically these processes for women of reproductive age with a diagnosis of any cancer, leaving a gap in the knowledge base. Given the expectation that care is patient-centred, our review aims to address this gap which may be of help to those managing patients struggling to make difficult decisions in the often brief period before potentially sterilizing cancer treatment is started. Underpinning this narrative review was the question 'What factors hinder the decision-making process for women with any cancer and contemplating FP treatment?' Our objectives were to (i) assess and summarize this existing literature, (ii) identify the factors that hinder this decision-making process, (iii) explore to what extent these factors may differ for women choosing different methods of FP and (iv) make recommendations for service delivery and future research. A systematic search of the medical and social science literature from the 1 January 2005 up to the end of January 2016 was carried out using three electronic databases (Web of Science (PubMed), Ovid SP Medline and CINAHL via Ebsco). Included in the review were quantitative, qualitative and mixed-method studies. Reference lists of relevant papers were also hand searched. From the 983 papers identified, 46 papers were included. Quality assessment was undertaken using the Mixed Methods Appraisal Tool and thematic analysis was used to analyse the data. From the analysis, 6 key themes with 15 sub-themes emerged: (i) fertility information provision (lack of information, timing of the information, patient

  11. What hinders teachers in using computer and video games in the classroom? Exploring factors inhibiting the uptake of computer and video games.

    Science.gov (United States)

    Baek, Young Kyun

    2008-12-01

    The purpose of this study is to identify factors inhibiting teachers' use of computer and video games in the classroom setting and to examine the degree to which teaching experience and gender affect attitudes toward using games. Six factors that hinder teachers' use of games in the classroom were discovered: Inflexibility of curriculum, Negative effects of gaming, Students' lack of readiness, Lack of supporting materials, Fixed class schedules, and Limited budgets. Lack of supporting material, Fixed class schedules, and Limited budgets were factors that female teachers believed to be more serious obstacles to game use in the classroom than male teachers did. Experienced teachers, more so than inexperienced teachers, believed that adopting games in teaching was hindered by Inflexibility of curriculum and Negative effects of gaming. On the other hand, inexperienced teachers, more so than experienced teachers, believed that adopting games in teaching is less hindered by Lack of supporting materials and Fixed class schedules.

  12. Anodal tDCS to Right Dorsolateral Prefrontal Cortex Facilitates Performance for Novice Jazz Improvisers but Hinders Experts

    Science.gov (United States)

    Rosen, David S.; Erickson, Brian; Kim, Youngmoo E.; Mirman, Daniel; Hamilton, Roy H.; Kounios, John

    2016-01-01

    Research on creative cognition reveals a fundamental disagreement about the nature of creative thought, specifically, whether it is primarily based on automatic, associative (Type-1) or executive, controlled (Type-2) processes. We hypothesized that Type-1 and Type-2 processes make differential contributions to creative production that depend on domain expertise. We tested this hypothesis with jazz pianists whose expertise was indexed by the number of public performances given. Previous fMRI studies of musical improvisation have reported that domain expertise is characterized by deactivation of the right-dorsolateral prefrontal cortex (r-DLPFC), a brain area associated with Type-2 executive processing. We used anodal, cathodal, and sham transcranial direct current stimulation (tDCS) applied over r-DLPFC with the reference electrode on the contralateral mastoid (1.5 mA for 15 min, except for sham) to modulate the quality of the pianists' performances while they improvised over chords with drum and bass accompaniment. Jazz experts rated each improvisation for creativity, esthetic appeal, and technical proficiency. There was no main effect of anodal or cathodal stimulation on ratings compared to sham; however, a significant interaction between anodal tDCS and expertise emerged such that stimulation benefitted musicians with less experience but hindered those with more experience. We interpret these results as evidence for a dual-process model of creativity in which novices and experts differentially engage Type-1 and Type-2 processes during creative production. PMID:27899889

  13. What hinder the further development of wind power in China?—A socio-technical barrier study

    International Nuclear Information System (INIS)

    Zhao, Zhen-Yu; Chang, Rui-Dong; Chen, Yu-Long

    2016-01-01

    Promoting wind power is a long-term strategy of China to respond to both energy shortage and environmental pollution. Stimulated by various incentive policies, wind power generation in China has achieved tremendous growth, with the cumulative installed capacity being the largest worldwide for five consecutive years since 2010. However, obstructed by various barriers, wind power provides only 2.6% of national electricity generation in China, despite the strong support from the government. From a socio-technical transition perspective, this paper aims to systematically analyze the barriers hindering the further development of China's wind power. A wind power niche model is established to illustrate the complex interactions among actors in the wind power industry and electricity supply regime. Then, qualitative content analysis is adopted to process the related evidence and data, and four categories of socio-technical barriers are identified, including technology, governance, infrastructure and culture barriers. The study shows that various interrelated barriers form a blocking mechanism which prohibits the further development of wind power in China. Policy suggestions are proposed to eliminate the barriers and further empower the wind power niche. The lesson learned from China can offer useful references for other economies to promote wind power industries of their own. - Highlights: • Use wind power niche model to illustrate the interactions among actors in the industry. • Analyze technological, governance, infrastructural and cultural barriers. • Multidimensionality and interconnectedness of the barriers are illustrated. • Policy suggestions are proposed to deal with the wind power development barriers.

  14. Antivertiginous drug therapy does not hinder the efficacy of individualized vibrotactile neurofeedback training for vestibular rehabilitation - a randomized trial.

    Science.gov (United States)

    Basta, Dietmar; Borsellino, Liliana; Ernst, Arne

    2017-12-01

    Vestibular rehabilitation using individualized vibrotactile neurofeedback training (IVNT) can lead to significant improvement in the postural stability of patients with vestibular symptoms of different origins. However, some of these patients have complex, severe dizziness, meaning that a pharmacological pretreatment or parallel (to vestibular rehabilitation) treatment can help them perform the rehabilitation exercises. Hence, the present study investigated the influence of a pharmacological treatment on the efficacy of vibrotactile neurofeedback training in patients with chronic, noncompensated vestibulopathies. All participants performed IVNT for ∼10 min each day for 2 weeks. In addition, every second participant was selected randomly to receive oral medication (20 mg cinnarizine and 40 mg dimenhydrinate per tablet), taking three tables per day. Trunk and ankle sway and postural stability were measured. In addition, the dizziness handicap inventory was evaluated immediately before training on the last day of training and 6 months after training. After the 10-day period of IVNT, both groups showed a statistically significant improvement in all parameters tested. A follow-up analysis after 6 months showed a long-term efficacy for the IVNT, that is, the patients remained significantly improved in their postural stability. The antivertiginous therapy did not hinder the efficacy of the IVNT. The present results indicate that IVNT even in combination with an antivertiginous drug therapy is an effective treatment regime for patients with disabling vertigo of different origins.

  15. Student Academic Performance: The Role of Motivation, Strategies, and Perceived Factors Hindering Liberian Junior and Senior High School Students Learning

    Directory of Open Access Journals (Sweden)

    Charles Gbollie

    2017-01-01

    Full Text Available The nature of motivation and learning strategy use is vital to improving student learning outcomes. This study was intended to explore the motivational beliefs and learning strategy use by Liberian junior and senior high school students in connection with their academic performance. It also solicited students’ self-reports about presumed factors hindering their learning. Utilizing a cross-sectional quantitative research design, 323 participants took part in the study from 2 counties. Motivated Strategies for Learning Questionnaire (MSLQ was adapted and 12 potential learning hindrances were identified and used as instruments. Data analyses were conducted using SPSS 17.0. The results showed the motivational belief component of extrinsic goal orientation as the most preferred belief and test anxiety was the least possessed belief. Rehearsal strategies were found to be the most frequently used, while help seeking was reported to be the least strategy considered. The result also showed significant relationships between the two constructs. In addition, the study found some learning hindrances. A number of conclusions as well as some practical recommendations for action relative to the improvement of student performance have been advanced.

  16. Anodal tDCS to Right Dorsolateral Prefrontal Cortex Facilitates Performance for Novice Jazz Improvisers but Hinders Experts.

    Science.gov (United States)

    Rosen, David S; Erickson, Brian; Kim, Youngmoo E; Mirman, Daniel; Hamilton, Roy H; Kounios, John

    2016-01-01

    Research on creative cognition reveals a fundamental disagreement about the nature of creative thought, specifically, whether it is primarily based on automatic, associative (Type-1) or executive, controlled (Type-2) processes. We hypothesized that Type-1 and Type-2 processes make differential contributions to creative production that depend on domain expertise. We tested this hypothesis with jazz pianists whose expertise was indexed by the number of public performances given. Previous fMRI studies of musical improvisation have reported that domain expertise is characterized by deactivation of the right-dorsolateral prefrontal cortex (r-DLPFC), a brain area associated with Type-2 executive processing. We used anodal, cathodal, and sham transcranial direct current stimulation (tDCS) applied over r-DLPFC with the reference electrode on the contralateral mastoid (1.5 mA for 15 min, except for sham) to modulate the quality of the pianists' performances while they improvised over chords with drum and bass accompaniment. Jazz experts rated each improvisation for creativity, esthetic appeal, and technical proficiency. There was no main effect of anodal or cathodal stimulation on ratings compared to sham; however, a significant interaction between anodal tDCS and expertise emerged such that stimulation benefitted musicians with less experience but hindered those with more experience. We interpret these results as evidence for a dual-process model of creativity in which novices and experts differentially engage Type-1 and Type-2 processes during creative production.

  17. The Role of Organisational Phenomena in Software Cost Estimation: A Case Study of Supporting and Hindering Factors

    Directory of Open Access Journals (Sweden)

    Jurka Rahikkala

    2018-01-01

    Full Text Available Despite the fact that many researchers and practitioners agree that organisational issues are equally important as technical issues from the software cost estimation (SCE success point of view, most of the research focus has been put on the development of methods, whereas organisational factors have received surprisingly little academic scrutiny. This study aims to identify organisational factors that either support or hinder meaningful SCE, identifying their impact on estimation success. Top management’s role is specifically addressed. The study takes a qualitative and explorative case study based approach. In total, 18 semi-structured interviews aided the study of three projects in three organisations. Hence, the transferability of the results is limited. The results suggest that the role of the top management is important in creating prerequisites for meaningful estimation, but their day-to-day participation is not required for successful estimation. Top management may also induce undesired distortion in estimation. Estimation maturity and estimation success seem to have an interrelationship with software process maturity, but there seem to be no significant individual organisational factors, which alone would make estimation successful. Our results validate several distortions and biases reported in the previous studies, and show the SCE research focus has remained on methodologies and technical issues.

  18. Systematic review and meta-analysis of factors that help or hinder treatment decision-making capacity in psychosis.

    Science.gov (United States)

    Larkin, Amanda; Hutton, Paul

    2017-10-01

    Background The evidence on factors that may influence treatment decisional capacity ('capacity') in psychosis has yet to be comprehensively synthesised, which limits the development of effective strategies to improve or support it. Aims To determine the direction, magnitude and reliability of the relationship between capacity in psychosis and a range of clinical, demographic and treatment-related factors, thus providing a thorough synthesis of current knowledge. Method We conducted a systematic review, meta-analytical and narrative synthesis of factors that help or hinder treatment decision-making capacity in psychosis, assessing the direction, magnitude, significance and reliability of reported associations. Results We identified 23 relevant studies ( n = l823). Psychotic symptoms had small, moderate and strong associations with appreciation, understanding and reasoning respectively. Both verbal cognitive functioning and duration of education had small to moderate correlations with understanding and reasoning. Better capacity was also associated with better insight, better metacognitive ability, higher anxiety and lower perceived coercion. No linear relationship with depression was observed. Interventions linked to improved capacity over time were in-patient care, information simplification, shared decision-making and metacognitive training. Conclusions Although much is known about the role of symptoms and other clinical variables, effective and acceptable psychological interventions to support capacity in this group are lacking. © The Royal College of Psychiatrists 2017.

  19. Anodal tDCS to right dorsolateral prefrontal cortex facilitates performance for novice jazz improvisers but hinders experts

    Directory of Open Access Journals (Sweden)

    David S Rosen

    2016-11-01

    Full Text Available Research on creative cognition reveals a fundamental disagreement about the nature of creative thought, specifically, whether it is primarily based on automatic, associative (Type-1 or executive, controlled (Type-2 processes. We hypothesized that Type-1 and Type-2 processes make differential contributions to creative production that depend on domain expertise. We tested this hypothesis with jazz pianists whose expertise was indexed by the number of public performances given. Previous fMRI studies of musical improvisation have reported that domain expertise is characterized by deactivation of the right-dorsolateral prefrontal cortex (r-DLPFC, a brain area associated with Type-2 executive processing. We used anodal, cathodal, and sham transcranial direct-current stimulation (tDCS applied over r-DLPFC with the reference electrode on the contralateral mastoid (1.5mA for 15 min., except for sham to modulate the quality of the pianists’ performances while they improvised over chords with drum and bass accompaniment. Jazz experts rated each improvisation for creativity, aesthetic appeal, and technical proficiency. There was no main effect of anodal or cathodal stimulation on ratings compared to sham; however, a significant interaction between anodal tDCS and expertise emerged such that stimulation benefitted musicians with less experience but hindered those with more experience. We interpret these results as evidence for a dual-process model of creativity in which novices and experts differentially engage Type-1 and Type-2 processes during creative production.

  20. Kinetics and structure-activity relationship of dendritic bridged hindered phenol antioxidants to protect styrene against free radical induced peroxidation

    Science.gov (United States)

    Li, Cui-Qin; Guo, Su-Yue; Wang, Jun; Shi, Wei-Guang; Zhang, Zhi-Qiu; Wang, Peng-Xiang

    2017-12-01

    A series of dendritic poly(amido-amine) (PAMAM) bridged hindered phenols antioxidants were synthesized. The active antioxidant group (3-(3,5-di- tert-butyl-4-hydroxyphenyl)propionic acid) was attached to two generations of PAMAM dendrimers, and their structure was verified by nuclear magnetic resonance (NMR) and fourier transform infrared spectra (FT-IR). The antioxidant abilities of the dendritic phenols to inhibit the oxidation of styrene were evaluated and the relationships between the length of core, the generation of dendrimers and the antioxidant activities were established. The reaction kinetics of scavenging peroxyl radicals was followed by oxygen consumption. The inhibition time ( t inh) values showed the dendritic phenols had the ability of scavenging peroxyl radicals, and that the antioxidant ability increased with the increasing length of the core and the generation. The kinetic analysis demonstrated that dendritic phenols could slow the rate of styrene peroxidation induced by AIBN, as shown by the number of trapping ROO· ( n), and this role was in accordance with that of the t inh values.

  1. Ward social workers' views of what facilitates or hinders collaboration with specialist palliative care team social workers: A grounded theory.

    Science.gov (United States)

    Firn, Janice; Preston, Nancy; Walshe, Catherine

    2017-07-14

    Inpatient, generalist social workers in discharge planning roles work alongside specialist palliative care social workers to care for patients, often resulting in two social workers being concurrently involved in the same patient's care. Previous studies identifying components of effective collaboration, which impacts patient outcomes, care efficiency, professional job satisfaction, and healthcare costs, were conducted with nurses and physicians but not social workers. This study explores ward social workers' perceptions of what facilitates or hinders collaboration with palliative care social workers. Grounded theory was used to explore the research aim. In-depth qualitative interviews with masters trained ward social workers (n = 14) working in six hospitals located in the Midwest, United States were conducted between February 2014 and January 2015. A theoretical model of ward social workers' collaboration with palliative care social workers was developed. The emerging model of collaboration consists of: 1) trust, which is comprised of a) ability, b) benevolence, and c) integrity, 2) information sharing, and 3) role negotiation. Effective collaboration occurs when all elements of the model are present. Collaboration is facilitated when ward social workers' perceptions of trust are high, pertinent information is communicated in a time-sensitive manner, and a flexible approach to roles is taken. The theoretical model of collaboration can inform organisational policy and social work clinical practice guidelines, and may be of use to other healthcare professionals, as improvements in collaboration among healthcare providers may have a positive impact on patient outcomes.

  2. Limits on same-day billing in Medicaid hinders integration of behavioral health into the medical home model.

    Science.gov (United States)

    Roby, Dylan H; Jones, Erynne E

    2016-02-01

    The potential expansion of insurance coverage through the Patient Protection and Affordable Care Act of 2010 can facilitate the reduction of access barriers and improved quality for behavioral health care. More than 5 million of the newly insured are expected to have mental health and substance use disorders. In addition, state and federal efforts to integrate behavioral and medical health needs through patient-centered medical home models and innovations in payment strategies provide an unprecedented opportunity to use federal financial support to improve not only access to care, but also improve quality through active care coordination, use of interdisciplinary teams, colocating services, and engaging in warm hand-offs between providers in the same setting. These potential advances are hindered in 24 different states because of Medicaid payment policy, with 7 explicitly limiting the ability to reimburse for physical health and behavioral health services on the same day for all providers. Without the ability for providers to be reimbursed for different services on the same day to improve behavioral and medical health care coordination, these states could be limited in their ability to improve care via patient-centered approaches and interdisciplinary team-based care that would involve physicians, clinical psychologists, psychiatrists, and other mental health professionals. Limits on same-day billing in Medicaid programs could impact up to 36.7 million people in 24 states, which is approximately 52.6% of all Medicaid enrollees. (c) 2016 APA, all rights reserved).

  3. The impact of intramolecular π-coupling and steric flexibility on the ordering of organic films at solid/liquid-interfaces

    Science.gov (United States)

    Saracino, Martino; Breuer, Stephan; Barati, Gholamreza; Sak, Emilia; Hingerl, Kurt; Müller, Ute; Müller, Manfred; Höger, Sigurd; Wandelt, Klaus

    2013-01-01

    In the present work the effect of the intramolecular steric flexibility on the structural self-assembly of organic cations and their redox activity at a chloride precovered Cu(100) electrode is investigated. In particular the adsorption of 1,1‧-dibenzyl-4,4‧-(propane-1,3-diyl)dipyridinium (C3-DBDP) is studied by means of cyclic voltametry (CV), in situ scanning tunneling microscopy (EC-STM) and ex situ X-ray photoelectron spectroscopy (XPS) and the experimental results are compared to previously published findings on related bipyridinium (“viologen”) molecules. The CV measurements reveal a loss of the redox activity of the more flexible C3-DBDP2 + compared to dibenzylviologen (DBV2 +), as the first electron reduction step of C3-DBDP2 + does not appear within the potential window of the Cu(100), but is shifted below the hydrogen evolution regime. This reduced redox activity is the result of the lifting of the extended π-system of the bipyridinium core by introducing the propyl chain between the two pyridinium rings. In agreement with this result, XP spectra prove that the C3-DBDP2 + cations retain their initial dicationic charge within the entire potential window in solution but also upon adsorption on the Cl-c(2x2)/Cu(100) substrate, where they are found to form an inter-linked stripe phase. The building blocks of each stripe are attributed to one pyridinium-benzyl moiety, which represents half of one C3-DBDP2 + molecule. The resulting consecutive arrangement of half C3-DBDP2 + molecules along one stripe is stabilized by electrostatic attraction between the positively charged pyridinium rings and the negatively charged π-system of the benzyl rings.

  4. Steric Clash in the SET Domain of Histone Methyltransferase NSD1 as a Cause of Sotos Syndrome and Its Genetic Heterogeneity in a Brazilian Cohort

    Directory of Open Access Journals (Sweden)

    Kyungsoo Ha

    2016-11-01

    Full Text Available Most histone methyltransferases (HMTase harbor a predicted Su(var3–9, Enhancer-of-zeste, Trithorax (SET domain, which transfers a methyl group to a lysine residue in their substrates. Mutations of the SET domains were reported to cause intellectual disability syndromes such as Sotos, Weaver, or Kabuki syndromes. Sotos syndrome is an overgrowth syndrome with intellectual disability caused by haploinsufficiency of the nuclear receptor binding SET domain protein 1 (NSD1 gene, an HMTase at 5q35.2–35.3. Here, we analyzed NSD1 in 34 Brazilian Sotos patients and identified three novel and eight known mutations. Using protein modeling and bioinformatic approaches, we evaluated the effects of one novel (I2007F and 21 previously reported missense mutations in the SET domain. For the I2007F mutation, we observed conformational change and loss of structural stability in Molecular Dynamics (MD simulations which may lead to loss-of-function of the SET domain. For six mutations near the ligand-binding site we observed in simulations steric clashes with neighboring side chains near the substrate S-Adenosyl methionine (SAM binding site, which may disrupt the enzymatic activity of NSD1. These results point to a structural mechanism underlying the pathology of the NSD1 missense mutations in the SET domain in Sotos syndrome. NSD1 mutations were identified in only 32% of the Brazilian Sotos patients in our study cohort suggesting other genes (including unknown disease genes underlie the molecular etiology for the majority of these patients. Our studies also found NSD1 expression to be profound in human fetal brain and cerebellum, accounting for prenatal onset and hypoplasia of cerebellar vermis seen in Sotos syndrome.

  5. 1H NMR spectra. Part 30(+): 1H chemical shifts in amides and the magnetic anisotropy, electric field and steric effects of the amide group.

    Science.gov (United States)

    Abraham, Raymond J; Griffiths, Lee; Perez, Manuel

    2013-03-01

    The (1)H spectra of 37 amides in CDCl(3) solvent were analysed and the chemical shifts obtained. The molecular geometries and conformational analysis of these amides were considered in detail. The NMR spectral assignments are of interest, e.g. the assignments of the formamide NH(2) protons reverse in going from CDCl(3) to more polar solvents. The substituent chemical shifts of the amide group in both aliphatic and aromatic amides were analysed using an approach based on neural network data for near (≤3 bonds removed) protons and the electric field, magnetic anisotropy, steric and for aromatic systems π effects of the amide group for more distant protons. The electric field is calculated from the partial atomic charges on the N.C═O atoms of the amide group. The magnetic anisotropy of the carbonyl group was reproduced with the asymmetric magnetic anisotropy acting at the midpoint of the carbonyl bond. The values of the anisotropies Δχ(parl) and Δχ(perp) were for the aliphatic amides 10.53 and -23.67 (×10(-6) Å(3)/molecule) and for the aromatic amides 2.12 and -10.43 (×10(-6) Å(3)/molecule). The nitrogen anisotropy was 7.62 (×10(-6) Å(3)/molecule). These values are compared with previous literature values. The (1)H chemical shifts were calculated from the semi-empirical approach and also by gauge-independent atomic orbital calculations with the density functional theory method and B3LYP/6-31G(++) (d,p) basis set. The semi-empirical approach gave good agreement with root mean square error of 0.081 ppm for the data set of 280 entries. The gauge-independent atomic orbital approach was generally acceptable, but significant errors (ca. 1 ppm) were found for the NH and CHO protons and also for some other protons. Copyright © 2013 John Wiley & Sons, Ltd.

  6. Solution NMR characterization of magnetic/electronic properties of azide and cyanide-inhibited substrate complexes of human heme oxygenase: implications for steric ligand tilt.

    Science.gov (United States)

    Peng, Dungeng; Ogura, Hiroshi; Ma, Li-Hua; Evans, John P; de Montellano, Paul R Ortiz; La Mar, Gerd N

    2013-04-01

    Solution 2D (1)H NMR was carried out on the azide-ligated substrate complex of human heme oxygenase, hHO, to provide information on the active site molecular structure, chromophore electronic/magnetic properties, and the distal H-bond network linked to the exogenous ligand by catalytically relevant oriented water molecules. While 2D NMR exhibited very similar patterns of two-dimensional nuclear Overhauser spectroscopy cross peaks of residues with substrate and among residues as the previously characterized cyanide complex, significant, broadly distributed chemical shift differences were observed for both labile and non-labile protons. The anisotropy and orientation of the paramagnetic susceptibility tensor, χ, were determined for both the azide and cyanide complexes. The most significant difference observed is the tilt of the major magnetic axes from the heme normal, which is only half as large for the azide than cyanide ligand, with each ligand tilted toward the catalytically cleaved α-meso position. The difference in chemical shifts is quantitatively correlated with differences in dipolar shifts in the respective complexes for all but the distal helix. The necessity of considering dipolar shifts, and hence determination of the orientation/anisotropy of χ, in comparing chemical shifts involving paramagnetic complexes, is emphasized. The analysis shows that the H-bond network cannot detect significant differences in H-bond acceptor properties of cyanide versus azide ligands. Lastly, significant retardation of distal helix labile proton exchange upon replacing cyanide with azide indicates that the dynamic stability of the distal helix is increased upon decreasing the steric interaction of the ligand with the distal helix. Copyright © 2013. Published by Elsevier Inc.

  7. Quantitative conformational analysis of the core region of N-glycans using residual dipolar couplings, aqueous molecular dynamics, and steric alignment

    International Nuclear Information System (INIS)

    Almond, Andrew; Duus, Jens O.

    2001-01-01

    A method is described for quantitatively investigating the dynamic conformation of small oligosaccharides containing an α(1 → 6) linkage. It was applied to the oligosaccharide Man-α(1 → 3) {Man-α (1 → 6)}Man-α-O-Me, which is a core region frequently observed in N-linked glycans. The approach tests an aqueous molecular dynamics simulation, capable of predicting microscopic dynamics, against experimental residual dipolar couplings, by assuming that alignment is caused purely by steric hindrance. The experimental constraints were heteronuclear and homonuclear residual dipolar couplings, and in particular those within the α(1 → 6) linkage itself. Powerful spin-state-selective pulse sequences and editing schemes were used to obtain the most relevant couplings for testing the model. Molecular dynamics simulations in water over a period of 50 ns were not able to predict the correct rotamer population at the α(1 → 6) linkage to agree with the experimental data. However, this sampling problem could be corrected using a simple maximum likelihood optimisation, indicating that the simulation was modelling local dynamics correctly. The maximum likelihood prediction of the residual dipolar couplings was found to be an almost equal population of the gg and gt rotamer conformations at the α(1 → 6) linkage, and the tg conformation was predicted to be unstable and unpopulated in aqueous solution. In this case all twelve measured residual dipolar couplings could be satisfied. This conformer population could also be used to make predictions of scalar couplings with the use of a previously derived empirical equation, and is qualitatively in agreement with previous predictions based on NMR, X-ray crystallography and optical data

  8. Do accountable care organizations (ACOs) help or hinder primary care physicians' ability to deliver high-quality care?

    Science.gov (United States)

    Berenson, Robert A; Burton, Rachel A; McGrath, Megan

    2016-09-01

    Many view advanced primary care models such as the patient-centered medical home as foundational for accountable care organizations (ACOs), but it remains unclear how these two delivery reforms are complementary and how they may produce conflict. The objective of this study was to identify how joining an ACO could help or hinder a primary care practice's efforts to deliver high-quality care. This qualitative study involved interviews with a purposive sample of 32 early adopters of advanced primary care and/or ACO models, drawn from across the U.S. and conducted in mid-2014. Interview notes were coded using qualitative data analysis software, permitting topic-specific queries which were then summarized. Respondents perceived many potential benefits of joining an ACO, including care coordination staff, data analytics, and improved communication with other providers. However, respondents were also concerned about added "bureaucratic" requirements, referral restrictions, and a potential inability to recoup investments in practice improvements. Interviewees generally thought joining an ACO could complement a practice's efforts to deliver high-quality care, yet noted some concerns that could undermine these synergies. Both the advantages and disadvantages of joining an ACO seemed exacerbated for small practices, since they are most likely to benefit from additional resources yet are most likely to chafe under added bureaucratic requirements. Our identification of the potential pros and cons of joining an ACO may help providers identify areas to examine when weighing whether to enter into such an arrangement, and may help ACOs identify potential areas for improvement. Copyright © 2016 Elsevier Inc. All rights reserved.

  9. Friend or Foe: Variability in How Sea Ice Can Both Hinder and Enhance Phytoplankton Blooms Across the Southern Ocean

    Science.gov (United States)

    Rohr, T.

    2016-02-01

    Globally, a suite of physical and biogeochemical controls govern the structure, size, and timing of seasonal phytoplankton blooms. In the Southern Ocean, the introduction of seasonal sea ice provides an additional constraining factor. From a bottom-up perspective, a reduction in sea ice can both enhance bloom development by permitting greater levels of surface PAR uninhibited by ice and suppress a bloom when reduced fresh melt-water inputs and increased vulnerability to wind stress combine to create deeper mixed layers and decrease depth integrated light availability. Regions along the Western Antarctic Peninsula have already seen a contradictory response to reduced ice cover, with enhanced summertime chlorophyll concentrations in the South, and large declines to the North. This dichotomy is thought to arise from differences in the interannual mean sea ice state, with extensively ice covered regions benefiting from reduced coverage and more sparsely covered regions hindered by further reductions. The questions arises: 1) At what threshold does a reduction in sea ice transition from amplifying blooms to suppressing them? 2) How do additional environmental considerations such as nutrient availability and trophic interactions complicate this transition? Here, we combine remote sensing observations and in-situ data (from PAL LTER) with a hierarchy of 1-D water column and global general circulation (CESM) models to access the variability in how regional differences in mean ice state combine with other environmental forcings to dictate how interannual variability (or long term trends) in ice coverage will affect bloom structure, size and dynamics. In doing so we will gain a better understanding of how predicted changes in sea ice will effect Southern Ocean productivity, which of course will have important consequences in the global carbon cycle and sustainability of healthy marine ecosystems.

  10. Influence of a hindered amine stabilizer (HAS) and inorganic salt mixture on degradation of poly(methyl methacrylate)

    International Nuclear Information System (INIS)

    Silva, Williams B. da; Vasconcelos, Henrique M. de; Aquino, Katia Aparecida da S.; Araujo, Elmo S.

    2009-01-01

    Commercial poly(methyl methacrylate) (PMMA) is used as medical supplies, which is sterilized by gamma irradiation at 25 kGy dose. However, when the PMMA is exposed to gamma rays it undergoes main chain scissions with changes in its properties. Samples of commercial PMMA containing a Hindered Amine Stabilizer (PMMA-HAS) and samples containing a salt mixture of CuCl 2 /KI (PMMA-salt) both at 0.3wt% concentration were investigated. The PMMA samples were purified by re-precipitation in methanol. The samples were irradiated with gamma radiation ( 60 Co) at room temperature in air at dose range of 15-100 kGy. The viscosity- average molecular weight (M v ) was analyzed by viscosity technique. Comparison of viscosity results obtained before and after irradiation of PMMA showed a decrease in Mv values on irradiated samples with the increase in dose, reflecting the random scissions that occurred in the main chain. However the decrease on M v is less in PMMA-HAS samples than control PMMA. The G value (scissions/100 eV of energy transferred to the system) obtained by viscosity analysis were used to calculated the protection value of HAS on PMMA matrix. The HAS showed a protection of 61% on PMMA molecules exposed to gamma irradiation. No efficiency action of salt mixture was observed on radiolytic degradation of PMMA. On the other hand the CuCl 2 /KI mixture influenced the mechanical behavior of PMMA and the HAS additive increased the maximum thermal degradation temperature of PMMA matrix. (author)

  11. Treatment with paracetamol, ketorolac or etoricoxib did not hinder alveolar bone healing: a histometric study in rats

    Directory of Open Access Journals (Sweden)

    Ricardo Nogueira Fracon

    2010-12-01

    Full Text Available Prostaglandins control osteoblastic and osteoclastic function under physiological or pathological conditions and are important modulators of the bone healing process. The non-steroidal anti-inflammatory drugs (NSAIDs inhibit cyclooxygenase (COX activity and consequently prostaglandins synthesis. Experimental and clinical evidence has indicated a risk for reparative bone formation related to the use of non-selective (COX-1 and COX-2 and COX-2 selective NSAIDs. Ketorolac is a non-selective NSAID which, at low doses, has a preferential COX-1 inhibitory effect and etoricoxib is a new selective COX-2 inhibitor. Although literature data have suggested that ketorolac can interfere negatively with long bone fracture healing, there seems to be no study associating etoricoxib with reparative bone formation. Paracetamol/acetaminophen, one of the first choices for pain control in clinical dentistry, has been considered a weak anti-inflammatory drug, although supposedly capable of inhibiting COX-2 activity in inflammatory sites. OBJECTIVE: The purpose of the present study was to investigate whether paracetamol, ketorolac and etoricoxib can hinder alveolar bone formation, taking the filling of rat extraction socket with newly formed bone as experimental model. MATERIAL AND METHODS: The degree of new bone formation inside the alveolar socket was estimated two weeks after tooth extraction by a differential point-counting method, using an optical microscopy with a digital camera for image capture and histometry software. Differences between groups were analyzed by ANOVA after confirming a normal distribution of sample data. RESULTS AND CONCLUSIONS: Histometric results confirmed that none of the tested drugs had a detrimental effect in the volume fraction of bone trabeculae formed inside the alveolar socket.

  12. Increase of glucocorticoids is not required for the acquisition, but hinders the extinction, of lithium-induced conditioned taste aversion.

    Science.gov (United States)

    Kim, Kyu-Nam; Kim, Bom-Taeck; Kim, Young-Sang; Lee, Jong-Ho; Jahng, Jeong Won

    2014-05-05

    Lithium chloride at doses sufficient to induce conditioned taste aversion (CTA) causes c-Fos expression in the paraventricular nucleus and increases the plasma level of corticosterone with activation of the hypothalamic-pituitary-adrenal axis. This study was conducted to define the role of glucocorticoid in the acquisition and extinction of lithium-induced CTA. In experiment 1, Sprague-Dawley rats received dexamethasone (2mg/kg) or RU486 (20mg/kg) immediately after 5% sucrose access, and then an intraperitoneal injection of isotonic lithium chloride (12ml/kg) was followed with 30min interval. Rats had either 1 or 7 days of recovery period before the daily sucrose drinking tests. In experiment 2, rats were conditioned with the sucrose-lithium pairing, and then received dexamethasone or vehicle at 30min before each drinking test. In experiment 3, adrenalectomized (ADX or ADX+B) rats were subjected to sucrose drinking tests after the sucrose-lithium pairing. Dexamethasone, but not RU486, pretreatment blunted the formation of lithium-induced CTA memory. Dexamethasone prior to each drinking test suppressed sucrose consumption and prolonged the extinction of lithium-induced CTA. Sucrose consumption was significantly suppressed not only in ADX+B rats but also in ADX rats during the first drinking session; however, a significant decrease was found only in ADX rats on the fourth drinking session. These results reveal that glucocorticoid is not a necessary component in the acquisition, but an important player in the extinction, of lithium-induced CTA, and suggest that a pulse increase of glucocorticoid may hinder the extinction memory formation of lithium-induced CTA. Copyright © 2014 Elsevier B.V. All rights reserved.

  13. DNA unwinding by ring-shaped T4 helicase gp41 is hindered by tension on the occluded strand.

    Science.gov (United States)

    Ribeck, Noah; Saleh, Omar A

    2013-01-01

    The replicative helicase for bacteriophage T4 is gp41, which is a ring-shaped hexameric motor protein that achieves unwinding of dsDNA by translocating along one strand of ssDNA while forcing the opposite strand to the outside of the ring. While much study has been dedicated to the mechanism of binding and translocation along the ssDNA strand encircled by ring-shaped helicases, relatively little is known about the nature of the interaction with the opposite, 'occluded' strand. Here, we investigate the interplay between the bacteriophage T4 helicase gp41 and the ss/dsDNA fork by measuring, at the single-molecule level, DNA unwinding events on stretched DNA tethers in multiple geometries. We find that gp41 activity is significantly dependent on the geometry and tension of the occluded strand, suggesting an interaction between gp41 and the occluded strand that stimulates the helicase. However, the geometry dependence of gp41 activity is the opposite of that found previously for the E. coli hexameric helicase DnaB. Namely, tension applied between the occluded strand and dsDNA stem inhibits unwinding activity by gp41, while tension pulling apart the two ssDNA tails does not hinder its activity. This implies a distinct variation in helicase-occluded strand interactions among superfamily IV helicases, and we propose a speculative model for this interaction that is consistent with both the data presented here on gp41 and the data that had been previously reported for DnaB.

  14. Common attributes in retired professional cricketers that may enhance or hinder quality of life after retirement: a qualitative study.

    Science.gov (United States)

    Filbay, Stephanie R; Bishop, Felicity; Peirce, Nicholas; Jones, Mary E; Arden, Nigel K

    2017-07-26

    Retired professional cricketers shared unique experiences and may possess specific psychological attributes with potential to influence quality of life (QOL). Additionally, pain and osteoarthritis can be common in retired athletes which may negatively impact QOL. However, QOL in retired athletes is poorly understood. This study explores the following questions from the personal perspective of retired cricketers: How do retired cricketers perceive and experience musculoskeletal pain and function in daily life? Are there any psychological attributes that might enhance or hinder retired cricketers' QOL? A qualitative study using semistructured interviews, which were subject to inductive, thematic analysis. A data-driven, iterative approach to data coding was employed. All participants had lived and played professional cricket in the UK and were living in the UK or abroad at the time of interview. Eighteen male participants, aged a mean 57±11 (range 34-77) years had played professional cricket for a mean 12±7 seasons and had been retired from professional cricket on average 23±9 years. Fifteen participants reported pain or joint difficulties and all but one was satisfied with their QOL. Most retired cricketers reflected on experiences during their cricket career that may be associated with the psychological attributes that these individuals shared, including resilience and a positive attitude. Additional attributes included a high sense of body awareness, an ability to self-manage pain and adapt lifestyle choices to accommodate physical limitations. Participants felt fortunate and proud to have played professional cricket, which may have further contributed to the high QOL in this group of retired cricketers. Most retired cricketers in this study were living with pain or joint difficulties. Despite this, all but one was satisfied or very satisfied with their QOL. This may be partly explained by the positive psychological attributes that these retired cricketers

  15. The co-delivery of a low-dose P-glycoprotein inhibitor with doxorubicin sterically stabilized liposomes against breast cancer with low P-glycoprotein expression

    Directory of Open Access Journals (Sweden)

    Gao W

    2014-07-01

    Full Text Available Wei Gao,1 Zhiqiang Lin,1 Meiwan Chen,2 Xiucong Yang,1 Zheng Cui,1 Xiaofei Zhang,1 Lan Yuan,3 Qiang Zhang11State Key Laboratory of Natural and Biomimetic Drugs, School of Pharmaceutical Sciences, Peking University, Beijing, 2State Key Laboratory of Quality Research in Chinese Medicine, Institute of Chinese Medical Sciences, University of Macau, Macau, 3Medical and Healthy Analytical Center, Peking University, Beijing, People's Republic of China Introduction: P-glycoprotein (P-gp inhibitors are usually used to treat tumors that overexpress P-gps. However, most common types of breast cancers, such as Luminal A, are low-P-gp expressing, at least during the initial phases of treatment. Therefore, it would be interesting to know if P-gp inhibitors are still useful in treating low-P-gp-expressing tumors. Methods: In the study reported here, the human breast-cancer cell line MCF-7, chosen as a model of Luminal A, was found to be low-P-gp expressing. We designed a novel doxorubicin (DOX sterically stabilized liposome system co-loaded with the low-dose P-gp inhibitor cyclosporine A (CsA (DOX/CsA/SSL. Results: The co-delivery system showed good size uniformity, high encapsulation efficiency, and a desirable release profile. The cell-uptake and cytotoxicity studies demonstrated that CsA could significantly enhance the intracellular accumulation and toxicity of free DOX and the liposomal DOX in MCF-7 cells. The confocal microscopy and in vivo imaging study confirmed the intracellular and in vivo targeting effect of DOX/CsA/SSL, respectively. Finally, the in vivo study proved that DOX/CsA/SSL could achieve significantly better antitumor effect against MCF-7 tumor than controls, without inducing obvious systemic toxicity. Conclusion: This study demonstrated that the co-delivery of a low-dose P-gp inhibitor and liposomal DOX could improve the therapy of low-P-gp-expressing cancer, which is of significance in clinical tumor therapy. Keywords: liposomes, low

  16. Preparation of New 2,3-Diphenylpropenoic Acid Esters – Good Yields Even for the More Hindered Z Isomers

    Directory of Open Access Journals (Sweden)

    István Pálinkó

    2004-03-01

    Full Text Available The potassium salt of E- and Z-2,3-diphenylpropenoic acids prepared in situ could be esterified efficiently in DMSO with the appropriate alkyl halides at room temperature. In this way 10 previously undescribed esters of these acids were synthesised and characterised. Excellent yields were observed for most of the E isomers and the more hindered Z esters were also obtained in good yields, far better than those obtained applying the classical acid-catalysed esterification reaction.

  17. Steric and electronic parameters of a bulky yet flexible N-heterocyclic carbene: 1,3-bis(2,6-bis(1-ethylpropyl)phenyl)imidazol-2-ylidene (IPent)

    KAUST Repository

    Collado, Alba; Balogh, Já nos; Meiries, Sé bastien; Slawin, Alexandra M. Z.; Falivene, Laura; Cavallo, Luigi; Nolan, Steven P.

    2013-01-01

    The free N-heterocyclic carbene IPent (1; IPent = 1,3-bis(2,6-bis(1- ethylpropyl)phenyl)imidazol-2-ylidene) was prepared from the corresponding imidazolium chloride salt (2). The steric and electronic parameters of 1 were determined by synthesis of the gold(I) chloride complex [Au(IPent)Cl] (3) and the nickel-carbonyl complex [Ni(IPent)(CO)3] (4), respectively. 3 and 4 were fully characterized by NMR spectroscopy, elemental analysis, and X-ray diffraction studies on single crystals. © 2013 American Chemical Society.

  18. Steric and electronic parameters of a bulky yet flexible N-heterocyclic carbene: 1,3-bis(2,6-bis(1-ethylpropyl)phenyl)imidazol-2-ylidene (IPent)

    KAUST Repository

    Collado, Alba

    2013-06-10

    The free N-heterocyclic carbene IPent (1; IPent = 1,3-bis(2,6-bis(1- ethylpropyl)phenyl)imidazol-2-ylidene) was prepared from the corresponding imidazolium chloride salt (2). The steric and electronic parameters of 1 were determined by synthesis of the gold(I) chloride complex [Au(IPent)Cl] (3) and the nickel-carbonyl complex [Ni(IPent)(CO)3] (4), respectively. 3 and 4 were fully characterized by NMR spectroscopy, elemental analysis, and X-ray diffraction studies on single crystals. © 2013 American Chemical Society.

  19. The antitumor activity of a doxorubicin loaded, iRGD-modified sterically-stabilized liposome on B16-F10 melanoma cells: in vitro and in vivo evaluation

    Directory of Open Access Journals (Sweden)

    Yu KF

    2013-07-01

    Full Text Available Ke-Fu Yu,1 Wei-Qiang Zhang,1 Li-Min Luo,1 Ping Song,1 Dan Li,1 Ruo Du,1 Wei Ren,1 Dan Huang,1 Wan-Liang Lu,1,2 Xuan Zhang,1 Qiang Zhang1,2 1Department of Pharmaceutics, School of Pharmaceutical Sciences, Peking University, Beijing, People’s Republic of China; 2State Key Laboratory of Natural and Biomimetic Drugs, School of Pharmaceutical Sciences, Peking University, Beijing, People’s Republic of China Abstract: Considering the fact that iRGD (tumor-homing peptide demonstrates tumor-targeting and tumor-penetrating activity, and that B16-F10 (murine melanoma cells overexpress both αv integrin receptor and neuropilin-1 (NRP-1, the purpose of this study was to prepare a novel doxorubicin (DOX-loaded, iRGD-modified, sterically-stabilized liposome (SSL (iRGD-SSL-DOX in order to evaluate its antitumor activity on B16-F10 melanoma cells in vitro and in vivo. The iRGD-SSL-DOX was prepared using a thin-film hydration method. The characteristics of iRGD-SSL-DOX were evaluated. The in vitro leakage of DOX from iRGD-SSL-DOX was tested. The in vitro tumor-targeting and tumor-penetrating characteristics of iRGD-modified liposomes on B16-F10 cells were investigated. The in vivo tumor-targeting and tumor-penetrating activities of iRGD-modified liposomes were performed in B16-F10 tumor-bearing nude mice. The antitumor effect of iRGD-SSL-DOX was evaluated in B16-F10 tumor-bearing C57BL/6 mice in vivo. The average particle size of the iRGD-SSL-DOX was found to be 91 nm with a polydispersity index (PDI of 0.16. The entrapment efficiency of iRGD-SSL-DOX was 98.36%. The leakage of DOX from iRGD-SSL-DOX at the 24-hour time point was only 7.5%. The results obtained from the in vitro flow cytometry and confocal microscopy, as well as in vivo biodistribution and confocal immunofluorescence microscopy experiments, indicate that the tumor-targeting and tumor-penetrating activity of the iRGD-modified SSL was higher than that of unmodified SSL. In vivo antitumor activity

  20. Reflections on the role of consultant radiographers in the UK: The perceived impact on practice and factors that support and hinder the role

    International Nuclear Information System (INIS)

    Henwood, S.; Booth, L.; Miller, P.K.

    2016-01-01

    Study context: This paper is the third paper arising from a two year long, in-depth case study exploring various components of the role of consultant radiographers in the UK. This paper focuses particularly upon the perceived impact of the role and factors that support and hinder the role in practice. Methods: A longitudinal case study method was used to explore the role of consultant radiographers. Interviewing was informed and guided by a phenomenological approach to promote a deeper understanding of consultants' experiences in the role. Eight consultant radiographers participated, with six involved throughout the whole study. Over an 18 month period each of those six consultants was interviewed three times. Two consultants only participated in the first interview; these interviews are also reported here. A total of 20 interviews were conducted. Findings: Interviews explored the impact of the consultant role as perceived by consultants themselves, and encouraged individual reflection on factors which had both supported and hindered success therein. Analysis demonstrated that there was substantial variation in the experiences communicated yet, and without any exception, all consultants reported that the introduction of their role had been beneficial to service delivery and quality of patient care. A number of obstacles were outlined, as well as a range of support mechanisms. Recommendations are thus made as to how the consultant role might be more effectively supported in the future. - Highlights: • The perceived impact of the consultant radiographer role in practice. • Reflections upon what supported the consultants in their role. • Reflections upon what hindered the consultants in their role.

  1. Reprint of: A numerical investigation of fine sediment resuspension in the wave boundary layer-Uncertainties in particle inertia and hindered settling

    Science.gov (United States)

    Cheng, Zhen; Yu, Xiao; Hsu, Tian-Jian; Balachandar, S.

    2016-05-01

    The wave bottom boundary layer is a major conduit delivering fine terrestrial sediments to continental margins. Hence, studying fine sediment resuspensions in the wave boundary layer is crucial to the understanding of various components of the earth system, such as carbon cycles. By assuming the settling velocity to be a constant in each simulation, previous turbulence-resolving numerical simulations reveal the existence of three transport modes in the wave boundary layer associated with sediment availabilities. As the sediment availability and hence the sediment-induced stable stratification increases, a sequence of transport modes, namely, (I) well-mixed transport, (II) formulation of lutocline resembling a two-layer system, and (III) completely laminarized transport are observed. In general, the settling velocity is a flow variable due to hindered settling and particle inertia effects. Present numerical simulations including the particle inertia suggest that for a typical wave condition in continental shelves, the effect of particle inertia is negligible. Through additional numerical experiments, we also confirm that the particle inertia tends (up to the Stokes number St = 0.2) to attenuate flow turbulence. On the other hand, for flocs with lower gelling concentrations, the hindered settling can play a key role in sustaining a large amount of suspended sediments and results in the laminarized transport (III). For the simulation with a very significant hindered settling effect due to a low gelling concentration, results also indicate the occurrence of gelling ignition, a state in which the erosion rate is always higher than the deposition rate. A sufficient condition for the occurrence of gelling ignition is hypothesized for a range of wave intensities as a function of sediment/floc properties and erodibility parameters.

  2. The Attitude of Math Teachers toward Cooperative Learning and Institutional Elements that May Help or Hinder its Use as a Teaching Methodology

    Directory of Open Access Journals (Sweden)

    Luis Gerardo Meza-Cascante

    2015-01-01

    Full Text Available This paper presents the results of research conducted in high schools in the central region of the Cartago province, Costa Rica. The goal of the research was to determine the attitude of high school math teachers toward cooperative learning in math and identify factors in secondary education institutions that can help or hinder the implementation of cooperative learning as a strategy for teaching mathematics. The research was conducted with 39 secondary education math teachers, who participated in a workshop on cooperative learning in mathematics. The attitude toward this methodology was measured by using semantic differential. This information was triangulated with data obtained from non-participant observation. A combination of in-depth interviews and non-participant observation was used to access data that identifies institutional factors helping or hindering the implementation of math cooperative learning. Findings suggest a positive attitude from teachers toward integrating cooperative work as a teaching strategy to promote math learning and toward the role played by school principals in the adoption of educational innovations. It also reveals that high schools have adequate material conditions to implement the methodology, although the need for training is considered. This finding should be taken into account by the proponents of this methodological option.

  3. The inhibition of lactate dehydrogenase A hinders the transcription of histone 2B gene independently from the block of aerobic glycolysis

    International Nuclear Information System (INIS)

    Brighenti, Elisa; Carnicelli, Domenica; Brigotti, Maurizio; Fiume, Luigi

    2017-01-01

    Most cancer cells use aerobic glycolysis to fuel their growth and many efforts are made to selectively block this metabolic pathway in cancer cells by inhibiting lactate dehydrogenase A (LDHA). However, LDHA is a moonlighting protein which exerts functions also in the nucleus as a factor associated to transcriptional complexes. Here we found that two small molecules which inhibit the enzymatic activity of LDHA hinder the transcription of histone 2B gene independently from the block of aerobic glycolysis. Moreover, we observed that silencing this gene reduces cell replication, hence suggesting that the inhibition of LDHA can also affect the proliferation of normal non-glycolysing dividing cells. - Highlights: • Blocking aerobic glycolysis is an approach to impair proliferation of cancer cells. • Small inhibitors of LDHA block aerobic glycolysis. • LDHA is also involved in the transcription of histone 2B gene. • LDHA inhibitors block histone 2B transcription. • LDHA inhibitors can hinder the proliferation also of non-glycolysing normal cells.

  4. Examination of near-wall hindered Brownian diffusion of nanoparticles: Experimental comparison to theories by Brenner (1961) and Goldman et al. (1967)

    International Nuclear Information System (INIS)

    Choi, C. K.; Margraves, C. H.; Kihm, K. D.

    2007-01-01

    Multilayered distributions of hindered mean square displacement (MSD) for nanoparticles are measured in the near-wall region within 500 nm from the solid surface using total internal reflection fluorescence microscopy, an evanescent wave microscopic imaging technique. Examined particles are yellow-green (505/515) polystyrene fluorescent nanospheres of 100, 250, and 500 nm radii with a specific gravity of 1.055. To ensure the measurement accuracy, special care is taken to minimize photobleaching of fluorescent particles by adding neutral density filters to optimally reduce the excitation power. The experimental results for parallel MSDs to the solid surface validate the theory of hindered diffusion [A. J. Goldman, R. G. Cox, and H. Brenner, 'Slow viscous motion of a sphere parallel to a plane - I: Motion through a quiescent fluid', Chem. Eng. Sci. 22, 637 (1967)] of spheres based on viscous slow-down in the near-wall region. It is also reported that the effect of adding sodium chloride up to 10 mM to the solution has little effect on the parallel diffusive motion of the tested nanoparticles. Experimental evidence shows that normal MSDs, for submicroscopic charged nanoparticles, are substantially different from Einstein's 2DΔt due to the deterministic motion arising from electrostatic forces

  5. Synthesis and structural characterization of PHP[(C(5)Me(4))(2)], a monodentate chiral phosphine derived from intramolecular C-C coupling of tetramethylcyclopentadienyl groups: an evaluation of steric and electronic properties.

    Science.gov (United States)

    Shin, J H; Bridgewater, B M; Churchill, D G; Parkin, G

    2001-10-22

    The chiral monodentate phosphine PhP[(C(5)Me(4))(2)] is readily obtained by oxidation of the lithium complex Li(2)[PhP(C(5)Me(4))(2)] with I(2), which couples the two cyclopentadienyl groups to form a five-membered heterocyclic ring. The steric and electronic properties of PhP[(C(5)Me(4))(2)] have been evaluated by X-ray diffraction and IR spectroscopic studies on a variety of derivatives, including Ph[(C(5)Me(4))(2)]PE (E = S, Se), Cp*MCl(4)[P[(C(5)Me(4))(2)]Ph] (M = Mo, Ta), Ir[P[(C(5)Me(4))(2)]Ph](2)(CO)Cl, and CpFe(CO)[PhP[(C(5)Me(4))(2)

  6. A structural study of [CpM(CO)3H] (M = Cr, Mo and W) by single-crystal X-ray diffraction and DFT calculations: sterically crowded yet surprisingly flexible molecules.

    Science.gov (United States)

    Burchell, Richard P L; Sirsch, Peter; Decken, Andreas; McGrady, G Sean

    2009-08-14

    The single-crystal X-ray structures of the complexes [CpCr(CO)3H] 1, [CpMo(CO)3H] 2 and [CpW(CO)3H] 3 are reported. The results indicate that 1 adopts a structure close to a distorted three-legged piano stool geometry, whereas a conventional four-legged piano stool arrangement is observed for 2 and 3. Further insight into the equilibrium geometries and potential energy surfaces of all three complexes was obtained by DFT calculations. These show that in the gas phase complex 1 also prefers a geometry close to a four-legged piano stool in line with its heavier congeners, and implying strong packing forces at work for 1 in the solid state. Comparison with their isolelectronic group 7 tricarbonyl counterparts [CpM(CO)3] (M = Mn 4 and Re 5) illustrates that 1, 2 and 3 are sterically crowded complexes. However, a surprisingly soft bending potential is evident for the M-H moiety, whose order (1 approximately = 2 < 3) correlates with the M-H bond strength rather than with the degree of congestion at the metal centre, indicating electronic rather than steric control of the potential. The calculations also reveal cooperative motions of the hydride and carbonyl ligands in the M(CO)3H unit, which allow the M-H moiety to move freely, in spite of the closeness of the four basal ligands, helping to explain the surprising flexibility of the crowded coordination sphere observed for this family of high CN complexes.

  7. The effects of gamma irradiation on the fate of hindered phenol antioxidants in food contact polymers. Analytical and 14C-labelling studies

    International Nuclear Information System (INIS)

    Allen, D.W.; Leathard, D.A.; Smith, C.

    1991-01-01

    The extractable levels of two hindered phenol antioxidants (Irganox 1076 and Irganox 1010) present in PVC, polyethylene and polypropylene have been monitored by HPLC techniques following progressive exposure of the polymers to 60 Co(gamma) radiation. There is a gradual diminution in the extractable levels of each antioxidant as irradiation progresses as a result of transformation of the antioxidants in the oxidation reactions ensuing during irradiation. Experiments involving the use of a 14 C-labelled sample of Irganox 1076 in polyolefins have provided evidence of covalent binding of antioxidant degradation products to the polymer following gamma irradiation. However, there is also evidence of the formation of extractable degradation products, the identity of which is as yet unknown. (author)

  8. The effects of gamma irradiation on the fate of hindered phenol antioxidants in food contact polymers. Analytical and 14C-labelling studies

    Science.gov (United States)

    Allen, David W.; Leathard, David A.; Smith, Christine

    The extractable levels of two hindered phenol antioxidants (Irganox 1076 and Irganox 1010) present in PVC, polyethylene and polypropylene, have been monitored by HPLC techniques following progressive exposure of the polymers to 60Co γ radiation. There is a gradual diminution in the extractable levels of each antioxidant as irradiation progresses as a result of transformation of the antioxidants in the oxidation reactions ensuing during irradiation. Experiments involving the use of a 14C-labelled sample of Irganox 1076 in polyolefins have provided evidence of covalent binding of antioxidant degradation products to the polymer following gamma irradiation. However, there is also evidence of the formation of extractable degradation products, the identity of which is as yet unknown.

  9. Highly efficient aerobic oxidation of alcohols by using less-hindered nitroxyl-radical/copper catalysis: optimum catalyst combinations and their substrate scope.

    Science.gov (United States)

    Sasano, Yusuke; Kogure, Naoki; Nishiyama, Tomohiro; Nagasawa, Shota; Iwabuchi, Yoshiharu

    2015-04-01

    The oxidation of alcohols into their corresponding carbonyl compounds is one of the most fundamental transformations in organic chemistry. In our recent report, 2-azaadamantane N-oxyl (AZADO)/copper catalysis promoted the highly chemoselective aerobic oxidation of unprotected amino alcohols into amino carbonyl compounds. Herein, we investigated the extension of the promising AZADO/copper-catalyzed aerobic oxidation of alcohols to other types of alcohol. During close optimization of the reaction conditions by using various alcohols, we found that the optimum combination of nitroxyl radical, copper salt, and solution concentration was dependent on the type of substrate. Various alcohols, including highly hindered and heteroatom-rich ones, were efficiently oxidized into their corresponding carbonyl compounds under mild conditions with lower amounts of the catalysts. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Septin 7 reduces nonmuscle myosin IIA activity in the SNAP23 complex and hinders GLUT4 storage vesicle docking and fusion

    Energy Technology Data Exchange (ETDEWEB)

    Wasik, Anita A.; Dumont, Vincent [Department of Pathology, University of Helsinki, 00014 Helsinki (Finland); Tienari, Jukka [Department of Pathology, University of Helsinki and Helsinki University Hospital, 00290 Helsinki, 05850 Hyvinkää (Finland); Nyman, Tuula A. [Institute of Biotechnology, University of Helsinki, 00014 Helsinki (Finland); Fogarty, Christopher L.; Forsblom, Carol; Lehto, Markku [Folkhälsan Institute of Genetics, Folkhälsan Research Center, 00290 Helsinki (Finland); Abdominal Center Nephrology, University of Helsinki and Helsinki University Hospital, 000290 Helsinki (Finland); Diabetes& Obesity Research Program, Research Program´s Unit, 00014 University of Helsinki (Finland); Lehtonen, Eero [Department of Pathology, University of Helsinki, 00014 Helsinki (Finland); Laboratory Animal Centre, University of Helsinki, 00014 Helsinki (Finland); Groop, Per-Henrik [Folkhälsan Institute of Genetics, Folkhälsan Research Center, 00290 Helsinki (Finland); Abdominal Center Nephrology, University of Helsinki and Helsinki University Hospital, 000290 Helsinki (Finland); Diabetes& Obesity Research Program, Research Program´s Unit, 00014 University of Helsinki (Finland); Baker IDI Heart & Diabetes Institute, 3004 Melbourne (Australia); Lehtonen, Sanna, E-mail: sanna.h.lehtonen@helsinki.fi [Department of Pathology, University of Helsinki, 00014 Helsinki (Finland)

    2017-01-15

    Glomerular epithelial cells, podocytes, are insulin responsive and can develop insulin resistance. Here, we demonstrate that the small GTPase septin 7 forms a complex with nonmuscle myosin heavy chain IIA (NMHC-IIA; encoded by MYH9), a component of the nonmuscle myosin IIA (NM-IIA) hexameric complex. We observed that knockdown of NMHC-IIA decreases insulin-stimulated glucose uptake into podocytes. Both septin 7 and NM-IIA associate with SNAP23, a SNARE protein involved in GLUT4 storage vesicle (GSV) docking and fusion with the plasma membrane. We observed that insulin decreases the level of septin 7 and increases the activity of NM-IIA in the SNAP23 complex, as visualized by increased phosphorylation of myosin regulatory light chain. Also knockdown of septin 7 increases the activity of NM-IIA in the complex. The activity of NM-IIA is increased in diabetic rat glomeruli and cultured human podocytes exposed to macroalbuminuric sera from patients with type 1 diabetes. Collectively, the data suggest that the activity of NM-IIA in the SNAP23 complex plays a key role in insulin-stimulated glucose uptake into podocytes. Furthermore, we observed that septin 7 reduces the activity of NM-IIA in the SNAP23 complex and thereby hinders GSV docking and fusion with the plasma membrane. - Highlights: • Septin 7, nonmuscle myosin heavy chain IIA (NMHC-IIA) and SNAP23 form a complex. • Knockdown of septin 7 increases NM-IIA activity in the SNAP23 complex. • Insulin decreases septin 7 level and increases NM-IIA activity in the SNAP23 complex. • Septin 7 hinders GSV docking/fusion by reducing NM-IIA activity in the SNAP23 complex.

  11. Septin 7 reduces nonmuscle myosin IIA activity in the SNAP23 complex and hinders GLUT4 storage vesicle docking and fusion

    International Nuclear Information System (INIS)

    Wasik, Anita A.; Dumont, Vincent; Tienari, Jukka; Nyman, Tuula A.; Fogarty, Christopher L.; Forsblom, Carol; Lehto, Markku; Lehtonen, Eero; Groop, Per-Henrik; Lehtonen, Sanna

    2017-01-01

    Glomerular epithelial cells, podocytes, are insulin responsive and can develop insulin resistance. Here, we demonstrate that the small GTPase septin 7 forms a complex with nonmuscle myosin heavy chain IIA (NMHC-IIA; encoded by MYH9), a component of the nonmuscle myosin IIA (NM-IIA) hexameric complex. We observed that knockdown of NMHC-IIA decreases insulin-stimulated glucose uptake into podocytes. Both septin 7 and NM-IIA associate with SNAP23, a SNARE protein involved in GLUT4 storage vesicle (GSV) docking and fusion with the plasma membrane. We observed that insulin decreases the level of septin 7 and increases the activity of NM-IIA in the SNAP23 complex, as visualized by increased phosphorylation of myosin regulatory light chain. Also knockdown of septin 7 increases the activity of NM-IIA in the complex. The activity of NM-IIA is increased in diabetic rat glomeruli and cultured human podocytes exposed to macroalbuminuric sera from patients with type 1 diabetes. Collectively, the data suggest that the activity of NM-IIA in the SNAP23 complex plays a key role in insulin-stimulated glucose uptake into podocytes. Furthermore, we observed that septin 7 reduces the activity of NM-IIA in the SNAP23 complex and thereby hinders GSV docking and fusion with the plasma membrane. - Highlights: • Septin 7, nonmuscle myosin heavy chain IIA (NMHC-IIA) and SNAP23 form a complex. • Knockdown of septin 7 increases NM-IIA activity in the SNAP23 complex. • Insulin decreases septin 7 level and increases NM-IIA activity in the SNAP23 complex. • Septin 7 hinders GSV docking/fusion by reducing NM-IIA activity in the SNAP23 complex.

  12. Personal interests hinder Rail Baltica

    Index Scriptorium Estoniae

    2011-01-01

    Läti seimi liige Janis Reirs leiab, et Rail Baltica ehitus on Moskva ja Riia vahelise raudtee ehitusest prioriteetsem, kuna esimest võib potentsiaalselt finantseerida Euroopa Liit. Transpordiminister Uldis Augulis kohtub oma Venemaa kolleegi Igor Levitiniga 7. aprillil. Peaminister Valdis Dombrovskise sõnul vajavad mõlemad projektid majandusanalüüsi

  13. Semiconducting perovskites (2-XC6H4C2H4NH3)2SnI4 (X = F, Cl, Br): steric interaction between the organic and inorganic layers.

    Science.gov (United States)

    Xu, Zhengtao; Mitzi, David B; Dimitrakopoulos, Christos D; Maxcy, Karen R

    2003-03-24

    Two new semiconducting hybrid perovskites based on 2-substituted phenethylammonium cations, (2-XC(6)H(4)C(2)H(4)NH(3))(2)SnI(4) (X = Br, Cl), are characterized and compared with the previously reported X = F compound, with a focus on the steric interaction between the organic and inorganic components. The crystal structure of (2-ClC(6)H(4)C(2)H(4)NH(3))(2)SnI(4) is solved in a disordered subcell [C2/m, a = 33.781(7) A, b = 6.178(1) A, c = 6.190(1) A, beta = 90.42(3)(o), and Z = 2]. The structure is similar to the known (2-FC(6)H(4)C(2)H(4)NH(3))(2)SnI(4) structure with regard to both the conformation of the organic cations and the bonding features of the inorganic sheet. The (2-BrC(6)H(4)C(2)H(4)NH(3))(2)SnI(4) system adopts a fully ordered monoclinic cell [P2(1)/c, a = 18.540(2) A, b = 8.3443(7) A, c = 8.7795(7) A, beta = 93.039(1)(o), and Z = 2]. The organic cation adopts the anti conformation, instead of the gauche conformation observed in the X = F and Cl compounds, apparently because of the need to accommodate the additional volume of the bromo group. The steric effect of the bromo group also impacts the perovskite sheet, causing notable distortions, such as a compressed Sn-I-Sn bond angle (148.7(o), as compared with the average values of 153.3 and 154.8(o) for the fluoro and chloro compounds, respectively). The optical absorption features a substantial blue shift (lowest exciton peak: 557 nm, 2.23 eV) relative to the spectra of the fluoro and chloro compounds (588 and 586 nm, respectively). Also presented are transport properties for thin-film field-effect transistors (TFTs) based on spin-coated films of the two hybrid semiconductors.

  14. Hindered rotational energy barriers of BH4- tetrahedra in β-Mg(BH4)2 from quasielastic neutron scattering and DFT calculations

    DEFF Research Database (Denmark)

    Blanchard, Didier; Maronsson, Jon Bergmann; Riktor, M.D.

    2012-01-01

    , around the 2-fold (C2) and 3-fold (C3) axes were observed at temperatures from 120 to 440 K. The experimentally obtained activation energies (EaC2 = 39 and 76 meV and EaC3 = 214 meV) and mean residence times between reorientational jumps are comparable with the energy barriers obtained from DFT......In this work, hindered rotations of the BH4- tetrahedra in Mg(BH4)2 were studied by quasielastic neutron scattering, using two instruments with different energy resolution, in combination with density functional theory (DFT) calculations. Two thermally activated reorientations of the BH4- units...... calculations. A linear dependency of the energy barriers for rotations around the C2 axis parallel to the Mg-Mg axis with the distance between these two axes was revealed by the DFT calculations. At the lowest temperature (120 K) only 15% of the BH4- units undergo rotational motion and from comparison with DFT...

  15. What hinders healthcare professionals in promoting physical activity towards cancer patients? The influencing role of healthcare professionals' concerns, perceived patient characteristics and perceived structural factors.

    Science.gov (United States)

    Haussmann, Alexander; Gabrian, Martina; Ungar, Nadine; Jooß, Stefan; Wiskemann, Joachim; Sieverding, Monika; Steindorf, Karen

    2018-05-09

    Despite a large body of evidence showing that physical activity (PA) is beneficial to patients with cancer, healthcare professionals (HCPs) are promoting it too scarcely. Factors that hinder HCPs from promoting PA have remained understudied so far. Using a qualitative approach, this study aimed at a comprehensive description of influencing factors for HCPs' PA promotion behaviour and at identifying the reasons and mechanisms behind them. Semi-structured interviews with 30 HCPs were undertaken with a focus on concerns, patient characteristics and structural factors. Answers were analysed using thematic analysis. Results revealed that HCPs had concerns regarding a physical overexertion and psychological stress for patients with cancer. A patient's physical condition and the assumed interest in PA, often derived from former PA, turned out to be the most crucial patient characteristics influencing if PA is addressed. Structural factors relevant for PA promotion pertained to in-house structures, HCPs' workload, timing and coordination, information material for HCPs and patients and availability of exercise programs. In conclusion, this study revealed undetected concerns of HCPs and underlined the relevance of patient characteristics and structural conditions for HCPs' PA promotion towards patients with cancer. A broader perspective is needed to assess these factors in their influence on HCPs' PA promotion. © 2018 John Wiley & Sons Ltd.

  16. Arthritis patients' motives for (not) wanting to be involved in medical decision-making and the factors that hinder or promote patient involvement.

    Science.gov (United States)

    Nota, Ingrid; Drossaert, Constance H C; Taal, Erik; van de Laar, Mart A F J

    2016-05-01

    The aim of this study is to gain insight into arthritis patients' motives for (not) wanting to be involved in medical decision-making (MDM) and the factors that hinder or promote patient involvement. In-depth semi-structured interviews were conducted with 29 patients suffering from Rheumatoid Arthritis (RA). Many patients perceived the questions about involvement in MDM as difficult, mostly because they were unaware of having a choice. Shared decision-making (SDM) was generally preferred, but the preferred level of involvement varied between and within individuals. Preference regarding involvement may vary according to the type of treatment and the severity of the complaints. A considerable group of respondents would have liked more participation than they had experienced in the past. Perceived barriers could be divided into doctor-related (e.g. a paternalistic attitude), patient-related (e.g. lack of knowledge) and context-related (e.g. too little time to decide) factors. This study demonstrates the complexity of predicting patients' preferences regarding involvement in MDM: most RA patients prefer SDM, but their preference may vary according to the situation they are in and the extent to which they experience barriers in getting more involved. Unawareness of having a choice is still a major barrier for patient participation. The attending physician seems to have an important role as facilitator in enhancing patient participation by raising awareness and offering options, but implementing SDM is a shared responsibility; all parties need to be involved and educated.

  17. Solution-phase synthesis of a hindered N-methylated tetrapeptide using Bts-protected amino acid chlorides: efficient coupling and methylation steps allow purification by extraction.

    Science.gov (United States)

    Vedejs, E; Kongkittingam, C

    2000-04-21

    N-Benzothiazole-2-sulfonyl (Bts)-protected amino acid chlorides were used to prepare the hindered cyclosporin 8-11 tetrapeptide subunit 1. The synthesis was performed via 3a and the deprotected amines 5a, 13, and 19, including three repeated cycles involving N-methylation using iodomethane/potassium carbonate, deprotection of the Bts group, and N-acylation with a N-Bts-amino acid chloride such as 9b or 9c. Among three Bts cleavage methods compared (H3PO2/THF; NaBH4/EtOH; PhSH/K2CO3), the third gave somewhat higher overall yields. N-Acylation of 5a with the Bts-protected N-methylamino acid chloride 10b followed by deprotection was also highly efficient and could be used as an alternative route to 11. Each of the deprotected amines was isolated without chromatography using simple extraction methods to remove neutral byproducts. The tetrapeptide 1 was obtained in analytically pure form as the monohydrate.

  18. Skeletal muscle microRNA and messenger RNA profiling in cofilin-2 deficient mice reveals cell cycle dysregulation hindering muscle regeneration.

    Directory of Open Access Journals (Sweden)

    Sarah U Morton

    Full Text Available Congenital myopathies are rare skeletal muscle diseases presenting in early age with hypotonia and weakness often linked to a genetic defect. Mutations in the gene for cofilin-2 (CFL2 have been identified in several families as a cause of congenital myopathy with nemaline bodies and cores. Here we explore the global messenger and microRNA expression patterns in quadriceps muscle samples from cofillin-2-null mice and compare them with sibling-matched wild-type mice to determine the molecular pathways and mechanisms involved. Cell cycle processes are markedly dysregulated, with altered expression of genes involved in mitotic spindle formation, and evidence of loss of cell cycle checkpoint regulation. Importantly, alterations in cell cycle, apoptosis and proliferation pathways are present in both mRNA and miRNA expression patterns. Specifically, p21 transcript levels were increased, and the expression of p21 targets, such as cyclin D and cyclin E, was decreased. We therefore hypothesize that deficiency of cofilin-2 is associated with interruption of the cell cycle at several checkpoints, hindering muscle regeneration. Identification of these pathways is an important step towards developing appropriate therapies against various congenital myopathies.

  19. Correction: β-Amyrin synthase from Euphorbia tirucalli L. functional analyses of the highly conserved aromatic residues Phe413, Tyr259 and Trp257 disclose the importance of the appropriate steric bulk, and cation-π and CH-π interactions for the efficient catalytic action of the polyolefin cyclization cascade.

    Science.gov (United States)

    Ito, Ryousuke; Nakada, Chika; Hoshino, Tsutomu

    2017-01-18

    Correction for 'β-Amyrin synthase from Euphorbia tirucalli L. functional analyses of the highly conserved aromatic residues Phe413, Tyr259 and Trp257 disclose the importance of the appropriate steric bulk, and cation-π and CH-π interactions for the efficient catalytic action of the polyolefin cyclization cascade' by Ryousuke Ito et al., Org. Biomol. Chem., 2017, 15, 177-188.

  20. Redox regulation of protein tyrosine phosphatase 1B (PTP1B): Importance of steric and electronic effects on the unusual cyclization of the sulfenic acid intermediate to a sulfenyl amide

    Science.gov (United States)

    Sarma, Bani Kanta

    2013-09-01

    The redox regulation of protein tyrosine phosphatase 1B (PTP1B) via the unusual transformation of its sulfenic acid (PTP1B-SOH) to a cyclic sulfenyl amide intermediate is studied by using small molecule chemical models. These studies suggest that the sulfenic acids derived from the H2O2-mediated reactions o-amido thiophenols do not efficiently cyclize to sulfenyl amides and the sulfenic acids produced in situ can be trapped by using methyl iodide. Theoretical calculations suggest that the most stable conformer of such sulfenic acids are stabilized by nO → σ*S-OH orbital interactions, which force the -OH group to adopt a position trans to the S⋯O interaction, leading to an almost linear arrangement of the O⋯S-O moiety and this may be the reason for the slow cyclization of such sulfenic acids to their corresponding sulfenyl amides. On the other hand, additional substituents at the 6-position of o-amido phenylsulfenic acids that can induce steric environment and alter the electronic properties around the sulfenic acid moiety by S⋯N or S⋯O nonbonded interactions destabilize the sulfenic acids by inducing strain in the molecule. This may lead to efficient the cyclization of such sulfenic acids. This model study suggests that the amino acid residues in the close proximity of the sulfenic acid moiety in PTP1B may play an important role in the cyclization of PTP1B-SOH to produce the corresponding sulfenyl amide.

  1. Two steps simultaneous analysis of reactivity of L-norvaline in the T-for-H exchange reaction. Application of Taft equation to influence of Polar effect and steric effect

    International Nuclear Information System (INIS)

    Kataoka, Noriaki; Imaizumi, Hiroshi; Saito, Hiroshi; Sato, Takayuki; Kano, Naoki

    2010-01-01

    In order to quantitatively evaluate the influence of tritium ( 3 H or T) on ecosystem and the reactivity of materials having H atoms, the hydrogen isotope exchange reaction (T-for-H exchange reaction) between L-norvaline and HTO vapor was observed at 50-70degC in the gas-solid system. Applying the A''-McKay plot method to data obtained in the reaction, the rate constants of the functional groups in the material were obtained. Comparing these rate constants, following seven matters have been found in the T-for-H exchange reaction. (1) The reactivity of the functional groups in L-norvaline increases with increasing temperature. (2) As to L-norvaline, 1) the temperature dependence of each functional group increases with the following order: COOH group > NH 2 one. 2) the reactivity of COOH group is 2.2 times greater than that of NH 2 one. (3) As to the influence of the substituent, the reactivity of COOH group is larger than that of the NH 2 one. (4) It seems that the reactivity of the amino acid follows Taft equation. (5) Applying Taft equation, the ratio of influence of polar effect to steric one is 10:0 in NH 2 group, and is 3:7 in COOH one. (6) Using the A - McKay plot method, the reactivity of each functional group in an amino acid is able to be nondestructively, quantitatively and simultaneously analyzed without using masking reagent. (7) The method used in this work may be useful to quickly determine the reactivity of the functional groups in the materials. (author)

  2. Helpful and hindering factors for remission in dysthymia and panic disorder at 9-year follow-up: A mixed methods study

    Directory of Open Access Journals (Sweden)

    Lützen Kim

    2008-07-01

    Full Text Available Abstract Background A better understanding is needed of factors behind the long-term outcome of dysthymic and panic disorders. Combining patients' perceptions of factors that help and hind remission with objective assessments of outcome may give greater insight into mechanisms for maintaining recovery. Methods Twenty-three dysthymic and 15 panic disorder patients participated in a 9-year follow-up investigation of a naturalistic study with psychotherapy and antidepressants. Degree of remission was determined by reassessments with SCID-I & II interviews, self-reported symptoms and life-charting (aided by case records. Qualitative content analysis of in-depth interviews with all 38 patients was done to examine the phenomenon of enduring remission by exploring: 1 perceived helpful and hindering factors, 2 factors common to and specific for the diagnostic groups, 3 convergence between patients' subjective views on remission with objective diagnostic assessments. Results About 50% of the patients were in full or partial remission. Subjective and objective views on degree of remission generally converged, and remission was perceived as receiving 'Tools to handle life'. Common helpful factors were self-understanding, enhanced flexibility of thinking, and antidepressant medication, as well as confidence in the therapist and social support. The perceived main obstacle was difficulty in negotiating treatments. Remitted had overcome the obstacles, whereas many non-remitted had problems expressing their needs. Patients with dysthymia and panic disorder described specific helpful relationships with the therapist: 'As a parent' versus 'As a coach', and specific central areas for change: self-acceptance and resolution of relational problems versus awareness and handling of feelings. Conclusion A general model for recovery from dysthymic and panic disorders is proposed, involving: 1 understanding self and illness mechanisms, 2 enhanced flexibility of thinking

  3. Helpful and hindering factors for remission in dysthymia and panic disorder at 9-year follow-up: a mixed methods study.

    Science.gov (United States)

    Svanborg, Cecilia; Bäärnhielm, Sofie; Aberg Wistedt, Anna; Lützen, Kim

    2008-07-01

    A better understanding is needed of factors behind the long-term outcome of dysthymic and panic disorders. Combining patients' perceptions of factors that help and hind remission with objective assessments of outcome may give greater insight into mechanisms for maintaining recovery. Twenty-three dysthymic and 15 panic disorder patients participated in a 9-year follow-up investigation of a naturalistic study with psychotherapy and antidepressants. Degree of remission was determined by reassessments with SCID-I & II interviews, self-reported symptoms and life-charting (aided by case records). Qualitative content analysis of in-depth interviews with all 38 patients was done to examine the phenomenon of enduring remission by exploring: 1) perceived helpful and hindering factors, 2) factors common to and specific for the diagnostic groups, 3) convergence between patients' subjective views on remission with objective diagnostic assessments. About 50% of the patients were in full or partial remission. Subjective and objective views on degree of remission generally converged, and remission was perceived as receiving 'Tools to handle life'. Common helpful factors were self-understanding, enhanced flexibility of thinking, and antidepressant medication, as well as confidence in the therapist and social support. The perceived main obstacle was difficulty in negotiating treatments. Remitted had overcome the obstacles, whereas many non-remitted had problems expressing their needs. Patients with dysthymia and panic disorder described specific helpful relationships with the therapist: 'As a parent' versus 'As a coach', and specific central areas for change: self-acceptance and resolution of relational problems versus awareness and handling of feelings. A general model for recovery from dysthymic and panic disorders is proposed, involving: 1) understanding self and illness mechanisms, 2) enhanced flexibility of thinking, and 3) change from avoidance coping to approach coping; and

  4. What factors help or hinder the achievement of low SES students? An international comparison using TIMSS 2011 8th grade science data

    Science.gov (United States)

    Bruner, Justin L.

    Focusing on science from a cross-country perspective, this study explores the relationship between 8th grade science achievement and student, teacher, and school characteristics. More specifically, this study will pay special attention to low socio-economic status (SES) students and seek to understand why some disadvantaged students are able to have higher than expected achievement in science given their SES while other disadvantaged students are not able to achieve beyond what would be expected given their background. This study will explore the multi-level relationship between the characteristics of students, their teachers, their schools, and student achievement in science. While looking at students in classrooms and in schools, this work will create as precise as possible a measure of student SES by drawing on recommendations of an expert panel commissioned by the National Association of Educational Progress (NAEP) study. The study uses the most recent cycle (2011) of the Trends in International Math and Science Study (TIMSS), to strategically select a six-country sample from the 45 participating countries. This six-country sample was selected by using the country level achievement and the standard deviation of that achievement. This will create a sample that has a range of equality in achievement and strength in achievement. This allows for making comparisons both across and within countries to better understand variations in the factors of student performance, especially for disadvantaged students. This paper builds on the existing research around socio-economic status (SES) and achievement by exploring in more detail the conditions in schools and classrooms around the world that might magnify or reduce the effect of SES on student achievement. The analysis looks at these questions: "What conditions help low SES students achieve higher than what would be expected given their SES?" and "What conditions hinder low SES students to achieve at or below what would

  5. Signal peptide prediction suggests Mycobacterium tuberculosis curli pilin subunit secretion via the Sec pathway may hinder MTP overexpression in Escherichia coli

    Energy Technology Data Exchange (ETDEWEB)

    Naidoo, N.; Pillay, B.; Bubb, M.; Kumar, A.; Chiliza, T.; Pillay, M.

    2017-07-01

    Introduction Mycobacterium tuberculosis curli pili (MTP) are novel, potential TB diagnostic biomarkers as they are important virulence attributes, unique to the M. tuberculosis complex (MTBC). The production of high quality recombinant transmembrane and secretory proteins that can serve as biomarkers may be challenging due to their secretion attributes. For example, the signal peptide of MTP governed by the classical secretion pathway may hinder the purification of the protein in E. coli systems. In this study, the secretion characteristics of MTP were determined and the cloning, expression and purification of MTP was attempted in E.coli. Materials and methods A fragment of MTP unique to MTBC was cloned into pet101 and pGEX-6P-1 vectors. The clones were confirmed by nucleotide sequencing and expression of the protein was attempted at IPTG concentrations ranging from 0.1mM to 1mM and at temperatures between 25 °C to 37 °C. The pGEX-6P-1/mtp clone expressed protein was purified, yielding a MTP-GST fusion protein and a free GST band that were analysed by LC/MS mass spectrometry. Inclusion body preparation attempted from the pet101/mtp clone yielded two bands at 10 kDa and below 10 kDa, both of which were analysed by LC/MS mass spectrometry. Transcription activity of both the clones was interrogated by real time PCR on the cDNA derived from the induced clones at various time points after induction with IPTG. The signal peptide and protein secretion characteristics of the MTP protein were determined by bioinformatics analysis of the amino acid sequence using publically available software. Results The truncated MTP fragments were successfully cloned in both the vectors as confirmed by nucleotide sequencing. Expression of the pGEX-6P-1/mtp clone using 0.5 mM IPTG at 27 °C demonstrated the presence of the expected fragment at approximately 35 kDa. This was confirmed by Western Blotting using anti-GST antibodies. However, purification of MTP in adequate quantities as a

  6. Signal peptide prediction suggests Mycobacterium tuberculosis curli pilin subunit secretion via the Sec pathway may hinder MTP overexpression in Escherichia coli

    International Nuclear Information System (INIS)

    Naidoo, N.; Pillay, B.; Bubb, M.; Kumar, A.; Chiliza, T.; Pillay, M.

    2017-01-01

    Introduction Mycobacterium tuberculosis curli pili (MTP) are novel, potential TB diagnostic biomarkers as they are important virulence attributes, unique to the M. tuberculosis complex (MTBC). The production of high quality recombinant transmembrane and secretory proteins that can serve as biomarkers may be challenging due to their secretion attributes. For example, the signal peptide of MTP governed by the classical secretion pathway may hinder the purification of the protein in E. coli systems. In this study, the secretion characteristics of MTP were determined and the cloning, expression and purification of MTP was attempted in E.coli. Materials and methods A fragment of MTP unique to MTBC was cloned into pet101 and pGEX-6P-1 vectors. The clones were confirmed by nucleotide sequencing and expression of the protein was attempted at IPTG concentrations ranging from 0.1mM to 1mM and at temperatures between 25 °C to 37 °C. The pGEX-6P-1/mtp clone expressed protein was purified, yielding a MTP-GST fusion protein and a free GST band that were analysed by LC/MS mass spectrometry. Inclusion body preparation attempted from the pet101/mtp clone yielded two bands at 10 kDa and below 10 kDa, both of which were analysed by LC/MS mass spectrometry. Transcription activity of both the clones was interrogated by real time PCR on the cDNA derived from the induced clones at various time points after induction with IPTG. The signal peptide and protein secretion characteristics of the MTP protein were determined by bioinformatics analysis of the amino acid sequence using publically available software. Results The truncated MTP fragments were successfully cloned in both the vectors as confirmed by nucleotide sequencing. Expression of the pGEX-6P-1/mtp clone using 0.5 mM IPTG at 27 °C demonstrated the presence of the expected fragment at approximately 35 kDa. This was confirmed by Western Blotting using anti-GST antibodies. However, purification of MTP in adequate quantities as a

  7. Application of steric exclusion chromatography for the separation of degradation products of the solvent used for the reprocessing of the nuclear fuels; Application de la chromatographie d`exclusion sterique a la separation de produits de degradation du solvant du retraitement des combustibles nucleaires

    Energy Technology Data Exchange (ETDEWEB)

    Pozo, C.

    1993-08-01

    The solvent, used in France in Purex reprocessing plants at La Hague is tributylphosphate (TBP) diluted to 30% with a mixture of branched alkanes, for which the main component is branched dodecane (70%). In order to minimize volumes of organic wastes, we have to maintain Purex solvent qualities and to get rid of degradation products. The subject of this memoir concerns among all the degradation products the heaviest molecules. The separation and the identification of these products have been carried out by preparative steric exclusion chromatography, followed by the analysis of the samples by various analytical methods. An inactive residue containing heavy degradation products was prepared according to the process used in the UP3 La Hague plant. The Analysis of this residue using steric exclusion chromatography and GPC/MS methods, shows the presence of three families of compounds heavier than TBP: the ``dimers of TBP`` (provided from the addition of two molecules of TBP), the ``TBP-alkanes`` (the main molecule is the result of the addition of dodecane with TBP), and ``the functionalized TBP`` (hydroxyled TBP, nitrous TBP, nitrated TBP). Plutonium (IV) retention tests were made on the various fractions generated by steric chromatography. They showed that ``the dimers of TBP`` and ``the functionalized TBP`` families are responsible for that retention. These results confirm the good efficiency of the solvent distillation system operated in UP3 plant which allow the elimination of heavy degradation products of the solvent with the residue and then restore excellent extracting properties for the recycled solvent. (author). 35 figs., 69 refs., 15 tabs.

  8. Two Palladium-Catalyzed Domino Reactions from One Set of Substrates/Reagents: Efficient Synthesis of Substituted Indenes and cis-Stilbenoid Hydrocarbons from the Same Internal Alkynes and Hindered Grignard Reagents

    Science.gov (United States)

    Dong, Cheng-Guo; Yeung, Pik; Hu, Qiao-Sheng

    2008-01-01

    Two types of domino reactions from the same internal alkynes and hindered Grignard reagents based on carbopalladation, Pd-catalyzed cross-coupling reaction and C-H activation strategy are described. The realization of these domino reactions relied on the control of the use of the ligand and the reaction temperature. Our study provides an efficient access to useful polysubstituted indenes and cis-substituted stilbenes, and may offer new means to the development of tandem/domino reactions in a more efficient way. PMID:17217305

  9. Steric Maps to Evaluate the Role of Steric Hindrance on the IPr NHC Ligand

    KAUST Repository

    Poater, Albert; Falivene, Laura; Urbina-Blanco, Cé sar A.; Manzini, Simone; Nolan, Steven P.; Cavallo, Luigi

    2013-01-01

    Density functional theory (DFT) calculations were used to predict and rationalize the effect of the modification of the structure of the prototype 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene) (IPr) N-heterocyclic carbene (NHC) ligand

  10. Packaging conditions hindering fungal growth on cheese

    DEFF Research Database (Denmark)

    Nielsen, Per Væggemose; Haasum, Iben

    1997-01-01

    Fungal contamination is one of the most important quality deteriorating factors on cheese. During the last 5 years we have studied in detail the underlying factors controlling these unwanted processes in a collaborative project financed by the Danish Dairy Board and the Ministry of Agriculture...

  11. Technical Challenges Hindering Development of Robust Wireless ...

    African Journals Online (AJOL)

    PROF. OLIVER OSUAGWA

    2015-12-01

    Dec 1, 2015 ... challenges remain to be resolved, in designing robust wireless networks that can deliver the performance ... demonstrated the first radio transmission from the Isle of ... distances with better quality, less power, and smaller ...

  12. Conformation of hindered piperidines: Spectroscopic evidence for ...

    Indian Academy of Sciences (India)

    Administrator

    presence of an equilibrium mixture of boat forms B1 and B2 for Z isomers of 5–8. For the E isomers of. 5–8, boat form B1 ... C NMR; conformational analysis; boat forms. 1. Introduction. Many piperidine derivatives are found to possess pharmacological activity and form an essential part of the molecular structure of important ...

  13. [What hinders the political participation of women?].

    Science.gov (United States)

    Ramirez, S

    1994-06-01

    Forty years after gaining the right to vote, Colombian women comprise scarcely 8% of persons recently elected to the Colombian Congress. At the municipal and departmental level, women occupy even fewer of the positions. Explanations of women's marginal political participation in terms of stereotypes such as their presumed disinterest or emotionalism reflect androcentric prejudices. Their lack of preparation and social conditioning is also a suspect argument, given that there are no objective forms of measuring preparation for political office, such as examinations or specific requirements. Centers for women's studies have sought explanation in terms of aspects of the social and political organization of society that impede access by women to positions of power. Laws assuring women their political rights have not been sufficient to allow them to participate under equal conditions. The assignment of responsibility for domestic labor exclusively to women is a powerful handicap to their full participation. Moreover, public life has become a costly career in terms of resources, time, and energy. The problem is not that women do not participate in politics, but that they are underrepresented in the centers of power. They comprise half of voters and the majority of members of community and civic associations dealing with problems of everyday life. But the number of women declines as the scale of power increases. Feminists suggest that the problem will not be solved by women assuming the behavior patterns of men. Rather, the governmental and civil elites must overcome norms and practices that perpetuate the subordination of women. Women achieving positions of power should maintain a gender perspective and assist in transforming conditions.

  14. China’s Bureaucracy Hinders Environmental Recovery

    Science.gov (United States)

    Lixin Guan; Ge Sun; Shixiong Cao

    2010-01-01

    Ecosystem restoration efforts have become a booming business in China. Billions of dollars are being spent annually to restore polluted waterways and ecosystems that have been degraded, fragmented, or paved over (Fu et al. 2007; Wang et al. 2007). However, China’s environmental sustainability index remains among the lowest in the world (World Bank 2009; Liu 2010). For...

  15. Undefined cellulase formulations hinder scientific reproducibility.

    Science.gov (United States)

    Himmel, Michael E; Abbas, Charles A; Baker, John O; Bayer, Edward A; Bomble, Yannick J; Brunecky, Roman; Chen, Xiaowen; Felby, Claus; Jeoh, Tina; Kumar, Rajeev; McCleary, Barry V; Pletschke, Brett I; Tucker, Melvin P; Wyman, Charles E; Decker, Stephen R

    2017-01-01

    In the shadow of a burgeoning biomass-to-fuels industry, biological conversion of lignocellulose to fermentable sugars in a cost-effective manner is key to the success of second-generation and advanced biofuel production. For the effective comparison of one cellulase preparation to another, cellulase assays are typically carried out with one or more engineered cellulase formulations or natural exoproteomes of known performance serving as positive controls. When these formulations have unknown composition, as is the case with several widely used commercial products, it becomes impossible to compare or reproduce work done today to work done in the future, where, for example, such preparations may not be available. Therefore, being a critical tenet of science publishing, experimental reproducibility is endangered by the continued use of these undisclosed products. We propose the introduction of standard procedures and materials to produce specific and reproducible cellulase formulations. These formulations are to serve as yardsticks to measure improvements and performance of new cellulase formulations.

  16. Analytic Morse/long-range potential energy surfaces and "adiabatic-hindered-rotor" treatment for a symmetric top-linear molecule dimer: A case study of CH3F-H2

    Science.gov (United States)

    Zhang, Xiao-Long; Ma, Yong-Tao; Zhai, Yu; Li, Hui

    2018-03-01

    A first effective six-dimensional ab initio potential energy surface (PES) for CH3F-H2 which explicitly includes the intramolecular Q3 stretching normal mode of the CH3F monomer is presented. The electronic structure computations have been carried out at the explicitly correlated coupled cluster level of theory [CCSD(T)-F12a] with an augmented correlation-consistent triple zeta basis set. Five-dimensional analytical intermolecular PESs for ν3(CH3F) = 0 and 1 are then obtained by fitting the vibrationally averaged potentials to the Morse/Long-Range (MLR) potential function form. The MLR function form is applied to the nonlinear molecule-linear molecule case for the first time. These fits to 25 015 points have root-mean-square deviations of 0.74 cm-1 and 0.082 cm-1 for interaction energies less than 0.0 cm-1. Using the adiabatic hindered-rotor approximation, three-dimensional PESs for CH3F-paraH2 are generated from the 5D PESs over all possible orientations of the hydrogen monomer. The infrared and microwave spectra for CH3F-paraH2 dimer are predicted for the first time. These analytic PESs can be used for modeling the dynamical behavior in CH3F-(H2)N clusters, including the possible appearance of microscopic superfluidity.

  17. MODIFICATION OF THE ANALYTIC HIERARCHY PROCESS (AHP METHOD USING FUZZY LOGIC: FUZZY AHP APPROACH AS A SUPPORT TO THE DECISION MAKING PROCESS CONCERNING ENGAGEMENT OF THE GROUP FOR ADDITIONAL HINDERING

    Directory of Open Access Journals (Sweden)

    Darko Božanić

    2015-11-01

    Full Text Available This paper presents the modification of the AHP method, which takes into account the degree of suspense of decision maker, that is it allows that decision maker, with a certain degree of conviction (which is usually less than 100%, defines which linguistic expression corresponds to optimality criteria comparison. To determine the criteria weights and alternative values, fuzzy numbers are used since they are very suitable for the expression of vagueness and uncertainty. In this way, after applying the AHP method, we obtained values of criterion functions for each of the examined alternatives, which corresponds to the value determined by the degree of conviction. This provides that for different values of the degree of conviction can be made generation of different sets of criterion functions values. The set model was tested on choosing directions of action of the Group for additional hindering, as a procedure wich is often accompanied by greater or lesser degree of uncertainty of criteria that are necessary in relevant decision making

  18. Accurate Prognostic Awareness Facilitates, Whereas Better Quality of Life and More Anxiety Symptoms Hinder End-of-Life Care Discussions: A Longitudinal Survey Study in Terminally Ill Cancer Patients' Last Six Months of Life.

    Science.gov (United States)

    Tang, Siew Tzuh; Chen, Chen Hsiu; Wen, Fur-Hsing; Chen, Jen-Shi; Chang, Wen-Cheng; Hsieh, Chia-Hsun; Chou, Wen-Chi; Hou, Ming-Mo

    2018-04-01

    Terminally ill cancer patients do not engage in end-of-life (EOL) care discussions or do so only when death is imminent, despite guidelines for EOL care discussions early in their disease trajectory. Most studies on patient-reported EOL care discussions are cross sectional without exploring the evolution of EOL care discussions as death approaches. Cross-sectional studies cannot determine the direction of association between EOL care discussions and patients' prognostic awareness, psychological well-being, and quality of life (QOL). We examined the evolution and associations of accurate prognostic awareness, functional dependence, physical and psychological symptom distress, and QOL with patient-physician EOL care discussions among 256 terminally ill cancer patients in their last six months by hierarchical generalized linear modeling with logistic regression and by arranging time-varying modifiable variables and EOL care discussions in a distinct time sequence. The prevalence of physician-patient EOL care discussions increased as death approached (9.2%, 11.8%, and 18.3% for 91-180, 31-90, and 1-30 days before death, respectively) but only reached significance in the last month. Accurate prognostic awareness facilitated subsequent physician-patient EOL care discussions, whereas better patient-reported QOL and more anxiety symptoms hindered such discussions. The likelihood of EOL care discussions was not associated with levels of physical symptom distress, functional dependence, or depressive symptoms. Physician-patient EOL care discussions for terminally ill Taiwanese cancer patients remain uncommon even when death approaches. Physicians should facilitate EOL care discussions by cultivating patients' accurate prognostic awareness early in their cancer trajectory when they are physically and psychologically competent, with better QOL, thus promoting informed and value-based EOL care decision making. Copyright © 2017 American Academy of Hospice and Palliative

  19. Job resumption status, hindering factors, and interpersonal relationship within post-heart transplant 1 to 4 years as perceived by heart transplant recipients in Taiwan: a between-method triangulation study.

    Science.gov (United States)

    Tseng, P H; Wang, S S; Chang, C L; Shih, F J

    2010-12-01

    This project examined heart transplant (HT) recipients' perspectives of (a) the changes in their working competence (WC), status for job resumption and related factors at 1- to 2-year, 2- to 3-year, and 3- to 4-year stages; and (b) impacts of HT on interpersonal relationships (IPR). We used a between-method triangulation (including qualitative and quantitative data) design. Quantitative data were collected using the Vertical Visual Analogue Scale and Taiwan's version of the World Health Organization Health-Related Quality-of-Life (HRQoL) questionnaire. Six qualitative semistructured questions were further applied to explore social and environmental domains. The Fifty subjects (86% males and 14% females) had an age range from 20 to 70 years old (mean, 47.68 years). Their post-HT time ranged from 1 to 4.1 years with 42%, 42%, and 16% at 1- to 2-, 2- to 3-, or 3- to 4-years post-HT, respectively. Within 6 months, 10% of administration or restaurant staff, and police resumed their jobs. At 6 to 12 months, 8% of administration, quality control, and design and planning staff resumed their jobs. At 12 months, 14% of educators, insurance personnel, managers, informatics engineers, and ironworkers resumed their jobs. Hindering factors to returning to work included (a) physical (ie, lack of energy, second heart attack, recurrence of rejection, physical discomforts of dizziness, memory lapses/lack of concentration or bone pain from osteoporosis); (b) psychological (ie, lack of confidence, worries about discrimination, being different, maladaptation); and (c) environmental (inadequate job opportunities due to poor socioeconomic conditions). Additionally, 34% reported worse IPR after HT due to diet limitations, slower pacing, less contacts with friends, and changes in personality. Reflections on both the meaning and value of life caused 10% to report better IPR with a better personality and positive mindset. By the end of the first postoperative year, the mean score of HRQoL in

  20. Closing the gaps to eliminate mothertochild transmission of HIV MTCT in South Africa: Understanding MTCT case rates factors that hinder the monitoring and attainment of targets and potential game changers

    Directory of Open Access Journals (Sweden)

    U Feucht

    2018-03-01

    Full Text Available Background. Ninety percent of the world’s HIV-positive pregnant women live in 22 countries. These 22 countries, including South Africa (SA have prioritised the elimination of mother-to-child transmission of HIV (EMTCT. Since 2016 all 22 countries recommend lifelong antiretroviral treatment for all HIV-positive pregnant and lactating women. To measure South African national, provincial and district-level progress towards attaining EMTCT, we analysed the number of in utero (IU paedatric HIV infections per 100 000 live births (IU case rate, and synthesised factors hindering the monitoring of EMTCT progress and attainment from the viewpoint of provincial and district-level healthcare managers and implementers. We highlight potential innovations to strengthen health systems and improve EMTCT programme delivery. Methods. We reviewed national-, provincial- and district-level birth HIV testing data from routine National Health Laboratory Services (NHLS records between April 2016 and March 2017. To obtain a qualitative perspective from healthcare managers and implementers, we synthesised information from the nine 2016 provincial-level EMTCT stock-taking workshops. These workshops involve key provincial and district-level staff, mentors and supporting partners. Lastly, we highlight potential innovations presented at these workshops to overcome operational challenges. Results. The national IU mother-to-child transmission (MTCT rate was 0.9%, which translated to an IU case rate of 245 HIV-positive neonates per 100 000 live births. Provincial IU percent MTCT risk ranged from 0.6% to 1.3%, with IU case rates ranging between 168 and 325 cases per 100 000 live births. District-level IU percent MTCT risk ranged from 0.4% to 1.9%. Potential game changers include: pre-conception counselling to optimise maternal-partner health, weekly dissemination of HIV polymerase chain reaction (PCR and viral load reports from the NHLS to specific individuals who

  1. Chlorin photosensitizers sterically designed to prevent self-aggregation.

    Science.gov (United States)

    Uchoa, Adjaci F; de Oliveira, Kleber T; Baptista, Mauricio S; Bortoluzzi, Adailton J; Iamamoto, Yassuko; Serra, Osvaldo A

    2011-11-04

    The synthesis and photophysical evaluation of new chlorin derivatives are described. The Diels-Alder reaction between protoporphyrin IX dimethyl ester and substituted maleimides furnishes endo-adducts that completely prevent the self-aggregation of the chlorins. Fluorescence, resonant light scattering (RLS) and (1)H NMR experiments, as well as X-ray crystallographic have demonstrated that the configurational arrangement of the synthesized chlorins prevent π-stacking interactions between macrocycles, thus indicating that it is a nonaggregating photosensitizer with high singlet oxygen (Φ(Δ)) and fluorescence (Φ(f)) quantum yields. Our results show that this type of synthetic strategy may provide the lead to a new generation of PDT photosensitizers.

  2. Picric acid sensing and capture by a sterically encumbered azo ...

    Indian Academy of Sciences (India)

    Dhananjayan Kaleeswaran

    2018-01-25

    Jan 25, 2018 ... above observations in mind, here we demonstrate how the presence of bulky ... can affect the azo-polymerization process, PNACs sens- ing ability and CO2 uptake ... on a JEOL model JSM-7600F electron microscope, operat- ing at the .... i PrTAPB is flanked by two isopropyl groups and hence results in a ...

  3. Picric acid sensing and capture by a sterically encumbered azo ...

    Indian Academy of Sciences (India)

    Dhananjayan Kaleeswaran

    2018-01-25

    Jan 25, 2018 ... leather, pesticide and pharmaceutical industries results in increased .... Experimental ... vents were purified according to standard procedures prior to their use.31 .... precipitate was filtered and washed with THF to remove the unreacted i ... is insoluble in most organic solvents, e.g., acetone, ace- tonitrile ...

  4. SAXS study of sterically stabilized lipid nanocarriers functionalized by DNA

    Czech Academy of Sciences Publication Activity Database

    Angelov, Borislav; Angelova, A.; Filippov, Sergey K.; Karlsson, G.; Terrill, N.; Lesieur, S.; Štěpánek, Petr

    2012-01-01

    Roč. 351, č. 1 (2012), s. 012004 ISSN 1742-6588. [SANS-YuMO User Meeting. Dubna, 27.05.2011-30.05.2011] Institutional research plan: CEZ:AV0Z40500505 Keywords : SAXS * vesicles * self-assembly Subject RIV: CD - Macromolecular Chemistry

  5. Electronic and steric effects in regioselective tritiation of anilides

    Energy Technology Data Exchange (ETDEWEB)

    OOhashi, Kunio; Udo, Masato (Chiba Univ. (Japan). Coll. of Arts and Sciences)

    1992-07-01

    Acetanilide, propionanilide and isobutyranilide were tritiated at the ortho positions with very high regioselectivity by heating with HTO in the presence of RhCl[sub 3][center dot]3H[sub 2]O in N, N-dimethylformamide (DMF). In this reaction for pivalanilide the specific activity alone was determined, because attempts to establish the regioselectivity were unsuccessful. The extent of tritium incorporation decreased with increasing bulkiness of the alkyl groups. Only slight tritium was introduced by the same reaction for trifluoroacetanilide, which would probably be attributed to a strong electron-attracting property of the trifluoromethyl group. The above findings give support to the previous suggestion that the present isotope exchange reaction proceeds via an initial coordination of the nitrogen atom of anilides to the rhodium (III) chloride trihydrate catalyst. (author).

  6. Sterically stabilized spongosomes for multidrug delivery of anticancer nanomedicines

    Czech Academy of Sciences Publication Activity Database

    Chen, Y.; Angelova, A.; Angelov, Borislav; Drechsler, M.; Garamus, V. M.; Willumeit-Römer, R.; Zou, A.

    2015-01-01

    Roč. 3, č. 39 (2015), s. 7734-7744 ISSN 2050-750X R&D Projects: GA ČR(CZ) GC15-10527J Institutional support: RVO:61389013 Keywords : SAXS * soft matter * nanoparticles Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 4.872, year: 2015

  7. Steric effects in peptide and protein exchange with activated disulfides.

    Science.gov (United States)

    Kerr, Jason; Schlosser, Jessica L; Griffin, Donald R; Wong, Darice Y; Kasko, Andrea M

    2013-08-12

    Disulfide exchange is an important bioconjugation tool, enabling chemical modification of peptides and proteins containing free cysteines. We previously reported the synthesis of a macromer bearing an activated disulfide and its incorporation into hydrogels. Despite their ability to diffuse freely into hydrogels, larger proteins were unable to undergo in-gel disulfide exchange. In order to understand this phenomenon, we synthesized four different activated disulfide-bearing model compounds (Mn = 300 Da to 10 kDa) and quantified their rate of disulfide exchange with a small peptide (glutathione), a moderate-sized protein (β-lactoglobulin), and a large protein (bovine serum albumin) in four different pH solutions (6.0, 7.0, 7.4, and 8.0) to mimic biological systems. Rate constants of exchange depend significantly on the size and accessibility of the thiolate. pH also significantly affects the rate of reaction, with the faster reactions occurring at higher pH. Surprisingly, little difference in exchange rates is seen between macromolecular disulfides of varying size (Mn = 2 kDa - 10 kDa), although all undergo exchange more slowly than their small molecule analogue (MW = 300 g/mol). The maximum exchange efficiencies (% disulfides exchanged after 24 h) are not siginificantly affected by thiol size or pH, but somewhat affected by disulfide size. Therefore, while all three factors investigated (pH, disulfide size, and thiolate size) can influence the exchange kinetics and extent of reaction, the size of the thiolate and its accessibility plays the most significant role.

  8. Iron Catalyzed Cycloaddition of Alkynenitriles and Alkynes

    Science.gov (United States)

    D’Souza, Brendan R.; Lane, Timothy K.

    2011-01-01

    The combination of Fe(OAc)2 and an electron-donating, sterically-hindered pyridyl bisimine ligand catalyzes the cycloaddition of alkynenitriles and alkynes. A variety of substituted pyridines were obtained in good yields. PMID:21557582

  9. Hindered El Transitions in Eu155 and Tb161

    International Nuclear Information System (INIS)

    Malmskog, Sven G.

    1965-02-01

    The absolute E1 transition probabilities from the 3/2 + (411), 5/2 - (532) and 7/2 - (523) single particle levels in Eu 155 and Tb 161 have been measured by the method of delayed coincidences. This gave half lives of T 1/2 1/2 = (1.38 ± 0.06) ns for the 104.4 and 246 keV levels in Eu 155 . T 1/2 = (0.84 ± 0.04) ns and T 1/2 161 . The result has been compared with the calculations of a single particle in a deformed potential made by Nilsson

  10. Ebola Policies That Hinder Epidemic Response by Limiting Scientific Discourse

    OpenAIRE

    Asgary, Ramin; Pavlin, Julie A.; Ripp, Jonathan A.; Reithinger, Richard; Polyak, Christina S.

    2015-01-01

    There is an unprecedented epidemic of Ebola virus disease (EVD) in west Africa. There has been a strong response from dedicated health professionals. However, there have also been irrational and fear-based responses that have contributed to misallocation of resources, stigma, and deincentivizing volunteers to combat Ebola at its source. Recently, the State of Louisiana Department of Health and Hospitals issued a ban on those coming from affected countries wishing to attend the annual meetings...

  11. Congressional Oversight of Homeland Security: Help or Hinderance?

    Science.gov (United States)

    2012-12-01

    1956, the SASC identified what they viewed as a duplication of efforts between the Army and the Air Force. The Army had sought to fund a Nike ...The “ Nike -Talos dispute” was only one of several disagreements between services Congress mediated in the late 1950s.218 As Thomas McNaugher wrote in

  12. Ethnic Minorities' Impression Management in the Interview: Helping or Hindering?

    Science.gov (United States)

    Derous, Eva

    2017-01-01

    Cross-cultural impression management (IM) has not been considered much, which is remarkable given the fast rate at which the labor market is becoming multicultural. This study investigated whether ethnic minorities and majorities differed in their preference for IM-tactics and how this affected ethnic minorities' interview outcomes. A preliminary study (focus groups/survey) showed that ethnic minorities (i.e., Arab/Moroccans) preferred 'entitlements' whereas majorities (i.e., Flemish/Belgians) preferred 'opinion conformity' as IM-tactics. An experimental follow-up study among 163 ethnic majority raters showed no main effect of IM-tactics on interview ratings. Ethnic minorities' use of IM-tactics only affected interview ratings if rater characteristics were considered. Specifically, interview ratings were higher when ethnic minorities used opinion conformity (i.e., majority-preferred IM-tactic) and lower when minorities used entitlements (i.e., minority-preferred IM-tactic) if recruiters were high in social dominance orientation, and when they felt more experienced/proficient with interviewing. IM-tactics are a human capital factor that might help applicants to increase their job chances on the labor market. It is concluded that ethnic minority applicants' preferences for certain IM-tactics might lead to bias even in structured interview settings, but that this depends on ethnic majority recruiters' interview experience and ingroup/outgroup attitudes. Implications for research and practice are discussed.

  13. High freight rates hinder oil markets' return to equilibrium

    International Nuclear Information System (INIS)

    Anon

    2005-01-01

    Hurricane damage to refineries in the US has created shortages of refined products there, boosting imports and sending freight rates across the Atlantic to record levels. The situation was made worse for a time by a strike at France's main oil terminals in the Mediterranean, which prevented some oil tankers from being rapidly redeployed to routes across the Atlantic. Worldscale (WS) rates for routes from the UK and Europe to the US Atlantic and Gulf Coasts rose well above WS500 for clean tonnage during October. High rates were nevertheless not simply confined to product tankers crossing the Atlantic. Rates for crude tankers to the US have also risen, and tightness has begun to appear in some other markets as well. The net result has been to slow down the movement of oil from regions of surplus to those of scarcity, depressing prices in the former and keeping them at high levels in the latter. Atlantic tanker markets look like remaining tight for the rest of the year and perhaps beyond. (author)

  14. Hindered protein dynamics in the presence of a cryoprotecting agent

    Energy Technology Data Exchange (ETDEWEB)

    Koeper, I. [Laboratoire Leon Brillouin, CEA Saclay, 91191 Gif-sur-Yvette (France); Physikdepartment E13, TU Muenchen, 85747 Garching (Germany); Bellissent-Funel, M.C. [Laboratoire Leon Brillouin, CEA Saclay, 91191 Gif-sur-Yvette (France)

    2002-07-01

    We present a study of the influence of trehalose, a well-known cryoprotecting disaccharide, on the dynamics of a protein, the C-phycocyanin. The dynamics is investigated in a time range from some picoseconds to several nanoseconds using different neutron-scattering techniques. Data obtained on samples containing hydrated powders of the protein in the presence of trehalose are compared to that of the protein alone, studied by neutron-scattering techniques as well as by molecular dynamics simulations. The analysis of time-of-flight data gives access to the geometry of the observed motions. These motions can be described via a model of a particle diffusing inside a sphere. We observe a slowing down of the movements of the protein due to the presence of trehalose of one to two orders of magnitude, while the geometry of the motions is conserved. (orig.)

  15. Corporal Punishment: Does It Hinder the Development of Children?

    Science.gov (United States)

    Chenoweth, T.; Just, H.

    Noting that parents' use of corporal punishment to discipline their children remains a strongly debated issue, this paper examines the impact of corporal punishment on children's development, focusing primarily on its long-term effectiveness. The paper presents the history of spanking in the United States, including public opinion on corporal…

  16. Action plans can interact to hinder or facilitate reach performance.

    Science.gov (United States)

    Fournier, Lisa R; Wiediger, Matthew D; Taddese, Ezana F

    2015-11-01

    Executing a reach action can be delayed while retaining another action in working memory (WM) if the two action plans partly overlap rather than do not overlap. This delay (partial repetition cost) occurs when reach responses are under cognitive control. In this study, we investigated whether facilitation (a partial repetition benefit) occurs when reach responses are automatic. We also examined whether the hemisphere controlling the limb or selection of the preferred limb (based on a free-reach task) influences reach performance when the actions partly overlap. Left- and right-handers reached to different stimulus locations to the left and right of body midline with their ipsilateral hand while maintaining an action plan in WM that required the same or the different hand. The results showed a partial repetition benefit for spatially compatible reaches to left and right stimulus locations far from the body midline, but not for those near the body midline. Also, no partial repetition cost was found at any of the stimulus-reach locations. This indicates that automatic reach responses that partly overlap with an action plan maintained in WM are not delayed, but instead can be facilitated (partial repetition benefit). The roles of hemisphere and reach-hand preference in action control and the importance of the degree of feature overlap in obtaining a partial repetition benefit (and cost) are discussed.

  17. Constraints that help or hinder creative performance : A motivational approach

    NARCIS (Netherlands)

    Roskes, Marieke

    2015-01-01

    Threatening situations, in which people fear negative outcomes or failure, evoke avoidance motivation. Avoidance motivation, in turn, evokes a focused, systematic and effortful way of information processing that has often been linked to reduced creativity. This harmful effect of avoidance motivation

  18. Focus on ecological weed management : what is hindering adoption?

    NARCIS (Netherlands)

    Bastiaans, L.; Paolini, R.; Baumann, D.T.

    2008-01-01

    Despite increased concerns regarding the heavy reliance of many cropping systems on chemical weed control, adoption of ecological weed management practices is only steadily progressing. For this reason, this paper reflects on both the possibilities and limitations of cultural weed control practices.

  19. Enemies at work : can they hinder your career?

    NARCIS (Netherlands)

    Moerbeek, H.H.S.; Need, A.

    2003-01-01

    This paper addresses the question to what extent foes deteriorate a person's labor market position and block persons in their labor market position. We improve upon earlier research by explicitly focusing on the negative effects of social capital. A second way to improve upon earlier findings is to

  20. Does genetic diversity hinder parasite evolution in social insect colonies?

    DEFF Research Database (Denmark)

    Hughes, William Owen Hamar; Boomsma, Jacobus Jan

    2006-01-01

    of host genetic diversity on parasite evolution by carrying out serial passages of a virulent fungal pathogen through leaf-cutting ant workers of known genotypes. Parasite virulence increased over the nine-generation span of the experiment while spore production decreased. The effect of host relatedness...... upon virulence appeared limited. However, parasites cycled through more genetically diverse hosts were more likely to go extinct during the experiment and parasites cycled through more genetically similar hosts had greater spore production. These results indicate that host genetic diversity may indeed...

  1. Factors Hindering the Accessibility of Agricultural Credit by Farmers ...

    African Journals Online (AJOL)

    The problems encountered in processing loan application include; high transaction cost, administrative bottleneck that leads to late disbursement of loan. In securing credit facilities, the study also identified some problems such as; inadequate credit information, bank stringent conditions, location of lending bank and ...

  2. The Threat of Security: Hindering Technology Integration in the Classroom

    Science.gov (United States)

    Robinson, LeAnne K.; Brown, Abbie; Green, Tim

    2007-01-01

    For the last year the authors have been gathering examples of how perceived "threats of security" are hampering the integration of technology in teaching and learning. They hope that educators will examine both the challenges of increased security demands and ways in which security might enhance, rather than detract from, the use of technology for…

  3. Parental Care Aids, but Parental Overprotection Hinders, College Adjustment

    Science.gov (United States)

    Klein, Matthew B.; Pierce, John D., Jr.

    2010-01-01

    Previous work has shown that students who have troublesome relationships with their parents show higher risk factors for poorer college adjustment. In the present study, we focused on the balance between two key aspects of parenting style, parental care and overprotection, as they affect the transition to college life. Eighty-three undergraduate…

  4. Visual Information Can Hinder Working Memory Processing of Speech

    Science.gov (United States)

    Mishra, Sushmit; Lunner, Thomas; Stenfelt, Stefan; Ronnberg, Jerker; Rudner, Mary

    2013-01-01

    Purpose: The purpose of the present study was to evaluate the new Cognitive Spare Capacity Test (CSCT), which measures aspects of working memory capacity for heard speech in the audiovisual and auditory-only modalities of presentation. Method: In Experiment 1, 20 young adults with normal hearing performed the CSCT and an independent battery of…

  5. Factors Motivating and Hindering Information and Communication Technologies Action Competence

    Science.gov (United States)

    Kurt, Adile Askim; Akbulut, Yavuz; Odabasi, H. Ferhan; Ceylan, Beril; Kuzu, Elif Bugra; Donmez, Onur; Izmirli, Ozden Sahin

    2013-01-01

    Information and Communication Technologies Action Competence (ICTAC) can be defined as "individuals' motivation and capacity to voluntarily employ their ICT skills for initiating or taking part in civic actions". Since academic staff and teachers in ICT related fields have crucial roles in training action-competent individuals, this…

  6. Diastereoselectivity in the reduction of bicyclic enones with hindered hydrides

    OpenAIRE

    Camozzato, Andreza C.; Tenius, Beatriz S. M.; Oliveira, Eduardo R. de; Viegas Jr., Cláudio; Victor, Maurício M.; Silveira, Leandro G. da

    2008-01-01

    Reduction of five substituted octalones employing lithium tri-sec-butylborohydride (L-selectride®) in THF and ethyl ether led to allylic alcohols with moderate diastereoselectivity. The stereoselectivity of addition of bulky hydrides showed to be different from most examples in the literature and was strongly influenced by substitution on the octalone ring.

  7. Diastereoselectivity in the reduction of bicyclic enones with hindered hydrides

    International Nuclear Information System (INIS)

    Camozzato, Andreza C.; Tenius, Beatriz S. M.; Oliveira, Eduardo R. de; Viegas Junior, Claudio; Victor, Mauricio M.; Silveira, Leandro G. da

    2008-01-01

    Reduction of five substituted octalones employing lithium tri-sec-butylborohydride (L-selectride R ) in THF and ethyl ether led to allylic alcohols with moderate diastereoselectivity. The stereoselectivity of addition of bulky hydrides showed to be different from most examples in the literature and was strongly influenced by substitution on the octalone ring. (author)

  8. Factors that Hinder Parents from the Communicating of Sexual ...

    African Journals Online (AJOL)

    Parent-adolescent communication about sexual matters is one of the means that encourages adolescents to adopt responsible sexual behaviour. However, parents do not discuss sexual matters with adolescents and those who discuss to some extent; little information about sexuality is provided. This study, was, therefore ...

  9. The nuclear invasion hinders coal's growth

    Energy Technology Data Exchange (ETDEWEB)

    Soras, C.G.; Stodden, J.R.

    1986-09-01

    Although there were favourable signs for coal at the start of the year, coal exports for the USA are now down and industry employment continues to dwindle; coal's prospects have been hurt by the arrival of more nuclear generating capacity and also the fall in world oil prices. Coal inventories have come under pressure: Discusses the possibility of growth in the context of the world economy and the effect of interest rates on the coal market.

  10. Ethnic Minorities’ Impression Management in the Interview: Helping or Hindering?

    Science.gov (United States)

    Derous, Eva

    2017-01-01

    Cross-cultural impression management (IM) has not been considered much, which is remarkable given the fast rate at which the labor market is becoming multicultural. This study investigated whether ethnic minorities and majorities differed in their preference for IM-tactics and how this affected ethnic minorities’ interview outcomes. A preliminary study (focus groups/survey) showed that ethnic minorities (i.e., Arab/Moroccans) preferred ‘entitlements’ whereas majorities (i.e., Flemish/Belgians) preferred ‘opinion conformity’ as IM-tactics. An experimental follow-up study among 163 ethnic majority raters showed no main effect of IM-tactics on interview ratings. Ethnic minorities’ use of IM-tactics only affected interview ratings if rater characteristics were considered. Specifically, interview ratings were higher when ethnic minorities used opinion conformity (i.e., majority-preferred IM-tactic) and lower when minorities used entitlements (i.e., minority-preferred IM-tactic) if recruiters were high in social dominance orientation, and when they felt more experienced/proficient with interviewing. IM-tactics are a human capital factor that might help applicants to increase their job chances on the labor market. It is concluded that ethnic minority applicants’ preferences for certain IM-tactics might lead to bias even in structured interview settings, but that this depends on ethnic majority recruiters’ interview experience and ingroup/outgroup attitudes. Implications for research and practice are discussed. PMID:28203211

  11. Ethnic Minorities? Impression Management in the Interview: Helping or Hindering?

    OpenAIRE

    Derous, Eva

    2017-01-01

    Cross-cultural impression management (IM) has not been considered much, which is remarkable given the fast rate at which the labor market is becoming multicultural. This study investigated whether ethnic minorities and majorities differed in their preference for IM-tactics and how this affected ethnic minorities’ interview outcomes. A preliminary study (focus groups/survey) showed that ethnic minorities (i.e., Arab/Moroccans) preferred ‘entitlements’ whereas majorities (i.e., Flemish/Belgians...

  12. What helps and what hinders team work - Perspectives of Nigerian ...

    African Journals Online (AJOL)

    LBS Management Review. Journal Home · ABOUT THIS JOURNAL · Advanced Search · Current Issue · Archives · Journal Home > Vol 7, No 2 (2002) >. Log in or Register to get access to full text downloads.

  13. Hindered Csbnd N bond rotation in triazinyl dithiocarbamates

    Science.gov (United States)

    Jung, Taesub; Do, Hee-Jin; Son, Jongwoo; Song, Jae Hee; Cha, Wansik; Kim, Yeong-Joon; Lee, Kyung-Koo; Kwak, Kyungwon

    2018-01-01

    The substituent and solvent effects on the rotation around a Csbnd N amide bond were studied for a series of triazine dibenzylcarbamodithioates. The Gibbs free energies (ΔG‡) were measured to be 16-18 kcal/mol in DMSO-d6 and toluene-d8 using variable-temperature nuclear magnetic resonance (VT-1H NMR) spectroscopy. Density functional theory (DFT) calculations reproduced the experimental observations with various substituents, as well as solvents. From the detailed analysis of the DFT results, we found that the electron donating dibenzyl amine group increased the electron population on the triazinyl ring, which decreased the rotational barrier of the Csbnd N bond in the dithiocarbamate group attached to the triazinyl ring. The higher electron population on the triazine moiety stabilizes the partial double bond character of the Ssbnd C bond, which competitively excludes the double bond character of the Csbnd N bond. Therefore, the rotational dynamics of the Csbnd N bond in dithiocarbamates can be a sensitive probe to small differences in the electron population of substituents on sulfur.

  14. Nuclear in Europe: waning appetites hinder new technology

    International Nuclear Information System (INIS)

    Anon.

    1993-01-01

    The nuclear industry's failure to produce new types of fission reactors which prove reliable and cost-effective within timescales acceptable to governments and public utilities is, it is argued, behind the current waning interest in new technology research programs. Public funds are less readily available to finance new reactor design development programs and this trend is likely to continue. Examples are given of these trends in the United States of America, the United Kingdom, France and Germany. (UK)

  15. An outbreak of sea cucumbers hinders coral recruitment

    Science.gov (United States)

    Zhang, Yu-Yang; McCook, Laurence; Jiang, Lei; Lian, Jian-Sheng; Liu, Sheng; Huang, Hui

    2018-06-01

    An outbreak of a small sessile sea cucumber, Ocnus sanya, occurred on the degraded Luhuitou coral reef in Sanya Bay, Hainan, China. This study explored the pattern of distribution of O. sanya on the reef and the impacts of the high abundance of O. sanya on post-settlement mortality of Pocillopora damicornis recruits. The density of O. sanya ranged from about 500 to over 2000 individuals m-2 with 10.95-23.69% cover on hard substrate. Terracotta tiles with O. sanya on the surface accumulated 19.7% more surface sediment than those without sea cucumbers. Post-settlement P. damicornis recruits had significantly higher mortality on terracotta tiles with O. sanya than those without O. sanya after 21 d. Overall, O. sanya appears to increase sediment stress and inhibit coral recruitment, exacerbating the degradation of Luhuitou Reef. This study raises the possibility that such novel outbreak species could contribute significant additional stress on coral reefs at larger scales.

  16. Is inexpensive natural gas hindering the grid energy storage industry?

    International Nuclear Information System (INIS)

    Hittinger, Eric; Lueken, Roger

    2015-01-01

    Grid energy storage is a maturing technology and forecasts of the industry's growth have been promising. However, recent years have realized little growth in actual deployments of grid-level storage and several high-profile storage companies and projects have failed. We hypothesize that falling natural gas prices have significantly reduced the potential profit from many U.S. energy storage projects since 2009 and quantify that effect. We use engineering–economic models to calculate the monthly revenue to energy storage devices providing frequency regulation and energy arbitrage in several electricity markets and compare that revenue to prevailing natural gas prices. We find that flywheel devices providing frequency regulation were profitable in months when natural gas prices were above $7/mcf, but face difficulties at current prices (around $4/mcf). For energy arbitrage alone, we find that the breakeven capital cost for large-scale storage was around $300/kWh in several key locations in 2004–2008, but is around $100/kWh in the same locations today. Though cost and performance improvements have been continually decreasing the effective cost of energy services from storage, fundamental market signals indicating the need for energy storage are at or near 10-year lows for both energy arbitrage and frequency regulation. - Highlights: • We use engineering–economic models to determine breakeven capital cost of storage. • Two applications are examined: frequency regulation and energy arbitrage. • For both services, potential revenue has decreased significantly since 2008. • We show a high correlation of revenue with natural gas price. • We demonstrate a causal relationship using the PHORUM grid modeling software.

  17. Tumor Vessel Compression Hinders Perfusion of Ultrasonographic Contrast Agents

    Directory of Open Access Journals (Sweden)

    Mirco Galiè

    2005-05-01

    Full Text Available Contrast-enhanced ultrasound (CEUS is an advanced approach to in vivo assessment of tumor vascularity and is being increasingly adopted in clinical oncology. It is based on 1- to 10 μm-sized gas microbubbles, which can cross the capillary beds of the lungs and are effective echo enhancers. It is known that high cell density, high transendothelial fluid exchange, and poorly functioning lymphatic circulation all provoke solid stress, which compresses vessels and drastically reduces tumor blood flow. Given their size, we supposed that the perfusion of microbubbles is affected by anatomic features of tumor vessels more than are contrast agents traditionally used in dynamic contrast-enhanced magnetic resonance imaging (DCE-MRI. Here, we compared dynamic information obtained from CEUS and DCE-MRI on two experimental tumor models exhibiting notable differences in vessel anatomy. We found that tumors with small, flattened vessels show a much higher resistance to microbubble perfusion than to MRI contrast agents, and appear scarcely vascularized at CEUS examination, despite vessel volume adequate for normal function. Thus, whereas CEUS alone could induce incorrect diagnosis when tumors have small or collapsed vessels, integrated analysis using CEUS and DCE-MRI allows in vivo identification of tumors with a vascular profile frequently associated with malignant phenotypes.

  18. Do Electronic Health Records Help or Hinder Medical Education?

    OpenAIRE

    Peled, Jonathan U.; Sagher, Oren; Morrow, Jay B.; Dobbie, Alison E.

    2009-01-01

    Background to the Debate Background to the debate: Many countries worldwide are digitizing patients' medical records. In the United States, the recent economic stimulus package (?the American Recovery and Reinvestment Act of 2009?), signed into law by President Obama, includes $US17 billion in incentives for health providers to switch to electronic health records (EHRs). The package also includes $US2 billion for the development of EHR standards and best-practice guidelines. What impact will ...

  19. Tumor Vessel Compression Hinders Perfusion of Ultrasonographic Contrast Agents1

    Science.gov (United States)

    Galiè, Mirco; D'Onofrio, Mirko; Montani, Maura; Amici, Augusto; Calderan, Laura; Marzola, Pasquina; Benati, Donatella; Merigo, Flavia; Marchini, Cristina; Sbarbati, Andrea

    2005-01-01

    Abstract Contrast-enhanced ultrasound (CEUS) is an advanced approach to in vivo assessment of tumor vascularity and is being increasingly adopted in clinical oncology. It is based on 1- to 10 µm-sized gas microbubbles, which can cross the capillary beds of the lungs and are effective echo enhancers. It is known that high cell density, high transendothelial fluid exchange, and poorly functioning lymphatic circulation all provoke solid stress, which compresses vessels and drastically reduces tumor blood flow. Given their size, we supposed that the perfusion of microbubbles is affected by anatomic features of tumor vessels more than are contrast agents traditionally used in dynamic contrast-enhanced magnetic resonance imaging (DCE-MRI). Here, we compared dynamic information obtained from CEUS and DCE-MRI on two experimental tumor models exhibiting notable differences in vessel anatomy. We found that tumors with small, flattened vessels show a much higher resistance to microbubble perfusion than to MRI contrast agents, and appear scarcely vascularized at CEUS examination, despite vessel volume adequate for normal function. Thus, whereas CEUS alone could induce incorrect diagnosis when tumors have small or collapsed vessels, integrated analysis using CEUS and DCE-MRI allows in vivo identification of tumors with a vascular profile frequently associated with malignant phenotypes. PMID:15967105

  20. Ebola policies that hinder epidemic response by limiting scientific discourse.

    Science.gov (United States)

    Asgary, Ramin; Pavlin, Julie A; Ripp, Jonathan A; Reithinger, Richard; Polyak, Christina S

    2015-02-01

    There is an unprecedented epidemic of Ebola virus disease (EVD) in west Africa. There has been a strong response from dedicated health professionals. However, there have also been irrational and fear-based responses that have contributed to misallocation of resources, stigma, and deincentivizing volunteers to combat Ebola at its source. Recently, the State of Louisiana Department of Health and Hospitals issued a ban on those coming from affected countries wishing to attend the annual meetings of American Society of Tropical Medicine and Hygiene and the American Public Health Association, both of which were held in New Orleans. We argue against such policies, question evidence and motivations, and discuss their practical and ethical implications in hampering effective responses to EVD by the scientific community. We aim to shed light on this issue and its implications for the future of public health interventions, reflect on the responsibility of health providers and professional societies as advocates for patients and the public health, and call for health professionals and societies to work to challenge inappropriate political responses to public health crises. © The American Society of Tropical Medicine and Hygiene.

  1. Factors that Hinder Parents from the Communicating of Sexual ...

    African Journals Online (AJOL)

    2Directorate of Research, Ethics and Consultancy, College of Medicine and Health Sciences, ... Parent-adolescent communication about sexual matters is one of the means that ... and media to promote the strategy of parent-adolescent.

  2. Does Inward FDI Promote or Hinder Outward FDI?

    DEFF Research Database (Denmark)

    Liu, Ying; Li, Ming Hua; Lu, Jiangyong

    In this paper we evaluate the mechanisms underlying dynamic linkages between inward FDI and outward internationalization in the Chinese automobile industry. While several studies have examined the relationship between outward and inward investment using empirical data, this is among the first to ...... may be more driven to expand internationally while firms with IJVs may face constraints from venturing abroad. Our study further delineates strategies for how automakers without IJVs may rely on external growth to springboard back into the domestic car market....

  3. Social Factors and Performance of Elite which Hinder Organizational Development

    Directory of Open Access Journals (Sweden)

    Vladimir Boguslavski

    2009-06-01

    Full Text Available Despite possible differences in official ideology the drawbacks of social organization and the absence of sound approach to social and personal conflicts cause constant demolition of existing formal institutions for the sake of the survival of the system. The neglect of these drawbacks brings about old problems to be transferred to the “new” state. The level of social and human capital and its proper utilization guarantees progressive development. The shifts in organizational policy is also reflected by the consequent shift in the theoretical paradigm, from treatment of a participant of the structure as an object, then as the user and finally as the client. The lack of social capital generates a vicious cycle, which brings about the necessity of object-based relations and the spread of all-pervasive protecting informality to compensate for object-based relations.

  4. Silencing of Carbohydrate Sulfotransferase 15 Hinders Murine Pulmonary Fibrosis Development

    Directory of Open Access Journals (Sweden)

    Yoshiro Kai

    2017-03-01

    Full Text Available Pulmonary fibrosis is a progressive lung disorder characterized by interstitial fibrosis, for which no effective treatments are available. Chondroitin sulfate proteoglycan (CSPG has been shown to be a mediator, but the specific component of glycosaminoglycan chains of CSPG has not been explored. We show that chondroitin sulfate E-type (CS-E is involved in fibrogenesis. Small interfering RNA (siRNA targeting carbohydrate sulfotransferase 15 (CHST15 was designed to inhibit CHST15 mRNA and its product, CS-E. CS-E augments cell contraction and CHST15 siRNA inhibits collagen production. We found that bleomycin treatment increased CHST15 expression in interstitial fibroblasts at day 14. CHST15 siRNA was injected intranasally on days 1, 4, 8, and 11, and CHST15 mRNA was significantly suppressed by day 14. CHST15 siRNA reduced lung CSPG and the grade of fibrosis. CHST15 siRNA repressed the activation of fibroblasts, as evidenced by suppressed expression of α smooth muscle actin (αSMA, connective tissue growth factor (CTGF, lysyl oxidase like 2 (LOXL2, and CC-chemokine ligand 2 (CCL2/monocyte chemoattractant protein-1 (MCP-1. Inflammatory infiltrates in the bronchoalveolar lavage fluid (BALF and interstitium were diminished by CHST15 siRNA. These results indicate a pivotal role for CHST15 in fibroblast-mediated lung fibrosis and suggest a possible new therapeutic role for CHST15 siRNA in pulmonary fibrosis.

  5. Does Home Hinder Professional Commitment? The Case of Early Education.

    Science.gov (United States)

    Seifert, Kelvin L.; Atkinson, Laura E.

    1991-01-01

    Uses classroom observations and interviews to examine three kindergarten teachers' perceptions, focusing on gender-related differences in the balance between home and work and the development of internalized commitment. Suggests ways to make teaching a more aesthetic experience for family caregivers. Includes 19 references. (MLH)

  6. Capacity shortfalls hinder the performance of marine protected areas globally

    Science.gov (United States)

    Gill, David A.; Mascia, Michael B.; Ahmadia, Gabby N.; Glew, Louise; Lester, Sarah E.; Barnes, Megan; Craigie, Ian; Darling, Emily S.; Free, Christopher M.; Geldmann, Jonas; Holst, Susie; Jensen, Olaf P.; White, Alan T.; Basurto, Xavier; Coad, Lauren; Gates, Ruth D.; Guannel, Greg; Mumby, Peter J.; Thomas, Hannah; Whitmee, Sarah; Woodley, Stephen; Fox, Helen E.

    2017-03-01

    Marine protected areas (MPAs) are increasingly being used globally to conserve marine resources. However, whether many MPAs are being effectively and equitably managed, and how MPA management influences substantive outcomes remain unknown. We developed a global database of management and fish population data (433 and 218 MPAs, respectively) to assess: MPA management processes; the effects of MPAs on fish populations; and relationships between management processes and ecological effects. Here we report that many MPAs failed to meet thresholds for effective and equitable management processes, with widespread shortfalls in staff and financial resources. Although 71% of MPAs positively influenced fish populations, these conservation impacts were highly variable. Staff and budget capacity were the strongest predictors of conservation impact: MPAs with adequate staff capacity had ecological effects 2.9 times greater than MPAs with inadequate capacity. Thus, continued global expansion of MPAs without adequate investment in human and financial capacity is likely to lead to sub-optimal conservation outcomes.

  7. Fatores que favorecem e dificultam o trabalho dos enfermeiros nos serviços de atenção à saúde Factores que favorecen y dificultan el trabajo de los enfermeros en los servicios de atención a la salud Factors that favor and hinder the work of nurses in services of health attention

    Directory of Open Access Journals (Sweden)

    Carmem Lúcia Colomé Beck

    2010-09-01

    fortificar las acciones que desarrolla frente al usuario del Sistema Único de Salud y buscar soluciones delante de las necesidades de la comunidad.The nurse faces factors that favor and hinder the performance of his work and interfere with the feelings before work. This is an exploratory-descriptive study with a qualitative approach. It aimed to sociodemographically characterize the nurses of the Services of Health Attention of a town in the State of Rio Grande do Sul and to identify the factors that favor and hinder the performance of the work. The data were collected from March to July 2007 through a survey. The sample was composed by 24 nurses. The data analysis enabled two build two theme axes: factors that favor and hinder the performance of nurse work. The results suggest that nurses perceive satisfaction at work. However, it is necessary to rethink the process of work of this Professional to strength the actions before the user of Single Health System's and search for resolutivity before the necessities of the community.

  8. Fatores que facilitam e dificultam a entrevista familiar no processo de doação de órgãos e tecidos para transplante Factores que facilitan y dificultan la entrevista familiar en el proceso de donación de órganos y tejidos para transplante Factors that facilitate and hinder family interviews in the process of donating organs and tissues for transplantation

    Directory of Open Access Journals (Sweden)

    Marcelo José dos Santos

    2011-01-01

    professionals working in Organ Procurement Organizations about the factors that facilitate and hinder family interviews in the process of donating organs and tissues for transplantation. METHODS: This qualitative, phenomenological research used the "structure of the situated-phenomenon" modality. The study included 18 professionals who worked in Organ Procurement Organizations. RESULTS: After analyzing the interviews, the factors that facilitate and hinder family interview were revealed. CONCLUSION: The proposals that emerged revealed that the factors that facilitate and hinder family interview were related to the interview site, assistance provided to potential donors and their families, the explanations provided to the family and the manifestations to the potential donors' lives on the decision regarding organ donation.

  9. In vivo determination of steric and electrostatic exclusion of albumin in rat skin and skeletal muscle.

    Science.gov (United States)

    Gyenge, Christina C; Tenstad, Olav; Wiig, Helge

    2003-11-01

    In order to estimate the magnitude of electrostatic exclusion provided by the fixed negative charges of the skin and muscle interstitia of rat in vivo we measured the distribution volumes of two differently charged albumin probes within these tissues. An implanted osmotic pump was used to reach and maintain a steady-state extracellular concentration of a mixture containing two iodine-labelled probes: a charged-modified human serum albumin, cHSA (i.e. a positive probe, isoelectirc point (pI) = 7.6) and a native human serum albumin, HSA (i.e. a normally charged, negative probe, pI = 5.0). Steady-state tissue concentrations were achieved after intravenous infusion of probes for 5-7 days. At the end of this period the animals were nephrectomized and a bolus of 51Cr-EDTA was administered for estimating the extracellular volume. Plasma volumes were measured as 5-min distribution volume of 125I-HSA in separate experiments. The steady-state interstitial fluid concentrations of all probes were determined using nylon wicks implanted postmortem. Calculations of labelled probes were made for interstitial fluid volumes (Vi), extravascular albumin distribution volumes (Vav,a) and relative interstitial excluded volume fractions (Vex,a/Vi). We found that the positive probe is excluded from a significantly smaller fraction of the interstitium. Specifically, the average relative albumin exclusion fractions obtained were: 16% and 26% in skeletal muscle and 30% and 40% in skin, for cHSA and HSA, respectively. On average, the fixed negative charges of the interstitium are responsible for about 40% of the total albumin exclusion in skeletal muscle and 25% in the whole skin tissue and thus, contribute significantly to volume exclusion in these tissues.

  10. Carbon-13 nuclear magnetic resonance of strained organic molecules: III estimates of steric effects

    International Nuclear Information System (INIS)

    Seidl, P.R.; Leal, K.Z.; Costa, V.E.U.; Rio Grande do Sul Univ., Porto Alegre

    1985-01-01

    A study of cyclic organic molecules using carbon-13 NMR spectroscopy is analysed. The preparation of compounds and the use of norbornyl compounds as a basis for chemical shifts, bicyclic, tricyclic and tetracyclic derivatives are compared. Relevant distances, angles and non-bonded interactions are shown. (M.J.C.) [pt

  11. Steric exclusion and protein conformation determine the localization of plasma membrane transporters

    NARCIS (Netherlands)

    Bianchi, Frans; Syga, Łukasz; Moiset, Gemma; Spakman, Dian; Schavemaker, Paul E; Punter, Christiaan M; Seinen, Anne-Bart; van Oijen, Antoine M; Robinson, Andrew; Poolman, Bert

    2018-01-01

    The plasma membrane (PM) of Saccharomyces cerevisiae contains membrane compartments, MCC/eisosomes and MCPs, named after the protein residents Can1 and Pma1, respectively. Using high-resolution fluorescence microscopy techniques we show that Can1 and the homologous transporter Lyp1 are able to

  12. Role of Steric Hindrance in the Crystal Packing of Z′ = 4 Superstructure of Trimethyltin Hydroxide

    KAUST Repository

    Dey, S.; Schö nleber, A.; Mondal, S.; Ali, S. I.; van Smaalen, S.

    2018-01-01

    The roomerature crystal structure of trimethyltin hydroxide, (CH)SnOH, has been described by Anderson et al. [Cryst. Growth Des. 2011, 11, 820-826] as a 2a × 2b × 8c, 32-fold superstructure. We report a a × b × 8c, eight-fold superstructure

  13. Hydrophilic luminescent silicon nanoparticles in steric colloidal solutions: Their size, agglomeration, and toxicity

    Czech Academy of Sciences Publication Activity Database

    Herynková, Kateřina; Šimáková, Petra; Cibulka, Ondřej; Fučíková, Anna; Kalbáčová, M.H.

    2017-01-01

    Roč. 14, č. 12 (2017), s. 1-4, č. článku 1700195. ISSN 1862-6351 Grant - others:AV ČR(CZ) DAAD-16-18 Program:Bilaterální spolupráce Institutional support: RVO:68378271 Keywords : silicon nanoparticles * agglomeration * toxicity Subject RIV: BO - Biophysics OBOR OECD: Biophysics

  14. Toward (-)-Enterocin: An Improved Cuprate Barbier Protocol To Overcome Strain and Sterical Hindrance.

    Science.gov (United States)

    Rizzo, Antonio; Trauner, Dirk

    2018-04-06

    An approach toward (-)-enterocin, an antibiotic isolated from Streptomyces hygroscopicus, is described. Its compact, heavily oxidized protoadamantane core represents a daunting challenge for an efficient synthesis. Convergent assembly of its 2-oxabicyclo[3.3.1]nonane core with a cuprate-mediated Barbier reaction is disclosed. Its functionalization to a suitable substrate for a biomimetic aldol to close the final ring of the natural product is evaluated.

  15. Inverting Steric Effects: Using "Attractive" Noncovalent Interactions To Direct Silver-Catalyzed Nitrene Transfer.

    Science.gov (United States)

    Huang, Minxue; Yang, Tzuhsiung; Paretsky, Jonathan D; Berry, John F; Schomaker, Jennifer M

    2017-12-06

    Nitrene transfer (NT) reactions represent powerful and direct methods to convert C-H bonds into amine groups that are prevalent in many commodity chemicals and pharmaceuticals. The importance of the C-N bond has stimulated the development of numerous transition-metal complexes to effect chemo-, regio-, and diastereoselective NT. An ongoing challenge is to understand how subtle interactions between catalyst and substrate influence the site-selectivity of the C-H amination event. In this work, we explore the underlying reasons why Ag(tpa)OTf (tpa = tris(pyridylmethyl)amine) prefers to activate α-conjugated C-H bonds over 3° alkyl C(sp 3 )-H bonds and apply these insights to reaction optimization and catalyst design. Experimental results suggest possible roles of noncovalent interactions (NCIs) in directing the NT; computational studies support the involvement of π···π and Ag···π interactions between catalyst and substrate, primarily by lowering the energy of the directed transition state and reaction conformers. A simple Hess's law relationship can be employed to predict selectivities for new substrates containing competing NCIs. The insights presented herein are poised to inspire the design of other catalyst-controlled C-H functionalization reactions.

  16. A latent ruthenium based olefin metathesis catalyst with a sterically demanding NHC ligand

    KAUST Repository

    Leitgeb, Anita; Abbas, Mudassar E.; Fischer, Roland C.; Poater, Albert; Cavallo, Luigi; Slugovc, Christian

    2012-01-01

    An olefin metathesis catalyst featuring a SIPr NHC and an ester chelating carbene ligand is introduced. In contrast to its previously published SIMes analogue, only the trans dichloro configurated isomer was obtained. The two counterparts are tested in various olefin metathesis reactions, revealing a striking superiority of the new complex in the cross metathesis of olefins with methyl vinyl ketone allowing for full conversion with only 500 ppm catalyst loading. © 2012 The Royal Society of Chemistry.

  17. Decadal trends in deep ocean salinity and regional effects on steric sea level

    Science.gov (United States)

    Purkey, S. G.; Llovel, W.

    2017-12-01

    We present deep (below 2000 m) and abyssal (below 4000 m) global ocean salinity trends from the 1990s through the 2010s and assess the role of deep salinity in local and global sea level budgets. Deep salinity trends are assessed using all deep basins with available full-depth, high-quality hydrographic section data that have been occupied two or more times since the 1980s through either the World Ocean Circulation Experiment (WOCE) Hydrographic Program or the Global Ship-Based Hydrographic Investigations Program (GO-SHIP). All salinity data is calibrated to standard seawater and any intercruise offsets applied. While the global mean deep halosteric contribution to sea level rise is close to zero (-0.017 +/- 0.023 mm/yr below 4000 m), there is a large regional variability with the southern deep basins becoming fresher and northern deep basins becoming more saline. This meridional gradient in the deep salinity trend reflects different mechanisms driving the deep salinity variability. The deep Southern Ocean is freshening owing to a recent increased flux of freshwater to the deep ocean. Outside of the Southern Ocean, the deep salinity and temperature changes are tied to isopycnal heave associated with a falling of deep isopycnals in recent decades. Therefore, regions of the ocean with a deep salinity minimum are experiencing both a halosteric contraction with a thermosteric expansion. While the thermosteric expansion is larger in most cases, in some regions the halosteric compensates for as much as 50% of the deep thermal expansion, making a significant contribution to local sea level rise budgets.

  18. Steric Effects in Reactions of Decamethyltitanocene Hydride with Internal Alkynes, Conjugated Diynes, and Conjugated Dienes

    Czech Academy of Sciences Publication Activity Database

    Pinkas, Jiří; Gyepes, Robert; Císařová, I.; Kubišta, Jiří; Horáček, Michal; Mach, Karel

    2014-01-01

    Roč. 33, č. 13 (2014), s. 3399-3413 ISSN 0276-7333 R&D Projects: GA ČR(CZ) GAP207/12/2368; GA ČR GP203/09/P276 Institutional support: RVO:61388955 Keywords : atoms * complexation * Electron spin resonance spectroscopy Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 4.126, year: 2014

  19. Sterically directed iridium-catalyzed hydrosilylation of alkenes in the presence of alkynes.

    Science.gov (United States)

    Muchnij, Jill A; Kwaramba, Farai B; Rahaim, Ronald J

    2014-03-07

    A selective iridium catalyzed hydrosilylation of alkenes in the presence of more reactive alkynes is described. By utilizing [IrCl(COD)]2 in the presence of excess COD, hydrosilylation of alkenes and alkynes with ethynylsilanes is achieved with good chemo- and regioselectivity. This approach goes against the traditional reactivity trends of platinum and rhodium catalysts and allows access to highly substituted silicon alkyne tethers.

  20. Cu-Mediated Stille Reactions of Sterically Congested Fragments: Towards the Total Synthesis of Zoanthamine

    DEFF Research Database (Denmark)

    Nielsen, Thomas E.; Le Quement, Sebastian; Juhl, Martin

    2005-01-01

    A study on the Stille reaction of alkenyl iodides and starmanes with structural resemblance to retrosynthetic fragments of a projected total synthesis of the marine alkaloid zoanthamine was carried out. A range of reaction conditions was examined, and a protocol developed by Corey utilizing excess...

  1. Protein-protein interactions in paralogues: Electrostatics modulates specificity on a conserved steric scaffold.

    Directory of Open Access Journals (Sweden)

    Stefan M Ivanov

    Full Text Available An improved knowledge of protein-protein interactions is essential for better understanding of metabolic and signaling networks, and cellular function. Progress tends to be based on structure determination and predictions using known structures, along with computational methods based on evolutionary information or detailed atomistic descriptions. We hypothesized that for the case of interactions across a common interface, between proteins from a pair of paralogue families or within a family of paralogues, a relatively simple interface description could distinguish between binding and non-binding pairs. Using binding data for several systems, and large-scale comparative modeling based on known template complex structures, it is found that charge-charge interactions (for groups bearing net charge are generally a better discriminant than buried non-polar surface. This is particularly the case for paralogue families that are less divergent, with more reliable comparative modeling. We suggest that electrostatic interactions are major determinants of specificity in such systems, an observation that could be used to predict binding partners.

  2. Protein-protein interactions in paralogues: Electrostatics modulates specificity on a conserved steric scaffold.

    Science.gov (United States)

    Ivanov, Stefan M; Cawley, Andrew; Huber, Roland G; Bond, Peter J; Warwicker, Jim

    2017-01-01

    An improved knowledge of protein-protein interactions is essential for better understanding of metabolic and signaling networks, and cellular function. Progress tends to be based on structure determination and predictions using known structures, along with computational methods based on evolutionary information or detailed atomistic descriptions. We hypothesized that for the case of interactions across a common interface, between proteins from a pair of paralogue families or within a family of paralogues, a relatively simple interface description could distinguish between binding and non-binding pairs. Using binding data for several systems, and large-scale comparative modeling based on known template complex structures, it is found that charge-charge interactions (for groups bearing net charge) are generally a better discriminant than buried non-polar surface. This is particularly the case for paralogue families that are less divergent, with more reliable comparative modeling. We suggest that electrostatic interactions are major determinants of specificity in such systems, an observation that could be used to predict binding partners.

  3. Synthesis of 1,3-cis-disubstituted sterically encumbered imidazolidinone organocatalysts

    Directory of Open Access Journals (Sweden)

    Jan Wallbaum

    2017-12-01

    Full Text Available A variety of novel imidazolidinone-based organocatalysts with bulky substituents were synthesized under mild reaction conditions starting from easily accessible substrates. Different natural and unnatural amino acid methyl amides were cyclized with aromatic carbaldehydes to yield two diastereomeric MacMillan-type catalysts. Special emphasis was put on bulky residues such as mesityl and pyrene moieties.

  4. Steric structure and thermodynamic aspects of Dy3+ complexes with aminobenzoic acids in aqueous solutions

    International Nuclear Information System (INIS)

    Kondrashina, Yu.G.; Mustafina, A.R.; Vul'fson, S.G.

    1994-01-01

    Stability and structure of dysprosium(3) aminobenzoate complexes with molar ratios Dy:L 1:1 and 1:2 (HL-aminobenzoic acid) in aqueous solutions are determined on the basis of pH-metric and paramagnetic birefringence data. The increase of conjugation effect in the series of benzoic, meta- ortho-, and para-aminobenzoic acid results in the increase of stability of 1:1 and 1:2 complexes. Features of the structure and coordination of ligands in dysprosium complexes with meta-, ortho-, and para-aminobenzoic acid are considered. 11 refs.; 4 figs.; 2 tabs

  5. Novel imines with tunable nucleophilicity and steric properties through metal coordination: applications as ligands and metalloorganocatalysts

    KAUST Repository

    Huang, Kuo-Wei

    2016-03-17

    The invention describes phospho-amino pincer-type ligands, metal complexes thereof, and catalytic methods comprising such metal complexes for conversion of carbon dioxide to methanol, conversion of aldehydes into alcohols, conversion of aldehydes in the presence of a trifluoromethylation agent into trifluorinated secondary alcohols, cycloaddition of carbon dioxide to an epoxide to provide cyclic carbonates or preparation of an amide from the combination of an alcohol and an amine.

  6. Study of interactions between lanthanides/actinides and humic substances by a steric exclusion chromatographic method

    International Nuclear Information System (INIS)

    Moulin, V.

    1986-01-01

    The knowledge of cation-humic matter interactions has a great importance in order to have a better understanding of the contribution of these substances to the possible transport of radioactive elements in the geosphere via groundwaters. The method chosen to study the formation of soluble species between lanthanides/actinides ions and humic acids from different origins is a chromatographic technique of gel filtration. This dynamic equilibrium method is based on the separation of the formed complex and the free cation by the porous packing gel. Different elements have been studied by this method: UO 2 2+ , Eu 3+ , Th 4+ and global interaction constants have been calculated. The application to transuranic elements is undertaken. (orig.)

  7. Novel imines with tunable nucleophilicity and steric properties through metal coordination: applications as ligands and metalloorganocatalysts

    KAUST Repository

    Huang, Kuo-Wei; Zhao, Qianyi

    2016-01-01

    The invention describes phospho-amino pincer-type ligands, metal complexes thereof, and catalytic methods comprising such metal complexes for conversion of carbon dioxide to methanol, conversion of aldehydes into alcohols, conversion of aldehydes in the presence of a trifluoromethylation agent into trifluorinated secondary alcohols, cycloaddition of carbon dioxide to an epoxide to provide cyclic carbonates or preparation of an amide from the combination of an alcohol and an amine.

  8. Steric control of reactivity: formation of oximes, benzodiazepinone N-oxides and isoxazoloquinolinones

    OpenAIRE

    Heaney, Frances; Bourke, Sharon; Cunningham, Desmond; McArdle, Patrick

    1998-01-01

    Reaction of the alkenyl carbonyl compounds 1 with hydroxylamine can lead to the formation of the oximes 2, the benzodiazepinone N-oxides 3 or the isoxazoloquinolinones 5. The product(s) of reaction are shown to depend on the electronic nature of the terminal olefinic substituent R3 and the space filling capacity of the substituents R1, R2 and R4. When the olefinic centre is electron poor (R3 = CO2Et) ketocarbonyls convert exclusively to bicyclic nitrones 3 whereas aldehydes are more sensitive...

  9. Crystallization and crystal manipulation of a steric chaperone in complex with its lipase substrate

    International Nuclear Information System (INIS)

    Pauwels, Kris; Loris, Remy; Vandenbussche, Guy; Ruysschaert, Jean-Marie; Wyns, Lode; Van Gelder, Patrick

    2005-01-01

    Crystals of the lipase of B. glumae in complex with its specific foldase were obtained in two forms. Crystallization, crystal manipulation and preliminary X-ray diffraction analysis are described. Bacterial lipases that are secreted via the type II secretion pathway require a lipase-specific foldase in order to obtain their native and biologically active conformation in the periplasmic space. The lipase–foldase complex from Burkholderia glumae (319 and 333 residues, respectively) was crystallized in two crystal forms. One crystal form belongs to space group P3 1 21 (P3 2 21), with unit-cell parameters a = b = 122.3, c = 98.2 Å. A procedure is presented which improved the diffraction of these crystals from ∼5 to 2.95 Å. For the second crystal form, which belonged to space group C2 with unit-cell parameters a = 183.0, b = 75.7, c = 116.6 Å, X-ray data were collected to 1.85 Å

  10. Rapid and convenient semi-automated microwave-assisted solid-phase synthesis of arylopeptoids

    DEFF Research Database (Denmark)

    Rasmussen, Jakob Ewald; Boccia, Marcello Massimo; Nielsen, John

    2014-01-01

    A facile and expedient route to the synthesis of arylopeptoid oligomers (N-alkylated aminomethyl benz-amides) using semi-automated microwave-assisted solid-phase synthesis is presented. The synthesis was optimized for the incorporation of side chains derived from sterically hindered or unreactive...

  11. Direct, Regioselective N-Alkylation of 1,3-Azoles.

    Science.gov (United States)

    Chen, Shuai; Graceffa, Russell F; Boezio, Alessandro A

    2016-01-04

    Regioselective N-alkylation of 1,3-azoles is a valuable transformation. Organomagnesium reagents were discovered to be competent bases to affect regioselective alkylation of various 1,3-azoles. Counterintuitively, substitution selectively occurred at the more sterically hindered nitrogen atom. Numerous examples are provided, on varying 1,3-azole scaffolds, with yields ranging from 25 to 95%.

  12. Bianthrone in a Single-Molecule Junction: Conductance Switching with a Bistable Molecule Facilitated by Image Charge Effects

    DEFF Research Database (Denmark)

    Bjørnholm, Thomas

    2010-01-01

    Bianthrone is a sterically hindered compound that exists in the form of two nonplanar isomers. Our experimental study of single-molecule junctions with bianthrone reveals persistent switching of electric conductance at low temperatures, which can be reasonably associated with molecular isomerizat...

  13. Carbonic Anhydrase Enhanced Carbon Capture: Kinetic Measurements and Pilot Plant Trials

    DEFF Research Database (Denmark)

    Gladis, Arne; Deslauriers, Maria Gundersen; Fosbøl, Philip Loldrup

    In this study the effect of carbonic anhydrase addition on the absorption of CO2 was investigated in a wetted wall column apparatus. Four different solvents: MEA (a primary amine), AMP (a sterically hindered primary amine), MDEA (a tertiary amine) and K2CO3 a carbonate salt solution were tested...

  14. Sulfonato-imino copper(ii) complexes: fast and general Chan-Evans-Lam coupling of amines and anilines.

    Science.gov (United States)

    Hardouin Duparc, V; Schaper, F

    2017-10-14

    Sulfonato-imine copper complexes with either chloride or triflate counteranions were prepared in a one-step reaction followed by anion-exchange. They are highly active in Chan-Evans-Lam couplings under mild conditions with a variety of amines or anilines, in particular with sterically hindered substrates. No optimization of reaction conditions other than time and/or temperature is required.

  15. Fused-Ring Formation by an Intramolecular "Cut-and-Sew" Reaction between Cyclobutanones and Alkynes.

    Science.gov (United States)

    Deng, Lin; Jin, Likun; Dong, Guangbin

    2018-03-01

    The development of a catalytic intramolecular "cut-and-sew" transformation between cyclobutanones and alkynes to construct cyclohexenone-fused rings is described herein. The challenge arises from the need for selective coupling at the more sterically hindered proximal position, and can be addressed by using an electron-rich, but less bulky, phosphine ligand. The control experiment and 13 C-labelling study suggest that the reaction may start with cleavage of the less hindered distal C-C bond of cyclobutanones, followed by decarbonylation and CO reinsertion to enable Rh insertion at the more hindered proximal position. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Understanding the Difficulties Hindering Inter-Agency Collaboration for Students with Special Needs in Quebec

    Science.gov (United States)

    Tetreault, Sylvie; Patenaude, David; McLaughlin, Dayna; Freeman, Andrew; Gascon, Hubert; Beaupré, Pauline; Carrière, Monique; Deschênes, Pascale Marier

    2015-01-01

    In 2003, the government of Quebec established the "Agreement for the Complementarity of Services Between the Health and Social Services Network and the Education Network" to define principles and obligations for inter-agency collaboration aimed at students with special needs and their families. This study documents the perspectives of…

  17. Displaced by development: How the state can hinder or help | IDRC ...

    International Development Research Centre (IDRC) Digital Library (Canada)

    2016-11-16

    Nov 16, 2016 ... In their 2015 paper “Changing Cities and Changing Lives: ... inequality, violence, and physical insecurity did not emerge as major concerns, various ... Learn more about IDRC's research support to make cities safer through ...

  18. What constitutes a nesting attempt? Variation in criteria causes bias and hinders comparisons across studies

    Science.gov (United States)

    Garcia, V.; Conway, C.J.

    2009-01-01

    Because reliable estimates of nesting success are very important to avian studies, the defnition of a “successful nest” and the use of different analytical methods to estimate success have received much attention. By contrast, variation in the criteria used to determine whether an occupied site that did not produce offspring contained a nesting attempt is a source of bias that has been largely ignored. This problem is especially severe in studies that deal with species whose nest contents are relatively inaccessible because observers cannot determine whether or not an egg was laid for a large proportion of occupied sites. Burrowing Owls (Athene cunicularia) often lay their eggs ≥3 m below ground, so past Burrowing Owl studies have used a variety of criteria to determine whether a nesting attempt was initiated. We searched the literature to document the extent of that variation and examined how that variation influenced estimates of daily nest survival. We found 13 different sets of criteria used by previous authors and applied each criterion to our data set of 1,300 occupied burrows. We found significant variation in estimates of daily nest survival depending on the criteria used. Moreover, differences in daily nest survival among populations were apparent using some sets of criteria but not others. These inconsistencies may lead to incorrect conclusions and invalidate comparisons of the productivity and relative site quality among populations. We encourage future authors working on cavity-, canopy-, or burrow-nesting birds to provide specific details on the criteria they used to identify a nesting attempt.

  19. Coaching individuals with perfectionistic tendencies When high standards help and hinder

    Directory of Open Access Journals (Sweden)

    Sarah Corrie

    2014-07-01

    Full Text Available Perfectionism has been widely recognised in the clinical field but has received less attention in the coaching psychology literature. Referring to overly high and unforgiving personal standards of performance that are accompanied by harsh self-evaluation when self-imposed standards are not met, perfectionism has the potential to undermine the coachee’s ability to achieve their goals as well as the coaching process itself. In consequence, it is important for practitioners to be able to identify and work effectively with those coachees whose perfectionistic tendencies represent an obstacle to progress. This paper discusses the current literature on perfectionism and provides recommendations on how to work effectively with coachees for whom unremittingly high personal standards are an impediment to personal growth and development.

  20. Coniferyl alcohol hinders the growth of tobacco BY-2 cells and Nicotiana benthamiana seedlings.

    Science.gov (United States)

    Väisänen, Enni E; Smeds, Annika I; Fagerstedt, Kurt V; Teeri, Teemu H; Willför, Stefan M; Kärkönen, Anna

    2015-09-01

    Externally added coniferyl alcohol at high concentrations reduces the growth of Nicotiana cells and seedlings. Coniferyl alcohol is metabolized by BY-2 cells to several compounds. Coniferyl alcohol (CA) is a common monolignol and a building block of lignin. The toxicity of monolignol alcohols has been stated in the literature, but there are only few studies suggesting that this is true. We investigated the physiological effects of CA on living plant cells in more detail. Tobacco (Nicotiana tabacum) Bright yellow-2 cells (BY-2) and Nicotiana benthamiana seedlings both showed concentration-dependent growth retardation in response to 0.5-5 mM CA treatment. In some cases, CA addition caused cell death in BY-2 cultures, but this response was dependent on the growth stage of the cells. Based on LC-MS/MS analysis, BY-2 cells did not accumulate the externally supplemented CA, but metabolized it to ferulic acid, ferulic acid glycoside, coniferin, and to some other phenolic compounds. In addition to growth inhibition, CA caused the formation of a lignin-like compound detected by phloroglucinol staining in N. benthamiana roots and occasionally in BY-2 cells. To prevent this, we added potassium iodide (KI, at 5 mM) to overcome the peroxidase-mediated CA polymerization to lignin. KI had, however, toxic effects on its own: in N. benthamiana seedlings, it caused reduction in growth; in BY-2 cells, reduction in growth and cell viability. Surprisingly, CA restored the growth of KI-treated BY-2 cells and N. benthamiana seedlings. Our results suggest that CA at high concentrations is toxic to plant cells.

  1. Hindering and buffering factors for parental sleep in neonatal care. A phenomenographic study.

    Science.gov (United States)

    Edéll-Gustafsson, Ulla; Angelhoff, Charlotte; Johnsson, Ewa; Karlsson, Jenny; Mörelius, Evalotte

    2015-03-01

    To explore and describe how parents of preterm and/or sick infants in neonatal care perceive their sleep. Parents experience many stressful situations when their newborn infant is preterm and/or sick. This affects bonding. By developing more family-centred care units with single-family rooms, parents are given the opportunity to stay and care for their newborn infant(s) 24 hours a day. Lack of sleep may affect new parents' ability to cope with the many challenges they face on a daily basis. A phenomenographic study with an inductive and exploratory design. Semi-structured interviews were conducted with twelve parents of infants in neonatal care between January-March 2012. To describe variations in perception of the phenomenon, data were analysed using phenomenography. Four descriptive categories were identified within the phenomenon sleep in parents of preterm and/or sick infants in neonatal care: impact of stress on sleep; how the environment affects sleep; keeping the family together improves sleep; and, how parents manage and prevent tiredness. Anxiety, uncertainty and powerlessness have a negative influence on sleep. This can be decreased by continuous information, guidance and practical support. Skin-to-skin care was perceived as a stress-reducing factor that improved relaxation and sleep and should be encouraged by the nurse. The parents also mentioned the importance of being together. Having a private place where they could relax and take care of themselves and their newborn infant improved sleep. It was also desirable to involve older siblings in order to decrease feelings of loneliness, sadness and isolation. Improved parental sleep in neonatal care may help the families cope with the situation and facilitate problem-solving, emotional regulation and the transition to parenthood. © 2014 John Wiley & Sons Ltd.

  2. Nursing curriculums may hinder a career in gerontological nursing: An integrative review.

    Science.gov (United States)

    Garbrah, William; Välimäki, Tarja; Palovaara, Marjo; Kankkunen, Päivi

    2017-09-01

    To investigate what prevents undergraduate nursing students from choosing gerontological nursing as a career option. This study utilised an integrative literature review, which allows the inclusion of previous studies with diverse research designs to gain a broader view of the reasons why nursing students do not choose a gerontological nursing career. An electronic database search of CINAHL (Ebsco), Scopus and Eric elicited 251 scientific peer-reviewed empirical studies, published from 2006 to March 2016 in English. After meeting the inclusion criteria, 97 qualified for closer examination. Following exclusion, the final analysis and synthesis included 21 articles. Four main themes described nursing students' contributing reasons for not selecting gerontological nursing as a career option: socio-demographic factors; experiences, perceptions and knowledge about ageing; perceptions concerning the nature or status of gerontological nursing; and theoretical studies and practical education of nursing curriculum. Lack of positive experiences with older people before and during nursing students' studies led to their disinterest in gerontological nursing as a career option. The nursing curriculum also reinforces the perception of modern nursing as technical, with more emphasis on acute and critical care. The findings emphasise the need to implement an age-friendly curriculum and have nurses that specialise in gerontology to serve as mentors and role models. It is important to assist nursing students in identifying the potentials for career advancement in terms of gerontological nursing. There is also a need for nursing faculties to liaise with other stakeholders to develop or improve upon the clinical atmosphere for nursing students during gerontological nursing placement. Nursing faculties must review their curriculum to ensure that there is sufficient focus on the needs of older people within the curriculum for every student. Furthermore, respected role models who are knowledgeable and enthusiastic about issues related to older people must teach gerontological nursing courses. © 2017 John Wiley & Sons Ltd.

  3. Pitfalls of the Past: Learning Disabilities that Hinder TRADOC’s Institutional Agility

    Science.gov (United States)

    2015-05-23

    they will not necessarily prevent TRADOC from transforming, they might generate unwanted pushback from the field and the nation’s policy directors. 15...TRADOC from transforming, they might generate unwanted pushback from the field and the nation’s policy directors. iv Contents Acknowledgments...the Army’s most comprehensive process of post-war boards and self-assessments conducted to that point in the Army’s history, which then informed the

  4. Factors That Facilitate Or Hinder Fuel-Saving Initiatives and Technology

    Science.gov (United States)

    2015-12-01

    more battery density. (Securing America’s Future Energy, 2013) Initially, the Fuel Sense program was met with much skepticism and pushback . The...59 example, when implementing electronic maps in earlier years, there was pushback from drivers who were used to paper maps. FedEx was able to

  5. Reaction of hydrogen peroxide with uranium zirconium oxide solid solution - Zirconium hinders oxidative uranium dissolution

    Science.gov (United States)

    Kumagai, Yuta; Takano, Masahide; Watanabe, Masayuki

    2017-12-01

    We studied oxidative dissolution of uranium and zirconium oxide [(U,Zr)O2] in aqueous H2O2 solution to estimate (U,Zr)O2 stability to interfacial reactions with H2O2. Studies on the interfacial reactions are essential for anticipating how a (U,Zr)O2-based molten fuel may chemically degrade after a severe accident. The fuel's high radioactivity induces water radiolysis and continuous H2O2 generation. Subsequent reaction of the fuel with H2O2 may oxidize the fuel surface and facilitate U dissolution. We conducted our experiments with (U,Zr)O2 powder (comprising Zr:U mole ratios of 25:75, 40:60, and 50:50) and quantitated the H2O2 reaction via dissolved U and H2O2 concentrations. Although (U,Zr)O2 reacted more quickly than UO2, the dissolution yield relative to H2O2 consumption was far less for (U,Zr)O2 compared to that of UO2. The reaction kinetics indicates that most of the H2O2 catalytically decomposed to O2 at the surface of (U,Zr)O2. We confirmed the H2O2 catalytic decomposition via O2 production (quantitative stoichiometric agreement). In addition, post-reaction Raman scattering spectra of the undissolved (U,Zr)O2 showed no additional peaks (indicating a lack of secondary phase formation). The (U,Zr)O2 matrix is much more stable than UO2 against H2O2-induced oxidative dissolution. Our findings will improve understanding on the molten fuels and provide an insight into decommissioning activities after a severe accident.

  6. From Mammy to Superwoman: Images that Hinder Black Women's Career Development

    Science.gov (United States)

    Reynolds-Dobbs, Wendy; Thomas, Kecia M.; Harrison, Matthew S.

    2008-01-01

    Black women, like other women of color, find themselves at the intersection of both racism and sexism in the workplace. Due to their unique dual status as racial and gender minorities, they encounter unique and unexplored barriers that inhibit their career as well as leadership development. The goal of this article is to highlight the emerging…

  7. How Hepatitis D Virus Can Hinder the Control of Hepatitis B Virus

    NARCIS (Netherlands)

    Xiridiou, M.; Borkent-Raven, B.; Hulshof, J.; Wallinga, J.

    2009-01-01

    Background: Hepatitis D (or hepatitis delta) virus is a defective virus that relies on hepatitis B virus (HBV) for transmission; infection with hepatitis D can occur only as coinfection with HBV or superinfection of an existing HBV infection. Because of the bond between the two viruses, control

  8. Some Factors Hindering Acceptance of Three Gamification Solutions in Motivation Systems, in Small and Medium Enterprises

    Directory of Open Access Journals (Sweden)

    Jacek WOŹNIAK

    2017-12-01

    Full Text Available Gamification, understood as a use of chosen game mechanisms for motivating actors in non-game contexts, is increasingly popular and has become one of the “hot topics” of managerial practice and science. Despite its widespread use in HRM, several barriers preventing its progress in certain types of organizations have been identified. Small and medium enterprises (SMEs, where employees are not accustomed to formal procedures are a specific example, as gamification is based on formal procedures. The goal of the text is to analyze employees’ opinions concerning the incorporation of chosen gaming mechanisms into their motivation systems, to check if not being accustomed to formal procedures is a barrier. Beside “typical” SMEs where the entrepreneur is present, direct relations within a team are also characteristic of company departments which achieve their goals almost without contact with the rest of the organization – as in the case of a discount stores chain. The study bases on two samples to check if being accustomed to formal procedures in the small team facilitates acceptance of gamification. Two questionnaires (one on a sample of 100 employees of a discount store chain, and the second on 73 “typical” SME employees asked respondents to declare their preferences for different types of rewards in motivation systems, including readiness to be involved in two gamification-type solutions: based on (i lotteries, or (ii BLAP gaming with non-material and material prizes. The effects of chosen factors: psychological (risk aversion and situational (dissatisfaction with current incentive system on the perception of two different ways of incorporating gamification into motivational systems, were analyzed. The results show that dissatisfaction with the current incentive system and not being risk-averse favor accepting the incorporation of gamification solutions into motivational systems. The responses of discount store employees and SME employees were similar to each other.

  9. Extrahepatic angiogenesis hinders recovery of portal hypertension and collaterals in rats with cirrhosis resolution.

    Science.gov (United States)

    Hsu, Shao-Jung; Tsai, Ming-Hung; Chang, Ching-Chih; Hsieh, Yu-Hsin; Huang, Hui-Chun; Lee, Fa-Yauh; Chuang, Chiao-Ling; Hou, Ming-Chih; Lee, Shou-Dong

    2018-03-30

    Liver cirrhosis is characterized by portal hypertension. However, the alteration of portal hypertension-related derangements during cirrhosis resolution is not well known. The present study aimed to establish animal models with cirrhosis resolution and to investigate the relevant changes during this process. Male Sprague-Dawley rats were applied. In reverse thioacetamide (rTAA) model, rats were randomly allocated into four groups with control, thioacetamide (TAA) cirrhosis and rTAA groups that discontinued TAA for 4 or 8 weeks after cirrhosis induction. In reverse bile duct ligation (rBDL) model, rats received choledochoduodenal shunt surgery upon the establishment of cirrhosis and 4, 8, or 16 weeks were allowed after the surgery. At the end, portal hypertension-related parameters were evaluated. Cirrhosis resolution was observed in rTAA groups. Portal pressure (PP) decreased after cirrhosis resolution but remained higher than control group (control, TAA, rTAA4, rTAA8 (mmHg): 5.4 ± 0.3, 12.9 ± 0.3, 8.6 ± 0.4, 7.6 ± 0.6). Further survey found the increased splanchnic blood flow did not reduce during cirrhosis resolution. The extrahepatic pathological angiogenesis was not ameliorated (% of mesenteric window area: 1.2 ± 0.3, 7.3 ± 1.1, 8.3 ± 1.0, 11.3 ± 2.7). In collateral system, the shunting degree reduced while the vessels structure remained. The vascular contractility of all systems and nitric oxide (NO) production were normalized. In rBDL series, PP decreased in rBDL16 groups but the extrahepatic angiogenesis persisted. In conclusion, cirrhosis resolution attenuates but not completely normalizes portal hypertension because of persistently high splanchnic inflow and angiogenesis. In clinical setting, vascular complications such as varices could persist after cirrhosis resolution and further investigation to define the follow-up and treatment strategies is anticipated. © 2018 The Author(s). Published by Portland Press Limited on behalf of the Biochemical Society.

  10. Hindering facial mimicry in ad viewing: effects on consumers’ emotions, attitudes and purchase intentions

    NARCIS (Netherlands)

    Lewinski, P.; Tan, E.S.; Fransen, M.L.; Czarna, K.; Butler, C.; Verlegh, P.; Voorveld, H.; Eisend, M.

    2016-01-01

    Recent findings in consumer psychology demonstrate that embodied cognition and bodily mimicry may influence consumers’ attitudes, intentions, and behavior (e.g. Hung & Labroo, 2011; Howard & Gengler, 2001). For example, when two friends (Bill and John) watch a funny advertisement and they both smile

  11. Direct observation of hindered eccentric rotation of an individual molecule : Cu-phthalocyanine on C60

    NARCIS (Netherlands)

    Stöhr, Meike; Wagner, T; Gabriel, M; Weyers, B; Moller, R

    2002-01-01

    Individual Cu-phthalocyanine molecules have been investigated by scanning tunnel microscopy on a closed packed film of C-60 at various temperatures. The molecules are found to bind asymmetrically to one C-60. While they remain in one position at low temperature, they can hop between six equivalent

  12. Hindered rotation of a copper phthalocyanine molecule on C60 : Experiments and molecular mechanics calculations

    NARCIS (Netherlands)

    Fendrich, M.; Wagner, Th.; Stöhr, M.; Möller, R.

    2006-01-01

    If copper phthalocyanine (CuPc) molecules are deposited on a Au(111) surface covered with a monolayer of C60, the molecules are found to adsorb individually onto the close-packed layer of C60. As the adsorption site of the CuPc is not symmetric with respect to the underlying C60 layer, the CuPc

  13. Democratizing intellectual property systems : how corruption hinders equal opportunities for firms

    NARCIS (Netherlands)

    Paunov, C.

    2014-01-01

    This paper analyses how corruption affects firms’ ownership of intellectual property titles that relate to firms’ technological, organizational and further innovation efforts: quality certificates and patents. Using firm-level data covering 48 developing and emerging countries, we show corruption

  14. Active-alkali metal promoted reductive desulfurization of dibenzothiophene and its hindered analogues

    OpenAIRE

    Pittalis, Mario; Azzena, Ugo Gavino; Carraro, Massimo; Pisano, Luisa

    2013-01-01

    Reductive desulfurisation of organic compounds is of importance both in organic synthesis and in industry. Benzo- and dibenzothiophenes are between the most abundant sulphur containing impurities in crude oils, and their desulfurization is a mandatory issue in the production of non polluting fuels. Following our interest in the development of efficient alkali metal-mediated synthetic procedures and alternative protocols for the chemical transformation of widespread environmental contaminants ...

  15. Too Much Stuff Can Hinder Children: What Do Children Really Want from Us?

    Science.gov (United States)

    Arnold, Johann Christoph

    2002-01-01

    Contends that our materialistic culture has drawn in families and created pampered, spoiled, and unhappy children which parents, child care providers, and educators are left to deal with. Asserts that parents should not be tempted by "things" to make their children happy; rather they should provide time, attentiveness, hugs, and an…

  16. Implementing Human Resources Management (HRM) within Dutch VET schools: Examining the fostering and hindering factors

    NARCIS (Netherlands)

    Runhaar, P.R.; Sanders, K.

    2013-01-01

    Vocational Education and Training (VET) Institutions face serious challenges, like the implementation of competence-based education and upcoming teacher shortages, which urge them to implement Human Resources Management policy and practices (HRM). The implementation of HRM, however, often stagnates.

  17. Could Some Geriatric Characteristics Hinder the Prescription of Anticoagulants in Atrial Fibrillation in the Elderly?

    Directory of Open Access Journals (Sweden)

    Paule Denoël

    2014-01-01

    Full Text Available Several studies have reported underprescription of anticoagulants in atrial fibrillation (AF. We conducted an observational study on 142 out of a total of 995 consecutive ≥75 years old patients presenting AF (14% when admitted in an emergency unit of a general hospital, in search of geriatric characteristics that might be associated with the underprescription of anticoagulation therapy (mostly antivitamin K at the time of the study. The following data was collected from patients presenting AF: medical history including treatment and comorbidities, CHADS2 score, ISAR scale (frailty, Lawton’s scale (ADL, GDS scale (mood status, MUST (nutrition, and blood analysis (INR, kidney function, and albumin. Among those patients for who anticoagulation treatment was recommended (73%, only 61% were treated with it. In the group with anticoagulation therapy, the following characteristics were observed more often than in the group without such therapy: a recent (≤6 months hospitalization and medical treatment including digoxin or based on >3 different drugs. Neither the value of the CHADS2 score, nor the geriatric characteristics could be correlated with the presence or the absence of an anticoagulation therapy. More research is thus required to identify and clarify the relative importance of patient-, physician-, and health care system-related hurdles for the prescription of oral anticoagulation therapy in older patients with AF.

  18. Responsible research and innovation in miniature: Information asymmetries hindering a more inclusive 'nanofood' development

    NARCIS (Netherlands)

    Bakker, de E.; Lauwere, de C.C.; Hoes, A.C.; Beekman, V.

    2014-01-01

    Responsible research and innovation (RRI) is about an interactive and comprehensive development of new technologies, also addressing social needs and ethical issues. But how do these ambitions of RRI relate to the practice of technological innovations? Nanotechnology is currently a large-scale

  19. The direct perception hypothesis: perceiving the intention of another’s action hinders its precise imitation

    Science.gov (United States)

    Froese, Tom; Leavens, David A.

    2014-01-01

    We argue that imitation is a learning response to unintelligible actions, especially to social conventions. Various strands of evidence are converging on this conclusion, but further progress has been hampered by an outdated theory of perceptual experience. Comparative psychology continues to be premised on the doctrine that humans and non-human primates only perceive others’ physical “surface behavior,” while mental states are perceptually inaccessible. However, a growing consensus in social cognition research accepts the direct perception hypothesis: primarily we see what others aim to do; we do not infer it from their motions. Indeed, physical details are overlooked – unless the action is unintelligible. On this basis we hypothesize that apes’ propensity to copy the goal of an action, rather than its precise means, is largely dependent on its perceived intelligibility. Conversely, children copy means more often than adults and apes because, uniquely, much adult human behavior is completely unintelligible to unenculturated observers due to the pervasiveness of arbitrary social conventions, as exemplified by customs, rituals, and languages. We expect the propensity to imitate to be inversely correlated with the familiarity of cultural practices, as indexed by age and/or socio-cultural competence. The direct perception hypothesis thereby helps to parsimoniously explain the most important findings of imitation research, including children’s over-imitation and other species-typical and age-related variations. PMID:24600413

  20. N-Formyl-Perosamine Surface Homopolysaccharides Hinder the Recognition of Brucella abortus by Mouse Neutrophils.

    Science.gov (United States)

    Mora-Cartín, Ricardo; Chacón-Díaz, Carlos; Gutiérrez-Jiménez, Cristina; Gurdián-Murillo, Stephany; Lomonte, Bruno; Chaves-Olarte, Esteban; Barquero-Calvo, Elías; Moreno, Edgardo

    2016-06-01

    Brucella abortus is an intracellular pathogen of monocytes, macrophages, dendritic cells, and placental trophoblasts. This bacterium causes a chronic disease in bovines and in humans. In these hosts, the bacterium also invades neutrophils; however, it fails to replicate and just resists the killing action of these leukocytes without inducing significant activation or neutrophilia. Moreover, B. abortus causes the premature cell death of human neutrophils. In the murine model, the bacterium is found within macrophages and dendritic cells at early times of infection but seldom in neutrophils. Based on this observation, we explored the interaction of mouse neutrophils with B. abortus In contrast to human, dog, and bovine neutrophils, naive mouse neutrophils fail to recognize smooth B. abortus bacteria at early stages of infection. Murine normal serum components do not opsonize smooth Brucella strains, and neutrophil phagocytosis is achieved only after the appearance of antibodies. Alternatively, mouse normal serum is capable of opsonizing rough Brucella mutants. Despite this, neutrophils still fail to kill Brucella, and the bacterium induces cell death of murine leukocytes. In addition, mouse serum does not opsonize Yersinia enterocolitica O:9, a bacterium displaying the same surface polysaccharide antigen as smooth B. abortus Therefore, the lack of murine serum opsonization and absence of murine neutrophil recognition are specific, and the molecules responsible for the Brucella camouflage are N-formyl-perosamine surface homopolysaccharides. Although the mouse is a valuable model for understanding the immunobiology of brucellosis, direct extrapolation from one animal system to another has to be undertaken with caution. Copyright © 2016, American Society for Microbiology. All Rights Reserved.

  1. Does it help or hinder? Promotion of Innovation on the Internet and Citizens’ Right to Privacy

    NARCIS (Netherlands)

    Cave, J.; Bodea, G.; Kool, K.; Lieshout, M. van

    2011-01-01

    This study investigates the interplay between Internet innovation and privacy. We propose working definitions of innovation and privacy and review the literature about their interaction. We interpret the possible tensions and problems in terms of market and system failures and analyse the relevant

  2. Doxycycline hinders phenylalanine fibril assemblies revealing a potential novel therapeutic approach in phenylketonuria.

    Science.gov (United States)

    De Luigi, Ada; Mariani, Alessandro; De Paola, Massimiliano; Re Depaolini, Andrea; Colombo, Laura; Russo, Luca; Rondelli, Valeria; Brocca, Paola; Adler-Abramovich, Lihi; Gazit, Ehud; Del Favero, Elena; Cantù, Laura; Salmona, Mario

    2015-10-29

    A new paradigm for the aetiopathology of phenylketonuria suggests the presence of amyloid-like assemblies in the brains of transgenic mouse models and patients with phenylketonuria, possibly shedding light on the selective cognitive deficit associated with this disease. Paralleling the amyloidogenic route that identifies different stages of peptide aggregation, corresponding to different levels of toxicity, we experimentally address for the first time, the physico-chemical properties of phenylalanine aggregates via Small Angle, Wide Angle X-ray Scattering and Atomic Force Microscopy. Results are consistent with the presence of well-structured, aligned fibres generated by milliMolar concentrations of phenylalanine. Moreover, the amyloid-modulating doxycycline agent affects the local structure of phenylalanine aggregates, preventing the formation of well-ordered crystalline structures. Phenylalanine assemblies prove toxic in vitro to immortalized cell lines and primary neuronal cells. Furthermore, these assemblies also cause dendritic sprouting alterations and synaptic protein impairment in neurons. Doxycycline counteracts these toxic effects, suggesting an approach for the development of future innovative non-dietary preventive therapies.

  3. Does emotion help or hinder reasoning? The moderating role of relevance.

    Science.gov (United States)

    Blanchette, Isabelle; Gavigan, Sarah; Johnston, Kathryn

    2014-06-01

    Some prior research has shown that emotion impairs logicality in deductive reasoning tasks, while other research suggests improved performance with emotional contents. We suggest that relevance, whether the affective state is associated with the semantic contents of the reasoning task, may be crucial in explaining these apparently inconsistent findings. This hypothesis is based on a framework distinguishing between integral emotions, where affective responses are evoked by the semantic contents of the target task, and incidental emotions, where affective responses are not related to the task. In 4 experiments we examined the effect of emotion on conditional reasoning when affective responses were relevant and irrelevant. We used images presented simultaneously with the reasoning stimuli (Experiments 1, 2, and 3) or videos presented prior to the reasoning stimuli (Experiment 4) that were either emotional or neutral and semantically related or not to the conditional statements. Results showed that emotion decreased the proportion of normatively correct responses only in the irrelevant condition. In the relevant condition, emotion did not produce reliable deleterious effects. We used reaction time and skin conductance measures to investigate the physiological and cognitive correlates of these effects. Results are discussed in terms of the distinction between incidental and integral emotions. PsycINFO Database Record (c) 2014 APA, all rights reserved.

  4. Does the concept of safety culture help or hinder systems thinking in safety?

    Science.gov (United States)

    Reiman, Teemu; Rollenhagen, Carl

    2014-07-01

    The concept of safety culture has become established in safety management applications in all major safety-critical domains. The idea that safety culture somehow represents a "systemic view" on safety is seldom explicitly spoken out, but nevertheless seem to linger behind many safety culture discourses. However, in this paper we argue that the "new" contribution to safety management from safety culture never really became integrated with classical engineering principles and concepts. This integration would have been necessary for the development of a more genuine systems-oriented view on safety; e.g. a conception of safety in which human, technological, organisational and cultural factors are understood as mutually interacting elements. Without of this integration, researchers and the users of the various tools and methods associated with safety culture have sometimes fostered a belief that "safety culture" in fact represents such a systemic view about safety. This belief is, however, not backed up by theoretical or empirical evidence. It is true that safety culture, at least in some sense, represents a holistic term-a totality of factors that include human, organisational and technological aspects. However, the departure for such safety culture models is still human and organisational factors rather than technology (or safety) itself. The aim of this paper is to critically review the various uses of the concept of safety culture as representing a systemic view on safety. The article will take a look at the concepts of culture and safety culture based on previous studies, and outlines in more detail the theoretical challenges in safety culture as a systems concept. The paper also presents recommendations on how to make safety culture more systemic. Copyright © 2013 Elsevier Ltd. All rights reserved.

  5. International piracy and armed robbery at sea : hindering maritime trade and water transportation around the world

    Science.gov (United States)

    2010-04-01

    Pirates prey upon targets of opportunity. Given optimal conditions (e.g., calm weather, slow cruising speed, and daylight4) relatively small, fast vessels (e.g., containerships) may be no less at risk than large, slower vessels (e.g., crude carriers)...

  6. High solar radiation hinders tree regeneration above the alpine treeline in northern Ecuador

    NARCIS (Netherlands)

    Bader, M.; Geloof, van I.; Rietkerk, M.

    2007-01-01

    Many tropical alpine treelines lie below their climatic potential, because of natural or anthropogenic causes. Forest extension above the treeline depends on the ability of trees to establish in the alpine environment. This ability may be limited by different factors, such as low temperatures,

  7. High solar radiation hinders tree regeneration above the alpine treeline in northern Ecuador

    NARCIS (Netherlands)

    Bader, M.Y.; Geloof, I. van; Rietkerk, M.G.

    2007-01-01

    Many tropical alpine treelines lie below their climatic potential, because of natural or anthropogenic causes. Forest extension above the treeline depends on the ability of trees to establish in the alpine environment. This ability may be limited by different factors, such as low

  8. The economic, political and social issues, hindering the adoption of bioenergy in Pakistan: a case study

    Energy Technology Data Exchange (ETDEWEB)

    Usman, Umair [UCH, Moonoo Chowk, Lahore (Pakistan)], e-mail: Umair@uch.com.pk

    2012-11-01

    The paper will inform the audience about the energy crisis that has crippled Pakistan's economic growth since the last 6 years, and the role that Bioenergy can play in resolving the issue. In order to help ease Pakistan in its effort to curb this crisis and to get useful insights into the role that Bioenergy can play in solving Pakistan's problems, Business planning for a Small or Medium sized enterprise was attempted. The results were not encouraging and shed light onto the financial and technical hindrances involved in creating and running Small or Medium bioenergy businesses in Pakistan. These issues themselves were linked to the more general Social, Economic and Political barriers for the adoption of Bioenergy in the country. The paper concludes by providing suggestions and recommendations, as to what the government, private sector as well as the international community can do in order to overcome the crisis.

  9. Does gender inequality hinder development and economic growth ? evidence and policy implications

    OpenAIRE

    Bandiera, Oriana; Natraj, Ashwini

    2013-01-01

    Does the existing evidence support policies that foster growth by reducing gender inequality? The authors argue that the evidence based on differences across countries is of limited use for policy design because it does not identify the causal link from inequality to growth. This, however does not imply that inequality-reducing policies are ineffective. In other words, the lack of evidence...

  10. Muslim Prison Ministry: Hindering the Spread of the Radical, Militant, Violent and Irreconcilable Wing of Islam

    National Research Council Canada - National Science Library

    Dooghan, James K

    2006-01-01

    .... However, addressing violent Islamic ideology at the grass roots level may decrease the number of terrorists recruited and increase the number of Muslims favoring a nonviolent interpretation of the Qur'an...

  11. Exogenous α-synuclein hinders synaptic communication in cultured cortical primary rat neurons

    NARCIS (Netherlands)

    Hassink, G. C.; Raiss, C. C.; Segers-Nolten, I. M.J.; Van Wezel, R. J.A.; Subramaniam, V.; Le Feber, J.; Claessens, M. M.A.E.

    2018-01-01

    Amyloid aggregates of the protein a-synuclein (aS) called Lewy Bodies (LB) and Lewy Neurites (LN) are the pathological hallmark of Parkinson's disease (PD) and other synucleinopathies. We have previously shown that high extracellular αS concentrations can be toxic to cells and that neurons take up

  12. Exogenous α-synuclein hinders synaptic communication in cultured cortical primary rat neurons.

    Science.gov (United States)

    Hassink, G C; Raiss, C C; Segers-Nolten, I M J; van Wezel, R J A; Subramaniam, V; le Feber, J; Claessens, M M A E

    2018-01-01

    Amyloid aggregates of the protein α-synuclein (αS) called Lewy Bodies (LB) and Lewy Neurites (LN) are the pathological hallmark of Parkinson's disease (PD) and other synucleinopathies. We have previously shown that high extracellular αS concentrations can be toxic to cells and that neurons take up αS. Here we aimed to get more insight into the toxicity mechanism associated with high extracellular αS concentrations (50-100 μM). High extracellular αS concentrations resulted in a reduction of the firing rate of the neuronal network by disrupting synaptic transmission, while the neuronal ability to fire action potentials was still intact. Furthermore, many cells developed αS deposits larger than 500 nm within five days, but otherwise appeared healthy. Synaptic dysfunction clearly occurred before the establishment of large intracellular deposits and neuronal death, suggesting that an excessive extracellular αS concentration caused synaptic failure and which later possibly contributed to neuronal death.

  13. Promote or hinder? The role of punishment in the emergence of cooperation.

    Science.gov (United States)

    Gao, Shiping; Wu, Te; Nie, Suli; Wang, Long

    2015-12-07

    Investigation of anti-social punishment has shaken the positive role of punishment in the evolution of cooperation. However, punishment is ubiquitous in nature, and the centralized, apposed to decentralized, punishment is more favored by certain modern societies in particular. To explore the underlying principle of such phenomenon, we study the evolution of cooperation in the context of pro- and anti-social punishments subject to two distinct patterns: costly centralized and decentralized punishments. The results suggest that the pattern of punishment has a great effect on the role of punishment in the evolution of cooperation. In the absence of anti-social punishment, the costly centralized punishment is more effective in promoting the emergence of cooperation. Anti-social punishment can subvert the positive role of punishment when anti- and pro-social punishments are in the same pattern. However, driven by centralized pro-social punishment, cooperation can be more advantageous than defection even in the presence of decentralized anti-social punishment. Copyright © 2015 Elsevier Ltd. All rights reserved.

  14. How hepatitis D virus can hinder the control of hepatitis B virus.

    Directory of Open Access Journals (Sweden)

    Maria Xiridou

    Full Text Available BACKGROUND: Hepatitis D (or hepatitis delta virus is a defective virus that relies on hepatitis B virus (HBV for transmission; infection with hepatitis D can occur only as coinfection with HBV or superinfection of an existing HBV infection. Because of the bond between the two viruses, control measures for HBV may have also affected the spread of hepatitis D, as evidenced by the decline of hepatitis D in recent years. Since the presence of hepatitis D is associated with suppressed HBV replication and possibly infectivity, it is reasonable to speculate that hepatitis D may facilitate the control of HBV. METHODOLOGY AND PRINCIPAL FINDINGS: We introduced a mathematical model for the transmission of HBV and hepatitis D, where individuals with dual HBV and hepatitis D infection transmit both viruses. We calculated the reproduction numbers of single HBV infections and dual HBV and hepatitis D infections and examined the endemic prevalences of the two viruses. The results show that hepatitis D virus modulates not only the severity of the HBV epidemic, but also the impact of interventions for HBV. Surprisingly we find that the presence of hepatitis D virus may hamper the eradication of HBV. Interventions that aim to reduce the basic reproduction number of HBV below one may not be sufficient to eradicate the virus, as control of HBV depends also on the reproduction numbers of dual infections. CONCLUSIONS AND SIGNIFICANCE: For populations where hepatitis D is endemic, plans for control programs ignoring the presence of hepatitis D may underestimate the HBV epidemic and produce overoptimistic results. The current HBV surveillance should be augmented with monitoring of hepatitis D, in order to improve accuracy of the monitoring and the efficacy of control measures.

  15. Beauty hinders attention switch in change detection: the role of facial attractiveness and distinctiveness.

    Directory of Open Access Journals (Sweden)

    Wenfeng Chen

    Full Text Available BACKGROUND: Recent research has shown that the presence of a task-irrelevant attractive face can induce a transient diversion of attention from a perceptual task that requires covert deployment of attention to one of the two locations. However, it is not known whether this spontaneous appraisal for facial beauty also modulates attention in change detection among multiple locations, where a slower, and more controlled search process is simultaneously affected by the magnitude of a change and the facial distinctiveness. Using the flicker paradigm, this study examines how spontaneous appraisal for facial beauty affects the detection of identity change among multiple faces. METHODOLOGY/PRINCIPAL FINDINGS: Participants viewed a display consisting of two alternating frames of four faces separated by a blank frame. In half of the trials, one of the faces (target face changed to a different person. The task of the participant was to indicate whether a change of face identity had occurred. The results showed that (1 observers were less efficient at detecting identity change among multiple attractive faces relative to unattractive faces when the target and distractor faces were not highly distinctive from one another; and (2 it is difficult to detect a change if the new face is similar to the old. CONCLUSIONS/SIGNIFICANCE: The findings suggest that attractive faces may interfere with the attention-switch process in change detection. The results also show that attention in change detection was strongly modulated by physical similarity between the alternating faces. Although facial beauty is a powerful stimulus that has well-demonstrated priority, its influence on change detection is easily superseded by low-level image similarity. The visual system appears to take a different approach to facial beauty when a task requires resource-demanding feature comparisons.

  16. An Investigation of the Factors Hindering Adults' Participation in Physical Activity

    Science.gov (United States)

    Dinç, Zeynep Filiz

    2017-01-01

    This study focuses on the non-participation of adults in physical activity and the reasons that have been preventing them to participate. The study is carried out with 283 participants (116 men and 167 women) who live in Adana, Turkey. Their ages range from 18-66. The average age of the adult participants is 31.81 ± 10.12. The demographical…

  17. Configuration changes and hindered decays in four- and six-quasiparticle isomers in 178Ta

    International Nuclear Information System (INIS)

    Kondev, F.G.; Dracoulis, G.D.; Byrne, A.P.; Kibedi, T.; Bayer, S.; Lane, G.J.

    1996-01-01

    A six-quasiparticle isomer with K π =21 - , a half-life of 290(12) ms, and the π 3 ν 3 configuration has been identified in the odd-odd nucleus 178 Ta, at an excitation energy of 2902 keV. The rotational bands built on the known K π =15 - isomer and on the newly found 16 + four-quasiparticle and 22 + six-quasiparticle states, have also been identified, allowing characterization of the configurations. The 15 - band is predominantly of πν 3 character with a π 3 ν admixture. When the mixing is taken into account the excitation energies of the main yrast multi-quasiparticle states can be reproduced. The multi-quasiparticle states observed are related essentially through the addition of the two-quasiparticle component ν 2 [6 + ] or π 2 [6 + ]. Depending on whether the transition between the states involves the change ν 2 [6 + ] → [0] or π 2 [6 + ] → [0], the E2 hindrance factors for decays between the six- and four-quasiparticle states are relatively large or small. This dependence mimics the pattern observed in the two-quasiparticle core transitions and, because the 15 - isomer is mainly πν 3 , the magnitude sequence is inverted compared to that observed in 176 Ta. copyright 1996 The American Physical Society

  18. Do comprehensive performance measurement systems help or hinder managers' mental model development?

    OpenAIRE

    Matthew Hall

    2011-01-01

    This study examines whether and how the process of updating and changing mental models (learning) helps to explain how performance measurement systems (PMS) affect individual performance. Although prior studies (e.g., Hall, 2008; Burney and Widener, 2007; Burney et al., 2009) highlight the important role of particular cognitive and motivational mechanisms, such as role clarity and organizational justice, they do not consider how PMS can improve performance by helping individuals to update the...

  19. Fermentation broth components influence droplet coalescence and hinder advanced biofuel recovery during fermentation

    NARCIS (Netherlands)

    Heeres, A.S.; Schroën, C.G.P.H.; Heijnen, J.J.; Wielen, van der L.A.M.; Cuellar, M.C.

    2015-01-01

    Developments in synthetic biology enabled the microbial production of long chain hydrocarbons, which can be used as advanced biofuels in aviation or transportation. Currently, these fuels are not economically competitive due to their production costs. The current process offers room for improvement:

  20. Common contaminants in next-generation sequencing that hinder discovery of low-abundance microbes.

    Directory of Open Access Journals (Sweden)

    Martin Laurence

    Full Text Available Unbiased high-throughput sequencing of whole metagenome shotgun DNA libraries is a promising new approach to identifying microbes in clinical specimens, which, unlike other techniques, is not limited to known sequences. Unlike most sequencing applications, it is highly sensitive to laboratory contaminants as these will appear to originate from the clinical specimens. To assess the extent and diversity of sequence contaminants, we aligned 57 "1000 Genomes Project" sequencing runs from six centers against the four largest NCBI BLAST databases, detecting reads of diverse contaminant species in all runs and identifying the most common of these contaminant genera (Bradyrhizobium in assembled genomes from the NCBI Genome database. Many of these microorganisms have been reported as contaminants of ultrapure water systems. Studies aiming to identify novel microbes in clinical specimens will greatly benefit from not only preventive measures such as extensive UV irradiation of water and cross-validation using independent techniques, but also a concerted effort to sequence the complete genomes of common contaminants so that they may be subtracted computationally.

  1. Teacher Practices: How They Promote or Hinder Student Engagement in Mathematics

    Science.gov (United States)

    Skilling, Karen

    2014-01-01

    With persistent concerns about student engagement, interest and participation in mathematics, this research investigated the range of practices 31 Year 7 mathematics teachers reported using and how they perceived these practices influenced student engagement in mathematics. In-depth interviews revealed similarities in teachers' perceptions of…

  2. Implementation of new skills to support lifestyle changes - what helps and what hinders?

    Science.gov (United States)

    Tinati, Tannaze; Lawrence, Wendy; Ntani, Georgia; Black, Christina; Cradock, Sue; Jarman, Megan; Pease, Anna; Inskip, Hazel; Cooper, Cyrus; Baird, Janis; Barker, Mary

    2013-01-01

    Effective communication is necessary for good relationships between healthcare practitioners and clients. This study examined barriers and facilitators to implementing new communication skills. One hundred and one Sure Start Children’s Centre staff attended one of 13 follow-up workshops to reflect on the use of new skills following a training course in communication, reflection and problem-solving. Barriers and facilitators were assessed with an adapted Problematic Experiences of Therapy scale (PETS). Staff reported frequency of skill use, and described what made it more difficult or easier to use the skills. The PETS indicated that staff had confidence in using the skills, but felt there were practical barriers to using them, such as lack of time. Skills were used less often when staff perceived parents not to be engaging with them (rs=−0.42, puse the skills (rs =−0.37, pskills. Facilitators included seeing the benefits of using the skills, finding opportunities and having good relationships with parents. Understanding the range of barriers and facilitators to implementation is essential when developing training to facilitate on-going support and sustain skill use. Special attention should be given to exploring trainees’ perceptions of time, in order to be able to address this significant barrier to skill implementation. Staff training requires a multifaceted approach to address the range of perceived barriers. PMID:22452549

  3. How Approaches to Stuck-in-the-Mud School Funding Hinder Improvement

    Science.gov (United States)

    Lazarín, Melissa

    2013-01-01

    Many state and education leaders continue to support and employ methods that prevent schools and principals from undertaking the efforts that they think are most needed to improve education in their classrooms. The use of state categorical grants--funds to school districts with strict limits on their use--exemplifies this lack of innovation in…

  4. Muslim Prison Ministry: Hindering the Spread of the Radical, Militant, Violent and Irreconcilable Wing of Islam

    Science.gov (United States)

    2006-05-25

    radical, militant, violent and irreconcilable wing of Islam Approved by: __________________________________ Monograph Director Timothy L . Challans, Ph.D...Honorable Harley Lapin (BOP), Dr. Michael Waller (Institute of World Politics), Mr. Paul Rogers (ACCA), and Mr. A. J. Sabree (ACCA). 78 Ibid., 12...London, United Kingdom: Verso books, 2005. Patai, Raphael. The Arab Mind, Long Island City, NY: Hatherleigh Press, 2002. Pederson , Dick. Defeating

  5. Myeloma-Derived Light Chain Paired with a Diagnostic Monoclonal Antibody Hinders Immunoassay Performance.

    Science.gov (United States)

    Tu, Bailin; Tieman, Bryan; Moore, Jeffrey; Pan, You; Muerhoff, A Scott

    2017-06-01

    Monoclonal antibodies are widely used as the capture and detection reagents in diagnostic immunoassays. In the past, myeloma fusion partners expressing endogenous heavy and/or light chains were often used to generate hybridoma cell lines. As a result, mixed populations of antibodies were produced that can cause inaccurate test results, poor antibody stability, and significant lot-to-lot variability. We describe one such scenario where the P3U1 (P3X63Ag8U.1) myeloma fusion partner was used in the generation of a hybridoma producing protein induced vitamin K absence/antagonist-II (PIVKA II) antibody. The hybridoma produces three subpopulations of immunoglobulin as determined by ion exchange (IEx) chromatography that exhibit varying degrees of immunoreactivity (0%, 50%, or 100%) to the target antigen as determined by Surface Plasmon Resonance. To produce an antibody with the highest possible sensitivity and specificity, the antigen-specific heavy and light chain variable domains (VH and VL) were cloned from the hybridoma and tethered to murine IgG1 and kappa scaffolds. The resulting recombinant antibody was expressed in Chinese hamster ovary cells and is compatible for use in a diagnostic immunoassay.

  6. The Englishnization of Business: Does This Help or Hinder Teaching Global Business?

    Science.gov (United States)

    Cavaliere, Frank J.; Glasscock, Kip; Sen, Kabir C.

    2014-01-01

    Globalization has been one of the most important movements in business since the end of World War II. The business education establishment, as represented by the AACSB accreditation agency, has been struggling to get its member schools to properly prepare their graduates for this new global business environment. It has generally been conceded that…

  7. Innovative Ways to Use Modern Technology to Enhance, Rather than Hinder, Physical Activity among Youth

    Science.gov (United States)

    Martin, Nicole J.; Ameluxen-Coleman, Evan J.; Heinrichs, Derikk M.

    2015-01-01

    It is recommended that each day youth get 60 minutes or more of moderate-to-vigorous physical activity that includes aerobic, muscle, and bone strengthening activities. The majority of youth, however, do not meet these physical activity guidelines. Children and adolescents spend on average seven hours engaging in sedentary "screen-based"…

  8. Children's Television Commercials Containing Nutritional Information: When Do They Help? When Do They Hinder?

    Science.gov (United States)

    Ross, Rhonda P.; And Others

    This study assessed the accuracy of judgments of 100 school-age children (5-11 years of age) as to the presence of real fruit content in three sets of cereals and beverages advertised on TV: real fruit, nonfruit, and artificially flavored products. In the baseline session accuracy increased with age, but children at each age misjudged the real…

  9. Hindering effects in diffusion of CO2/CH4 mixtures in ZIF-8 crystals

    NARCIS (Netherlands)

    Chmelik, C.; van Baten, J.; Krishna, R.

    2012-01-01

    Cage-type micro-porous materials such as LTA, CHA, SAPO-34, DDR, ERI, ZIF-7, and ZIF-8 have significant potential for use in membrane technologies for CO2 capture. The permeation selectivities are governed by a combination of adsorption and diffusion selectivities, each of which can be separately

  10. Traveling Companions Add Complexity and Hinder Performance in the Spatial Behavior of Rats

    DEFF Research Database (Denmark)

    Dorfman, Alex; Nielbo, Kristoffer Laigaard; Eilam, David

    2016-01-01

    -mate. It was found that the presence of another rat substantially altered the rats' spatial behavior. Lone rats collected the food items faster while traveling a shorter distance, reflecting a higher efficiency of task completion. When accompanied by a partner, however, the rats traveled together, visiting the same......We sought to uncover the impact of the social environment on the spatial behavior of rats. Food-deprived rats were trained in a spatial task of collecting food items from 16 equispaced objects. Following training, they were tested, first alone and then with a similarly-trained cage...... of rats’ natural behavior. Revisiting an object following food depletion implies that searching for food was not the main driving force in the rats' spatial behavior. Specifically, despite food deprivation, rats were more attentive to one another than to the food. This could be adaptive, since foraging...

  11. Globalization of authorship in the marketing discipline: Does it help or hinder the field?

    NARCIS (Netherlands)

    S. Stremersch (Stefan); P.C. Verhoef (Peter)

    2005-01-01

    textabstractMarketing scholars have reflected upon the marketing discipline's internal evolution before. However, no prior study has assessed the globalization of authorship in our discipline, let alone assessed its consequences for the field. This paper addresses the following two questions: (1) Is

  12. Globalization of authorship in the marketing discipline : Does it help or hinder the field?

    NARCIS (Netherlands)

    Stremersch, S; Verhoef, PC

    2005-01-01

    Marketing scholars have reflected upon the marketing discipline's internal evolution before. However, no prior study has assessed the globalization of authorship in our discipline, let alone assessed its consequences for the field. This paper addresses the following two questions: (1) Is there

  13. Does infrastructure provision hinder energy integration? The case of natural gas in the southern cone

    Energy Technology Data Exchange (ETDEWEB)

    Navajas, Fernando

    2010-09-15

    This paper uses evidence on policies, markets and private transactions to discuss the experience of natural gas infrastructure integration in the Southern Cone of Latin America. The argument is that contracts on international exchanges supported by infrastructure may become incomplete due to contingencies related to policy-induced price distortions not anticipated at the moment of writing. Beyond regulatory risk mitigation, it calls for back-up contract provisions designed to cope with aggregate imbalances and for some supranational coordination related to information about market conditions and on energy planning dialogues that test consistency and stress situations in markets where exports originate.

  14. Evaluating the predictivity of virtual screening for ABL kinase inhibitors to hinder drug resistance

    DEFF Research Database (Denmark)

    Gani, Osman A B S M; Narayanan, Dilip; Engh, Richard A

    2013-01-01

    decoy sets and tested with virtual screening approaches with and without explicit use of target structures (docking). We show how various scoring functions and choice of inactive ligand sets influence overall and early enrichment of the libraries. Although ligand-based methods, for example principal...... component analyses of chemical properties, can distinguish some decoy sets from active compounds, the addition of target structural information via docking improves enrichment, and explicit consideration of multiple target conformations (i.e. types I and II) achieves best enrichment of active versus...

  15. Comparing Strategies for Health Information Dissemination: Messengers That Can Help or Hinder.

    Science.gov (United States)

    Fishman, Jessica; Greenberg, Patricia; Bagga, Margy Barbieri; Casarett, David; Propert, Kathleen

    2018-05-01

    To test the effects of different messengers on the dissemination of health information. An experimental study exposed participants to 12 news articles pertaining to 1 of 3 health topics framed from the perspective of 4 generic messengers: religious figures, doctors, celebrity patients, or ordinary patients. Participants select as many of the 12 articles as desired. A cancer clinic within a large, urban hospital serving a sociodemographically diverse patient population. Eighty-nine patients with a history of cancer. The primary outcome was the frequency with which each news story was selected. Summary statistics and a general estimating equation model. For each health topic, news articles using celebrity messengers were the least likely to be selected; almost half of the participants (36 [41.4%] of 87) rejected all such articles. Articles linked to religious figures were equally unpopular ( P = .59). Articles that used doctors or ordinary patients as the messenger were very likely to be selected: Nearly all women (84 [96.6%] of 87) selected at least one of these. Furthermore, the odds of choosing articles linked to celebrities or religious leaders were statistically significantly lower than the odds of choosing those linked to ordinary patients or doctors ( P dissemination of information. Health materials linked to celebrities or religious figures were consistently less likely to be selected than those linked to ordinary patients, or doctors.

  16. The Achievement Gap among Newcomer Immigrant Adolescents: Life Stressors Hinder Latina/o Academic Success

    Science.gov (United States)

    Patel, Sita G.; Barrera, Alinne Z.; Strambler, Michael J.; Muñoz, Ricardo F.; Macciomei, Erynn

    2016-01-01

    This study compares life stressors and school outcomes among newcomer immigrant adolescents from Latin America, Asia, and the Caribbean. Participants attended a predominantly low-income, urban international public high school in the northeast. The Latina/o students were exposed to more life stressors and had lower attendance and achievement than…

  17. Coping Strategies to Hinder Intention to Leave in Iranian Nurses: A Qualitative Content Analysis

    Science.gov (United States)

    Valizadeh, Leila; Zamanzadeh, Vahid; Habibzadeh, Hosein; Alilu, Leyla; Shakibi, Ali

    2015-01-01

    Background: Due to the high clinical challenges, differences in coping strategies, and high workload in nurses, there is a need to develop strategies to keep them in the profession. The aim of the present study was to explore the Iranian nurses’ coping strategies to deal with intention to leave. Methods: A qualitative content analysis was used to obtain rich data. We performed 13 in-depth face-to-face semi-structured interviews with nurses working in hospitals affiliated to Tabriz and Urmia Universities of Medical Sciences in Iran, selected through purposive sampling. Constant comparative method was used for data analysis. Results: Three categories and eleven subcategories emerged during data analysis. The extracted categories and sub-categories consisted of (I) Self-empowerment (practical knowledge increase, responsibility, finding identification of the nurse, balancing work and life, seek support and humanitarian interests), (II) Self-controlling (tolerance, avoidance, the routine-based performance), and (III) Pursuing opportunities for advancement and promotion (community development, planning for higher education). Conclusion: Nurses make attempts to individually manage problems and stressors perceived from bedside that have led them to leave the bedside; these efforts have been effective in some cases but sometimes they are ineffective due to discontinuous training and relative competence in terms of how to manage and deal with problems. It is suggested that nurses should learn strategies scientifically to meet the challenges of bedside. Through enabling and supporting behaviors and creating opportunities for growth and professional development, nursery managers can help nurses to stay and achieve improvement of the quality of cares. PMID:26448959

  18. Home Health Care (HHC) Managers Perceptions About Challenges and Obstacles that Hinder HHC Services in Jordan

    Science.gov (United States)

    Ajlouni, Musa T.; Dawani, Hania; Diab, Salah M.

    2015-01-01

    Home care aims at supporting people with various degrees of dependency to remain at home rather than use residential, long-term, or institutional-based nursing care. Demographic, epidemiological, social, and cultural trends in Jordan as in other countries are changing the traditional patterns of care with growing emphasis on home care. The purpose of this study is to highlight the most common challenges related to home health care (HHC) services in Jordan as perceived by the managers of HHC agencies. Methods: a descriptive qualitative design that depends on focus group discussions has been used to collect data from a sample of 18 managers who met the selection criteria and who are willing to participate, the study found that, the main challenges of HHC services as perceived by managers were: shortage of female staff, lack of governance and regulation, poor management, unethical practices, lack of referral systems, and low accessibility of the poor and less privileged as HHC services are not included in health insurance schemes, it concludes also that the home health care industry in Jordan is facing many challenges and problems that may have negative effects on the effectiveness, efficiency, equity and quality of services and should be addressed by health policy makers. PMID:25946949

  19. Diversity, Equity, and Inclusion in Independent Schools: How Silence and Privilege Hinder the Work

    OpenAIRE

    Perez del Toro, Jessica

    2017-01-01

    Most private or independent schools originated as schools of privilege, serving the offspring of a culturally and socially elite group of white American families (Cookson, 2013; Flewelling, 2013; Slaughter-Defoe & Johnson, 1988). Since the 1960s these institutions have worked to change their predominantly White, elitist image by broadening their access and striving to become diverse and inclusive institutions that prepare all students to “thrive in a global, multicultural community” (Quanti, ...

  20. ‘Standard’ incentive regulation hinders the integration of renewable energy generation

    NARCIS (Netherlands)

    Nykamp, Stefan; Andor, Mark; Hurink, Johann L.

    The connection and distribution of growing, decentralized electricity generation from renewable energy sources (RES-E) is leading tomassive investment needs. Besides investing in additional ‘conventional’ assets (e.g. cables), grid operators can also invest in innovative ‘smart solutions’ like local

  1. Energy Choices. Efficient Energy Use - possibilities and barriers; Vaegval Energi. Energieffektivisering - moejligheter och hinder

    Energy Technology Data Exchange (ETDEWEB)

    Jagemar, Lennart (CIT Energy Management AB, Goeteborg (Sweden)); Pettersson, Bertil (Chalmers EnergiCentrum, CEC, Chalmers Univ. of Technology, Goeteborg (Sweden))

    2009-02-15

    Sweden's total energy supply in 2006 amounted to a total of 624 TWh and was dominated by crude oil, nuclear fuels, biofuels and hydropower. Different types of losses in the system accounts for one third of the energy. The final energy consumption, i.e. delivery minus losses, was divided in the following way: industry 157 TWh, the habitat of 145 TWh (of which 19 TWh relates to Agriculture, Forestry, Fishery and other service and secondary homes) and transport of 101 TWh. For the transport sector, studies show that combinations of various efficiency measures ideally can achieve an reduction in energy use by between 60 and 75 percent. The Governmental Energy Efficiency Inquiry (EnEff - 2008) estimated that the domestic transport techno-economic efficiency potential up to 2016 is 13 TWh (mainly fuel) of the total delivered energy is 87 TWh under EnEff. The potential about 5 TWh is expected to be completed by current instruments. The study assesses that despite the increased need for transport in 2016 the sector's energy use can remain at the same level or even be reduced. Buildings have a large technical and economic energy efficiency potential. According to EnEff's assessment, the streamlining potential is 33 TWh of which 8 TWh can implemented in 2016 with today's instruments. This compares with the total delivered energy is 151 TWh under EnEff. The total energy efficiency potential for buildings by 2020 is considered to be substantially higher, about 41 TWh, and affect the use of district heating, fuel and electricity. New powerful tools must be implemented for the building sector in order to realize the potential energy efficiency measures. Industry's total energy potential is assessed to be around 13 TWh by 2016. Industry's total energy use is 155 TWh according to EnEff. Only 2 TWh can realistically be saved up to 2016 taking into account a reasonable acceptance factor. The beneficiaries of the carbon emissions trade account for about four-fifths of industry fossil fuel use and therefore has the greatest energy efficiency potential in absolute terms. According Eneffs final report the total energy efficiency potential for that part of the industry is about 7 TWh. Efficiency potential to 2016 for the industry not covered by the emissions trading amounts to just 6 TWh per year. Eneff believe that the industry's total energy use by 2016 may correspond to the present use at an expected increased production output, provided that additional stimulating instruments are deployed. Such a development requires that almost all of the industry's profitable energy efficiency potential (nearly 11 TWh) is realized. Possible energy efficiency potential for the industry, based on previous studies (IVAs Energiframsyn) were 10 and 15 percent, which totals 15 to 20 TWh. Finally in this report, a qualitative analysis is made of the consequences of ambitious energy efficiency measures, mainly the effects on volumes and relative importance of the different energy carriers for a twenty year term

  2. Subtraction by Distraction: Publishing Value-Added Estimates of Teachers by Name Hinders Education Reform

    Science.gov (United States)

    Epstein, Diana; Miller, Raegen T.

    2011-01-01

    In August 2010 the "Los Angeles Times" published a special report on their website featuring performance ratings for nearly 6,000 Los Angeles Unified School District teachers. The move was controversial because the ratings were based on so-called value-added estimates of teachers' contributions to student learning. As with most…

  3. Coping Strategies to Hinder Intention to Leave in Iranian Nurses: A Qualitative Content Analysis.

    Science.gov (United States)

    Valizadeh, Leila; Zamanzadeh, Vahid; Habibzadeh, Hosein; Alilu, Leyla; Shakibi, Ali

    2015-10-01

    Due to the high clinical challenges, differences in coping strategies, and high workload in nurses, there is a need to develop strategies to keep them in the profession. The aim of the present study was to explore the Iranian nurses' coping strategies to deal with intention to leave. A qualitative content analysis was used to obtain rich data. We performed 13 in-depth face-to-face semi-structured interviews with nurses working in hospitals affiliated to Tabriz and Urmia Universities of Medical Sciences in Iran, selected through purposive sampling. Constant comparative method was used for data analysis. Three categories and eleven subcategories emerged during data analysis. The extracted categories and sub-categories consisted of (I) Self-empowerment (practical knowledge increase, responsibility, finding identification of the nurse, balancing work and life, seek support and humanitarian interests), (II) Self-controlling (tolerance, avoidance, the routine-based performance), and (III) Pursuing opportunities for advancement and promotion (community development, planning for higher education). Nurses make attempts to individually manage problems and stressors perceived from bedside that have led them to leave the bedside; these efforts have been effective in some cases but sometimes they are ineffective due to discontinuous training and relative competence in terms of how to manage and deal with problems. It is suggested that nurses should learn strategies scientifically to meet the challenges of bedside. Through enabling and supporting behaviors and creating opportunities for growth and professional development, nursery managers can help nurses to stay and achieve improvement of the quality of cares.

  4. Factors that enable and hinder the implementation of projects in the alcohol and other drug field.

    Science.gov (United States)

    MacLean, Sarah; Berends, Lynda; Hunter, Barbara; Roberts, Bridget; Mugavin, Janette

    2012-02-01

    Few studies systematically explore elements of successful project implementation across a range of alcohol and other drug (AOD) activities. This paper provides an evidence base to inform project implementation in the AOD field. We accessed records for 127 completed projects funded by the Alcohol, Education and Rehabilitation Foundation from 2002 to 2008. An adapted realist synthesis methodology enabled us to develop categories of enablers and barriers to successful project implementation, and to identify factors statistically associated with successful project implementation, defined as meeting all funding objectives. Thematic analysis of eight case study projects allowed detailed exploration of findings. Nine enabler and 10 barrier categories were identified. Those most frequently reported as both barriers and enablers concerned partnerships with external agencies and communities, staffing and project design. Achieving supportive relationships with partner agencies and communities, employing skilled staff and implementing consumer or participant input mechanisms were statistically associated with successful project implementation. The framework described here will support development of evidence-based project funding guidelines and project performance indicators. The study provides evidence that investing project hours and resources to develop robust relationships with project partners and communities, implementing mechanisms for consumer or participant input and attracting skilled staff are legitimate and important activities, not just in themselves but because they potentially influence achievement of project funding objectives. © 2012 The Authors. ANZJPH © 2012 Public Health Association of Australia.

  5. Factors that hinder organ donation: religio-cultural or lack of information and trust.

    Science.gov (United States)

    Tumin, Makmor; Noh, Abdillah; Jajri, Idris; Chong, Chin-Sieng; Manikam, Rishya; Abdullah, Nawi

    2013-06-01

    This paper examines factors that influence Malaysian persons with a tertiary level of education on their willingness to donate organs. A survey was done in the Klang Valley (Kuala Lumpur and its suburbs) at several designated locations. A total of 1420 people were approached, and we focused the sample of 688 respondents with a tertiary level of education. Respondents were given 2 sets of answers: (1) a religio-cultural category and (2) a structural category. They were allowed to choose more than 1 reason. Our findings revealed that only 47.5 percent of respondents declined becoming organ donors. The highest frequency recorded was "I am not convinced that my body part will be used beneficially " (30.1%), followed by "I do not have enough access to information " (29.2%), "I want my body to remain intact after death " (16.9%), and "It is against my religion " (9.9%). Our study revealed that religio-cultural factors are not a prime explanation for the lack of organ donation in the Malaysian case. This study suggests that better procurement methods used by dedicated agencies, as well as better education, could reduce the shortage between organ supply and demand.

  6. Advanced Beginner to Competent Practitioner: New Graduate Nurses' Perceptions of Strategies That Facilitate or Hinder Development.

    Science.gov (United States)

    St-Martin, Lyne; Harripaul, Anastasia; Antonacci, Rosetta; Laframboise, Devon; Purden, Margaret

    2015-09-01

    New graduate nurses (NGNs) are a precious resource, but their development from advanced beginners to competent nurses is challenging. This qualitative descriptive study explored NGNs' perceptions of strategies that influenced their development in the first 2 years of employment. Semistructured interviews were conducted with a sample of 13 nurses. The study revealed that NGNs learn to master aspects of the nursing role as they construct a professional identity. They identified organizational, educational, and personal strategies as being important to their development, including tailored orientation, opportunities for skill acquisition, and personal support. Few strategies supported the development of professional identity. Mastering the nursing role and constructing a professional identity is central to NGNs' development. Further attention from nursing leaders is needed to promote concurrent development in both dimensions. Nurses with a strong professional identity are more likely to remain in the profession. Copyright 2015, SLACK Incorporated.

  7. Does Scored VET in Schools Help or Hinder Access to Higher Education in Victoria?

    Science.gov (United States)

    Polidano, Cain; Tabasso, Domenico; Zhang, Rong

    2014-01-01

    Despite comprising only a small fraction of all vocational education and training (VET) in Schools enrolments, programs that count towards both national VET qualifications and university entry potentially fill an important role in the upper-secondary school curriculum. The aim of this study is to take a first step in gaining an understanding of…

  8. Academic Outcome Measures of a Dedicated Education Unit Over Time: Help or Hinder?

    Science.gov (United States)

    Smyer, Tish; Gatlin, Tricia; Tan, Rhigel; Tejada, Marianne; Feng, Du

    2015-01-01

    Critical thinking, nursing process, quality and safety measures, and standardized RN exit examination scores were compared between students (n = 144) placed in a dedicated education unit (DEU) and those in a traditional clinical model. Standardized test scores showed that differences between the clinical groups were not statistically significant. This study shows that the DEU model is 1 approach to clinical education that can enhance students' academic outcomes.

  9. Laptop Multitasking Hinders Classroom Learning for Both Users and Nearby Peers

    Science.gov (United States)

    Sana, Faria; Weston, Tina; Cepeda, Nicholas J.

    2013-01-01

    Laptops are commonplace in university classrooms. In light of cognitive psychology theory on costs associated with multitasking, we examined the effects of in-class laptop use on student learning in a simulated classroom. We found that participants who multitasked on a laptop during a lecture scored lower on a test compared to those who did not…

  10. Barriers that hinder the success of women entrepreneurs in Gauteng, South Africa

    OpenAIRE

    2012-01-01

    M.Tech. Women in South Africa account for more than half the population, yet traditionally have been excluded from the formal environments of business. Women entrepreneurs in play a critical and important role in the economy and their contribution is limited to more traditional businesses such as crafts, hawking, personal services and the retail sectors. For women entrepreneurs to contribute positively to the South African economy, the environment in which they operate needs to be understo...

  11. Hindered El Transitions in Eu{sup 155} and Tb{sup 161}

    Energy Technology Data Exchange (ETDEWEB)

    Malmskog, Sven G

    1965-02-15

    The absolute E1 transition probabilities from the 3/2{sup +} (411), 5/2{sup -} (532) and 7/2{sup -} (523) single particle levels in Eu{sup 155} and Tb{sup 161} have been measured by the method of delayed coincidences. This gave half lives of T{sub 1/2} < 0.2 ns and T{sub 1/2} = (1.38 {+-} 0.06) ns for the 104.4 and 246 keV levels in Eu{sup 155}. T{sub 1/2} = (0.84 {+-} 0.04) ns and T{sub 1/2} < 0. 2 ns for the 417.6 and 480.6 keV levels in Tb{sup 161}. The result has been compared with the calculations of a single particle in a deformed potential made by Nilsson.

  12. Hindered disulfide bonds to regulate release rate of model drug from mesoporous silica.

    Science.gov (United States)

    Nadrah, Peter; Maver, Uroš; Jemec, Anita; Tišler, Tatjana; Bele, Marjan; Dražić, Goran; Benčina, Mojca; Pintar, Albin; Planinšek, Odon; Gaberšček, Miran

    2013-05-01

    With the advancement of drug delivery systems based on mesoporous silica nanoparticles (MSNs), a simple and efficient method regulating the drug release kinetics is needed. We developed redox-responsive release systems with three levels of hindrance around the disulfide bond. A model drug (rhodamine B dye) was loaded into MSNs' mesoporous voids. The pore opening was capped with β-cyclodextrin in order to prevent leakage of drug. Indeed, in absence of a reducing agent the systems exhibited little leakage, while the addition of dithiothreitol cleaved the disulfide bonds and enabled the release of cargo. The release rate and the amount of released dye were tuned by the level of hindrance around disulfide bonds, with the increased hindrance causing a decrease in the release rate as well as in the amount of released drug. Thus, we demonstrated the ability of the present mesoporous systems to intrinsically control the release rate and the amount of the released cargo by only minor structural variations. Furthermore, an in vivo experiment on zebrafish confirmed that the present model delivery system is nonteratogenic.

  13. Hazelnut and neuroprotection: Improved memory and hindered anxiety in response to intra-hippocampal Aβ injection.

    Science.gov (United States)

    Bahaeddin, Zahra; Yans, Asal; Khodagholi, Fariba; Hajimehdipoor, Homa; Sahranavard, Shamim

    2017-07-01

    Corylus avellana L. (hazelnut) is known to be a delicious and nutritious food. This study was carried out to evaluate the use of hazelnut as a therapy for memory impairment because in Iranian traditional medicine, it is recommended for those suffering from a particular type of dementia, with symptoms of Alzheimer's disease. In this study, rats were fed with hazelnut kernel [(without skin) 800 mg/kg/day] during 1 week before stereotaxic surgery to 24 hours before behavioral testing (in general, for 16 consecutive days) and the effect of hazelnut eating on memory, anxiety, neuroinflammation and apoptosis was assessed in the amyloid beta-injected rat. The results of this study showed that feeding with hazelnut improved memory, (which was examined by using Y-maze test and shuttle box apparatus), and reduced anxiety-related behavior, that was evaluated using elevated plus maze. Also, western blotting analysis of cyclooxygenase-2, interleukin-1β, tumor necrosis factor-α, B-cell lymphoma 2 (Bcl-2), Bcl-2-associated X protein, and caspase-3 showed that hazelnut has an ameliorating effect on the neuroinflammation and apoptosis caused by Aβ. These findings suggest that hazelnut, as a dietary supplement, improves healthy aging and could be a beneficial diet for the treatment of AD.

  14. Facilitating or Hindering Social Cohesion? The Impact of the CWP in ...

    International Development Research Centre (IDRC) Digital Library (Canada)

    this kind is not done primarily to prevent crime, nor is it necessarily seen as such by community members. CWP participants play a significant role in organising recreational activities such as soccer that involve young men who are, as research has indicated, most likely to be involved in criminal activities.36. Participants said:.

  15. Experimental droughts: Are precipitation variability and methodological trends hindering our understanding of ecological sensitivities to drought?

    Science.gov (United States)

    Hoover, D. L.; Wilcox, K.; Young, K. E.

    2017-12-01

    Droughts are projected to increase in frequency and intensity with climate change, which may have dramatic and prolonged effects on ecosystem structure and function. There are currently hundreds of published, ongoing, and new drought experiments worldwide aimed to assess ecosystem sensitivities to drought and identify the mechanisms governing ecological resistance and resilience. However, to date, the results from these experiments have varied widely, and thus patterns of drought sensitivities have been difficult to discern. This lack of consensus at the field scale, limits the abilities of experiments to help improve land surface models, which often fail to realistically simulate ecological responses to extreme events. This is unfortunate because models offer an alternative, yet complementary approach to increase the spatial and temporal assessment of ecological sensitivities to drought that are not possible in the field due to logistical and financial constraints. Here we examined 89 published drought experiments, along with their associated historical precipitation records to (1) identify where and how drought experiments have been imposed, (2) determine the extremity of drought treatments in the context of historical climate, and (3) assess the influence of precipitation variability on drought experiments. We found an overall bias in drought experiments towards short-term, extreme experiments in water-limited ecosystems. When placed in the context of local historical precipitation, most experimental droughts were extreme, with 61% below the 5th, and 43% below the 1st percentile. Furthermore, we found that interannual precipitation variability had a large and potentially underappreciated effect on drought experiments due to the co-varying nature of control and drought treatments. Thus detecting ecological effects in experimental droughts is strongly influenced by the interaction between drought treatment magnitude, precipitation variability, and key physiological thresholds. The results from this study have important implication for the design and interpretation of drought experiments as well as integrating field results with land surface models.

  16. The Vocational Goals and Career Development of Criminally Involved Youth: Experiences That Help and Hinder

    Science.gov (United States)

    Bartlett, Jennifer; Domene, José F.

    2015-01-01

    Little is known about the career development of youth with a history of criminal activity and the factors that influence their career development. The ability to secure employment is important in predicting successful outcomes for this population, but unfortunately youth who have been involved in crime are likely to face a myriad of obstacles to…

  17. Implementing Human Resources Management (HRM) within Dutch VET Institutions: Examining the Fostering and Hindering Factors

    Science.gov (United States)

    Runhaar, Piety; Sanders, Karin

    2013-01-01

    Vocational Education and Training (VET) Institutions face serious challenges, like the implementation of competence-based education and upcoming teacher shortages, which urge them to implement Human Resources Management policy and practices (HRM). The implementation of HRM, however, often stagnates. This paper describes a qualitative study--in…

  18. Facilitating and hindering factors in Internet-delivered treatment for insomnia and depression

    Directory of Open Access Journals (Sweden)

    Kerstin Blom

    2016-05-01

    Proposed future research hypotheses: 1 A combination of CBT for insomnia and CBT for depression is more effective than only one of the treatments. 2 Additional therapist support increases outcomes for patients with more comorbidities. 3 Acceptance is a mechanism of change in CBT-i.

  19. THE FACTORS OF THE WORK PROCESS OF THE NURSE THAT HINDER HER LIFE QUALITY

    OpenAIRE

    Avanci, Barbara Soares; UNIPLI; Cortez, Elaine Antunes; EEAN/UFRJ; Belmont, Lívia Guimarães; UNIPLI; Taveira, Tamyris Maria Cremonez; UNIPLI; Reis, Letícia Carvalho; UNIPLI

    2010-01-01

    Objectives: To identify the actions carried through for the nurses who act in the ambulatory ones of prenatal and that they give assistance to the pregnant women that present high maternal and/or fetal risk; To understand the meaning that the nurse attributes to the actions to attend pregnant women that present high maternal and/or fetal risk and To analyze the importance of the nurse in the context of the prenatal one that it attends the pregnant women that present high maternal and/or fetal...

  20. Combined effects of plant competition and insect herbivory hinder invasiveness of an introduced thistle.

    Science.gov (United States)

    Suwa, Tomomi; Louda, Svata M

    2012-06-01

    The biotic resistance hypothesis is a dominant paradigm for why some introduced species fail to become invasive in novel environments. However, predictions of this hypothesis require further empirical field tests. Here, we focus on evaluating two biotic factors known to severely limit plants, interspecific competition and insect herbivory, as mechanisms of biotic resistance. We experimentally evaluated the independent and combined effects of three levels of competition by tallgrass prairie vegetation and two levels of herbivory by native insects on seedling regeneration, size, and subsequent flowering of the Eurasian Cirsium vulgare, a known invasive species elsewhere, and compared its responses to those of the ecologically similar and co-occurring native congener C. altissimum. Seedling emergence of C. vulgare was greater than that of C. altissimum, and that emergence was reduced by the highest level of interspecific competition. Insect leaf herbivory was also greater on C. vulgare than on C. altissimum at all levels of competition. Herbivory on seedlings dramatically decreased the proportion of C. vulgare producing flower heads at all competition levels, but especially at the high competition level. Competition and herbivory interacted to significantly decrease plant survival and biomass, especially for C. vulgare. Thus, both competition and herbivory limited regeneration of both thistles, but their effects on seedling emergence, survival, size and subsequent reproduction were greater for C. vulgare than for C. altissimum. These results help explain the unexpectedly low abundance recorded for C. vulgare in western tallgrass prairie, and also provide strong support for the biotic resistance hypothesis.

  1. Does hydrotherapy help or hinder adaptation to training in competitive cyclists?

    Science.gov (United States)

    Halson, Shona L; Bartram, Jason; West, Nicholas; Stephens, Jessica; Argus, Christos K; Driller, Matthew W; Sargent, Charli; Lastella, Michele; Hopkins, Will G; Martin, David T

    2014-08-01

    Cold water immersion (CWI) may be beneficial for acute recovery from exercise, but it may impair long-term performance by attenuating the stimuli responsible for adaptation to training. We compared effects of CWI and passive rest on cycling performance during a simulated cycling grand tour. Thirty-four male endurance-trained competitive cyclists were randomized to CWI for four times per week for 15 min at 15°C or control (passive recovery) groups for 7 d of baseline training, 21 d of intensified training, and an 11-d taper. Criteria for completion of training and testing were satisfied by 10 cyclists in the CWI group (maximal aerobic power, 5.13 ± 0.21 W·kg; mean ± SD) and 11 in the control group (5.01 ± 0.41 W·kg). Each week, cyclists completed a high-intensity interval cycling test and two 4-min bouts separated by 30 min. CWI was performed four times per week for 15 min at 15°C. Between baseline and taper, cyclists in the CWI group had an unclear change in overall 4-min power relative to control (2.7% ± 5.7%), although mean power in the second effort relative to the first was likely higher for the CWI group relative to control (3.0% ± 3.8%). The change in 1-s maximum mean sprint power in the CWI group was likely beneficial compared with control (4.4% ± 4.2%). Differences between groups for the 10-min time trial were unclear (-0.4% ± 4.3%). Although some effects of CWI on performance were unclear, data from this study do not support recent speculation that CWI is detrimental to performance after increased training load in competitive cyclists.

  2. The Disability Discrimination Act in the UK: helping or hindering employment among the disabled?

    Science.gov (United States)

    Bell, David; Heitmueller, Axel

    2009-03-01

    The enactment of the Americans with Disabilities Act (ADA) in 1990 triggered a substantial academic debate about its consequences on employment rates of disabled people. In contrast, the employment provision of the 1996 Disability Discrimination Act (DDA) in Britain has received little attention. Exploiting both pooled and longitudinal data, this paper provides robust evidence that, similar to the ADA in the USA, the DDA has had no impact on the employment rate of disabled people or possibly worsened it. Possible reasons for this are higher uncertainty around litigation costs, low levels of general awareness about the Act among disabled people and employers, and a lack of financial support.

  3. The Disability Discrimination Act in the UK : Helping or Hindering Employment Amongst the Disabled?

    OpenAIRE

    Bell, David N.F.; Heitmüller, Axel

    2005-01-01

    The enactment of the Americans with Disabilities Act (ADA) in 1990 triggered a substantial academic debate about its consequences on employment rates of disabled people. In contrast, the employment provision of the 1996 Disability Discrimination Act (DDA) in Britain has received little attention. This paper provides robust evidence that, similar to the ADA in the US, the DDA has had no impact on the employment rate of disabled people or possibly worsened it. Possible reasons for this are low ...

  4. Aneurysmal bone cyst does not hinder the success of kidney transplantation. A case report.

    Science.gov (United States)

    Giordano, Mario; Caloro, Giorgia; Gaeta, Alberto; Vergori, Antonio; Santangelo, Luisa; Giordano, Paolo; Ruggieri, Pietro

    2015-03-01

    Uremic osteodystrophy is an expected complication in subjects with chronic renal insufficiency. It develops gradually and progressively already during the conservative treatment and then during the dialysis treatment. It can present a wide histopathological spectrum including typical alterations (from osteitis fibrosa to osteomalacia and/or mixed lesions) or, more rarely, isolated bone lesions indicative of a brown tumor of the bone. These conditions must be clearly identified in the pretransplant phase, especially if a bone lesion indicative of a pathological condition possibly evolving into a neoplasm is detected fortuitously. We report the case of a 19-yr-old boy with renal insufficiency and candidate for a pre-emptive renal transplantation from a living donor, in whom the diagnosis of ABC of the pubic symphysis - asymptomatic and fortuitously detected while performing instrumental investigations - was suspected through the imaging studies (CT scan, MRI) and was confirmed by the histological examination. This made it possible to perform the renal transplant. The immunosuppressive treatment, which was subsequently administered, was based on steroids, calcineurin inhibitors (tacrolimus), and mycophenolate and did not determine any modification in the radiological aspect of the bone lesion, even after more than one yr from the transplant. © 2014 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.

  5. Feedback Both Helps and Hinders Learning: The Causal Role of Prior Knowledge

    Science.gov (United States)

    Fyfe, Emily R.; Rittle-Johnson, Bethany

    2016-01-01

    Feedback can be a powerful learning tool, but its effects vary widely. Research has suggested that learners' prior knowledge may moderate the effects of feedback; however, no causal link has been established. In Experiment 1, we randomly assigned elementary school children (N = 108) to a condition based on a crossing of 2 factors: induced strategy…

  6. Continuous microwave pasteurization of a vegetable smoothie improves its physical quality and hinders detrimental enzyme activity.

    Science.gov (United States)

    Arjmandi, Mitra; Otón, Mariano; Artés, Francisco; Artés-Hernández, Francisco; Gómez, Perla A; Aguayo, Encarna

    2017-01-01

    The effect of a pasteurization treatment at 90 ± 2 ℃ for 35 s provided by continuous microwave under different doses (low power/long time and high power/short time) or conventional pasteurization on the quality of orange-colored smoothies and their changes throughout 45 days of storage at 5 ℃ was investigated. A better color retention of the microwave pasteurization- treated smoothie using high power/short time than in conventionally processed sample was evidenced by the stability of the hue angle. The continuous microwave heating increased the viscosity of the smoothie more than the conventional pasteurization in comparison with non-treated samples. Lower residual enzyme activities from peroxidase, pectin methylesterase and polygalacturonase were obtained under microwave heating, specifically due to the use of higher power/shorter time. For this kind of smoothie, polygalacturonase was the more thermo-resistant enzyme and could be used as an indicator of pasteurization efficiency. The use of a continuous semi-industrial microwave using higher power and shorter time, such as 1600 W/206 s and 3600 W/93 s, resulted in better quality smoothies and greater enzyme reduction than conventional thermal treatment. © The Author(s) 2016.

  7. An examination of factors that hinder and programs that stimulate Papuan entrepreneurs

    NARCIS (Netherlands)

    Burg, van J.C.

    2007-01-01

    This report describes the results of a study on entrepreneurship in the Indonesian province Papua. The study was performed for Oikonomos Foundation to help evaluating the current entrepreneurship support programs and to identify future challenges. Seven important difficulties for Papuan

  8. Does the presence of priming hinder subsequent recognition or recall performance?

    Science.gov (United States)

    Stark, Shauna M; Gordon, Barry; Stark, Craig E L

    2008-02-01

    Declarative and non-declarative memories are thought be supported by two distinct memory systems that are often posited not to interact. However, Wagner, Maril, and Schacter (2000a) reported that at the time priming was assessed, greater behavioural and neural priming was associated with lower levels of subsequent recognition memory, demonstrating an interaction between declarative and non-declarative memory. We examined this finding using a similar paradigm, in which participants made the same or different semantic word judgements following a short or long lag and subsequent memory test. We found a similar overall pattern of results, with greater behavioural priming associated with a decrease in recognition and recall performance. However, neither various within-participant nor various between-participant analyses revealed significant correlations between priming and subsequent memory performance. These data suggest that both lag and task have effects on priming and declarative memory performance, but that they are largely independent and occur in parallel.

  9. Values in organizations as factors that promote or hinder socioeconomic convergence / Rebekka Vedina

    Index Scriptorium Estoniae

    Vedina, Rebekka, 1976-

    2002-01-01

    Bibliogr. lk. 141-142. - Kokkuvõte eesti k. lk. 143. Ülevaade, millised väärtused organisatsioonides soodustavad ja millised takistavad konvergentsi ning millist osa selles täidavad rahvuskultuuri väärtused

  10. Synthesis and Characterization of Block Copolymers with Unique Chemical Functionalities and Entropically-Hindering Moieties

    Science.gov (United States)

    2017-08-14

    methanol as a function of chemistry , morphology and hydration levels. Accomplishments: This section is included in the "upload" section. Training...Copolymer Blend Membranes.” In Press, Polymer Engineering and Science, DOI: 10.1002 /pen.24508, 2017. 5. M. Pérez-Pérez and D. Suleiman. “Synthesis and...Synthesis and Characterization of Sulfonated Amine Block Copolymers for Energy Efficient Applications". Chemical Engineering Symposium, University of

  11. Beauty hinders attention switch in change detection: the role of facial attractiveness and distinctiveness.

    Science.gov (United States)

    Chen, Wenfeng; Liu, Chang Hong; Nakabayashi, Kazuyo

    2012-01-01

    Recent research has shown that the presence of a task-irrelevant attractive face can induce a transient diversion of attention from a perceptual task that requires covert deployment of attention to one of the two locations. However, it is not known whether this spontaneous appraisal for facial beauty also modulates attention in change detection among multiple locations, where a slower, and more controlled search process is simultaneously affected by the magnitude of a change and the facial distinctiveness. Using the flicker paradigm, this study examines how spontaneous appraisal for facial beauty affects the detection of identity change among multiple faces. Participants viewed a display consisting of two alternating frames of four faces separated by a blank frame. In half of the trials, one of the faces (target face) changed to a different person. The task of the participant was to indicate whether a change of face identity had occurred. The results showed that (1) observers were less efficient at detecting identity change among multiple attractive faces relative to unattractive faces when the target and distractor faces were not highly distinctive from one another; and (2) it is difficult to detect a change if the new face is similar to the old. The findings suggest that attractive faces may interfere with the attention-switch process in change detection. The results also show that attention in change detection was strongly modulated by physical similarity between the alternating faces. Although facial beauty is a powerful stimulus that has well-demonstrated priority, its influence on change detection is easily superseded by low-level image similarity. The visual system appears to take a different approach to facial beauty when a task requires resource-demanding feature comparisons.

  12. ‘Standard’ incentive regulation hinders the integration of renewable energy generation

    International Nuclear Information System (INIS)

    Nykamp, Stefan; Andor, Mark; Hurink, Johann L.

    2012-01-01

    The connection and distribution of growing, decentralized electricity generation from renewable energy sources (RES-E) is leading to massive investment needs. Besides investing in additional ‘conventional’ assets (e.g. cables), grid operators can also invest in innovative ‘smart solutions’ like local storage capacities or voltage regulation appliances, which may be a more suitable way of integrating RES-E. This paper investigates the influence of incentive regulation on the investment decision of grid operators to integrate RES-E. We describe the technical and regulatory background, explain the advantages of ‘smart solutions’ and present an approach for comparing investment scenarios. As an example, we calculate the profitability of investments in a case study of the German electricity market. We apply Data Envelopment Analysis (DEA) and Stochastic Frontier Analysis (SFA) to show the influence of the investment alternatives on grid operator efficiency objectives. We demonstrate that under current ‘standard’ incentive regulation, the grid operators gain profitability by avoiding investments and – if they are forced to invest – by not implementing ‘smart solutions’. The results highlight the need to consider innovation in the regulation design. Further research should investigate specific instruments that can be used to account for innovation. Our brief discussion of such instruments provides a starting point. - Highlights: ► We measure the influence of investments on efficiency by applying DEA and SFA. ► We compare the profitability of alternative investments under incentive regulation. ► Incentive regulation gives incentives to refuse investment at all. ► If DSOs are forced to invest, reinforcement is preferable to smart solutions. ► Ways to consider innovation in incentive regulations are required and discussed.

  13. Steric Hindrance as a Basis for Structure-Based Design of Selective Inhibitors of Protein-Tyrosine Phosphatases

    DEFF Research Database (Denmark)

    Iversen, L. F.; Andersen, H. S.; Møller, K. B.

    2001-01-01

    Utilizing structure-based design, we have previously demonstrated that it is possible to obtain selective inhibitors of protein-tyrosine phosphatase 1B (PTP1B). A basic nitrogen was introduced into a general PTP inhibitor to form a salt bridge to Asp48 in PTP1B and simultaneously cause repulsion...... in PTPs containing an asparagine in the equivalent position [Iversen, L. F., et al. (2000) J. Biol. Chem. 275, 10300−10307]. Further, we have recently demonstrated that Gly259 in PTP1B forms the bottom of a gateway that allows easy access to the active site for a broad range of substrates, while bulky...... in accessibility to the active site among various PTPs. We show that a general, low-molecular weight PTP inhibitor can be developed into a highly selective inhibitor for PTP1B and TC-PTP by introducing a substituent, which is designed to address the region around residues 258 and 259. Detailed enzyme kinetic...

  14. Anion Transport in a Chemically Stable, Sterically Bulky alpha-C Modified Imidazolium Functionalized Anion Exchange Membrane

    Science.gov (United States)

    2014-06-24

    AEM is often inconvenient, as ambient carbon dioxide (at publication time, 400 ppm) will react with the OH− to form a mixture of CO3 2− and HCO3 − in... crystal . Spectra were obtained in the range 500−4000 cm−1, with 256 scans and a resolution of 8 cm−1. Figure 1. Structure of 1,4,5-trimethyl-2-(2,4,6...pulsed-field gradient nuclear magnetic resonance (PFG NMR) on an AVANCEIII NMR spectrometer with a 5 mm Bruker single -axis DIFF60L Z-diffusion probe. The

  15. Rh-Catalyzed Annulations of N-Methoxybenzamides and Ketenimines: Sterically and Electronically Controlled Synthesis of Isoquinolinones and Isoindolinones.

    Science.gov (United States)

    Zhou, Xiaorong; Zhang, Zhiyin; Zhao, Hongyang; Lu, Ping; Wang, Yanguang

    2017-04-07

    Rhodium-catalyzed C-H activation/annulation reactions of ketenimines with N-methoxybenzamides are reported. The outcome of reactions is dependent on the structure of ketenimines. The β-alkyl-substituted ketenimines furnish 3-iminoisoquinolin-1(2H)-ones in a formal [4 + 2] annulation manner, while the β-ester substituted ketenimines afford 3-aminoisoindolin-1-ones in a formal [4 + 1] annulation manner. The synthesized [4 + 2] products undergo an intramolecular Cu-catalyzed C-N coupling to be converted to benzo[4,5]imidazo[1,2-b]isoquinolin-11-ones, which can be directly prepared from ketenimines and N-methoxybenzamides by a one-pot Rh-catalyzed annulation/Cu-catalyzed C-N coupling sequence.

  16. Steric hindrance mutagenesis in the conserved extracellular vestibule impedes allosteric binding of antidepressants to the serotonin transporter

    DEFF Research Database (Denmark)

    Plenge, Per; Shi, Lei; Beuming, Thijs

    2012-01-01

    be involved in the allosteric binding in the extracellular vestibule located above the central substrate binding (S1) site. Indeed, mutagenesis of selected residues in the vestibule reduces the allosteric potency of (S)-citalopram and clomipramine. The identified site is further supported by the inhibitory...

  17. Sterically screened halogenocyclobutanones. I. Transformations of cyclopropyl-substituted 2,2-dichlorocyclobutanones under the influence of potassium hydroxide

    International Nuclear Information System (INIS)

    Donskaya, N.A.; Bessmertnykh, A.G.; Drobysh, V.A.; Shabarov, Yu.S.

    1987-01-01

    The reaction of 2,2-dichloro-3-cyclopropylcyclobutanones with potassium hydroxide was studied. The direction of the reaction depends on the concentration of the potassium hydroxide; with a 2% solution of potassium hydroxide 4,4-dichlorobutyric acids are formed with yields of up to 80%, and with a 15% solution of potassium hydroxide 5-hydroxydihydro-2-furanones are formed with yields of up to 80%. Proposals are made about the mechanism of formation of 5-hydroxydihydro-2-furanones

  18. Single-Step versus Stepwise Two-Electron Reduction of Polyarylpyridiniums: Insights from the Steric Switching of Redox Potential Compression

    Czech Academy of Sciences Publication Activity Database

    Fortage, J.; Peltier, C.; Perruchot, Ch.; Takemoto, Y.; Teki, Y.; Bedioui, F.; Marvand, V.; Dupeyre, G.; Pospíšil, Lubomír; Adamo, C.; Hromadová, Magdaléna; Ciofini, I.; Lainé, P. P.

    2012-01-01

    Roč. 134, č. 5 (2012), s. 2691-2705 ISSN 0002-7863 Institutional research plan: CEZ:AV0Z40400503 Keywords : FUNCTIONALIZED TERPYRIDYL LIGANDS * GATED PHOTOINDUCED PROCESSES * ONE-ELECTRON REDUCTION Subject RIV: CG - Electrochemistry Impact factor: 10.677, year: 2012

  19. Interplay of alternative conjugated pathways and steric interactions on the electronic and optical properties of donor-acceptor conjugated polymers

    KAUST Repository

    Lima, Igo T.; Risko, Chad; Aziz, Saadullah Gary; Da Silva Filho, Demé trio A Da Silva; Bredas, Jean-Luc

    2014-01-01

    Donor-acceptor π-conjugated copolymers are of interest for a wide range of electronic applications, including field-effect transistors and solar cells. Here, we present a density functional theory (DFT) study of the impact of varying the conjugation pathway on the geometric, electronic, and optical properties of donor-acceptor systems. We consider both linear ("in series"), traditional conjugation among the donor-acceptor moieties versus structures where the acceptor units are appended orthogonally to the linear, donor-only conjugated backbone. Long-range-corrected hybrid functionals are used in the investigation with the values of the tuned long-range separation parameters providing an estimate of the extent of conjugation as a function of the oligomer architecture. Considerable differences in the electronic and optical properties are determined as a function of the nature of the conjugation pathway, features that should be taken into account in the design of donor-acceptor copolymers.

  20. Improved syntheses of high hole mobility phthalocyanines: A case of steric assistance in the cyclo-oligomerisation of phthalonitriles

    Directory of Open Access Journals (Sweden)

    Daniel J. Tate

    2012-01-01

    Full Text Available It has been shown that the base-initiated cyclo-oligomerisation of phthalonitriles is favoured by bulky α-substituents making it possible to obtain the metal-free phthalocyanine directly and in high yield. The phthalocyanine with eight α-isoheptyl substituents gives a high time-of-flight hole mobility of 0.14 cm2·V−1·s−1 within the temperature range of the columnar hexagonal phase, that is 169–189 °C.

  1. Influence of electronic and steric effects on stability constants and electrochemical reversibility of divalent ion complexes with glycine and sarcosine

    International Nuclear Information System (INIS)

    Cukrowski, Ignacy; Marques, Helder M.; Mkwizu, Tumaini S.; Magampa, Philemon P.; Serge, Claudette

    2007-01-01

    Cd II complexes with glycine (gly) and sarcosine (sar) were studied by glass electrode potentiometry, direct current polarography, virtual potentiometry, and molecular modelling. The electrochemically reversible Cd II -glycine-OH labile system was best described by a model consisting of M(HL), ML, ML 2 , ML 3 , ML(OH) and ML 2 (OH) (M = Cd II , L = gly) with the overall stability constants, as log β, determined to be 10.30 ± 0.05, 4.21 ± 0.03, 7.30 ± 0.05, 9.84 ± 0.04, 8.9 ± 0.1, and 10.75 ± 0.10, respectively. In case of the electrochemically quasi-reversible Cd II -sarcosine-OH labile system, only ML, ML 2 and ML 3 (M = Cd II , L = sar) were found and their stability constants, as log β, were determined to be 3.80 ± 0.03, 6.91 ± 0.07, and 8.9 ± 0.4, respectively. Stability constants for the ML complexes, the prime focus of this work, were thus established with an uncertainty smaller than 0.05 log units. The observed departure from electrochemical reversibility for the Cd-sarcosine-OH system was attributed mainly to the decrease in the transfer coefficient α. The MM2 force field, supplemented by additional parameters, reproduced the reported crystal structures of diaqua-bis(glycinato-O,N)nickel(II) and fac-tri(glycinato)-nickelate(II) very well. These parameters were used to predict structures of all possible isomers of (i) [Ni(H 2 O) 4 (gly)] + and [Ni(H 2 O) 4 (sar)] + ; and (ii) [Ni(H 2 O) 3 (IDA)] and [Ni(H 2 O) 3 (MIDA)] (IDA = iminodiacetic acid, MIDA = N-methyl iminodiacetic acid) by molecular mechanics/simulated annealing methods. The change in strain energy, ΔU str , that accompanies the substitution of one ligand by another (ML + L' → ML' + L), was computed and a strain energy ΔU str = +0.28 kcal mol -1 for the reaction [Ni(H 2 O) 4 (gly)] + + sar → [Ni(H 2 O) 4 (sar)] + + gly was found. This predicts the monoglycine complex to be marginally more stable. By contrast, for the reaction [Ni(H 2 O) 3 IDA] + MIDA → [Ni(H 2 O) 3 MIDA] + IDA, ΔU str = -0.64 kcal mol -1 , and the monoMIDA complex is predicted to be more stable. This correlates well with (i) stability constants for Cd-gly and Cd-sar reported here; and (ii) known stability constants of ML complex for glycine, sarcosine, IDA, and MIDA

  2. Role of N-Donor Sterics on the Coordination Environment and Dimensionality of Uranyl Thiophenedicarboxylate Coordination Polymers

    Energy Technology Data Exchange (ETDEWEB)

    Thangavelu, Sonia G. [Department; Butcher, Ray J. [Department; Cahill, Christopher L. [Department

    2015-06-09

    Thiophene 2,5-dicarboxylic acid (TDC) was reacted with uranyl acetate dihydrate and one (or none) of six N-donor chelating ligands (2,2'-bipyridine (BPY), 4,4'-dimethyl-2,2'-bipyridine (4-MeBPY), 5,5'-dimethyl-2,2'-bipyridine (5-MeBPY), 6,6'-dimethyl-2,2'-bipyridine (6-MeBPY), 4,4',6,6'-tetramethyl-2,2'-bipyridine (4,6-MeBPY), and tetrakis(2-pyridyl)pyrazine (TPPZ) to result in the crystallization of seven uranyl coordination polymers, which were characterized by their crystal structures and luminescence properties. The seven coordination polymers, Na2[(UO2)2(C6H2O4S)3]·4H2O (1), [(UO2)4(C6H2O4S)5(C10H8N2)2]·C10H10N2·3H2O (2), [(UO2)(C6H2O4S)(C12H12N3)] (3), [(UO2)(C6H2O4S)(C12H12N3)]·H2O (4), [(UO2)2(C6H2O4S)3]·(C12H14N2)·5H2O (5), [(UO2)3(CH3CO2)(C6H2O4S)4](C14H17N2)3·(C14H16N2)·H2O (6), and [(UO2)2(C6H2O4S)3](C24H18N6) (7), consist of either uranyl hexagonal bipyramidal or pentagonal bipyramidal coordination geometries. In all structures, structural variations in the local and global structures of 1–7 are influenced by the positions (or number) of methyl groups or pyridyl rings on the N-donor species, thus resulting in a wide diversity of structures ranging from single chains, double chains, or 2-D sheets. Direct coordination of N-donor ligands to uranyl centers is observed in the chain structures of 2–4 using BPY, 4-MeBPY, and 5-MeBPY, whereas the N-donor species participate as guests (as either neutral or charge balancing species) in the chain and sheet structures of 5–7 using 6-MeBPY, 4,6-MeBPY, and TPPZ, respectively. Compound 1 is the only structure that does not contain any N-donor ligands and thus crystallizes as a 2-D interpenetrating sheet. The luminescent properties of 1–7 are influenced by the direct coordination or noncoordination of N-donor species to uranyl centers. Compounds 2–4 exhibit typical UO22+ emission upon direct coordination of N-donors, but its absence is observed in 1, 5, 6, and 7, when N-donor species participate as guest molecules. These results suggest that direct coordination of N-donor ligands participate as chromophores, thus resulting in possible UO22+ sensitization. The lack of emission in 1, 5, 6, and 7 may be explained by the extended conjugation of the TDC ligands within their structures.

  3. Steric effects of CO2 binding to transition metal-benzene complexes: a first-principles study

    OpenAIRE

    Bae, Hyeonhu; Huang, Bing; Lee, Hoonkyung

    2016-01-01

    Using density functional theory (DFT) calculations, we investigated the adsorption of CO2 molecules on 3d transition metal (TM)-benzene complexes. Our calculations show that the maximum number of CO2 molecules adsorbable on Sc or Ti atoms is three, but the 18-electron rule predicts it should be four. The 18-electron rule is generally successful in predicting the maximum H2 adsorption number for TM atoms including Sc or Ti atoms. We found that the 18-electron rule fails to correctly predict CO...

  4. Fluorescent organic dyes as radiation converters in scintillation counting and laser techniques

    International Nuclear Information System (INIS)

    Guesten, H.

    1989-01-01

    PMP (1-phenyl-3-mesityl-2-pyrazoline) was selected as color quenching from the category of the sterically hindered 1,3-diphenyl-2-pyrazoline by means of comparative optimization between photo-physical and scintillation-spectroscopic and chemical properties and the costs of synthesis. It is applied in liquid scintillation detectors for the detection of β (T, C-14) and in large-volume liquid scintillators for the detection of neutrinos (Rutherford Lab.). (HP) [de

  5. Black Women in the New Services Economy: Help or Hinderance in Economic Self-Sufficiency? Working Paper No. 196.

    Science.gov (United States)

    Woody, Bette

    This report of a study based on research and analysis of U.S. Census data examines how the services economy and its component industrial sectors have spurred employment growth and with its gains and losses for black women. The report is divided into three parts. The first part looks at current theories related to work and workforce participation…

  6. Smartphones as assistive technology following traumatic brain injury: a preliminary study of what helps and what hinders.

    Science.gov (United States)

    Wong, Dana; Sinclair, Kelly; Seabrook, Elizabeth; McKay, Adam; Ponsford, Jennie

    2017-11-01

    Smartphones have great potential as a convenient, multifunction tool to support cognition and independence following traumatic brain injury (TBI). However, there has been limited investigation of their helpful and less helpful aspects for people with TBI. We aimed to investigate patterns of smartphone use amongst individuals with TBI, identify potential barriers to use, and examine the relationships between smartphone use and daily functioning. Twenty-nine participants with TBI and 33 non-injured participants completed the Smartphone Survey, and measures of subjective and objective cognitive functioning, mood, and community integration. Smartphone use was equally common in both groups, and patterns of app use were similar. More participants with TBI than the comparison group listed using their smartphone as a memory aid as its main benefit. Difficulty in learning how to use the smartphone was identified by participants with TBI, however only 10% had been shown how to use it by a clinician. Those with poorer subjective cognitive function used memory/organisational apps more frequently; and higher communication app use with better social integration, in participants with TBI. These findings suggest that smartphones have potential in improving independence following TBI, but receiving support in using them is vital. Implications for Rehabilitation Smartphones are accessible, acceptable, convenient devices for most individuals with traumatic brain injury (TBI), and are perceived as a useful memory and organizational aid as well as having multiple other helpful functions. Use of communication apps such as text messages and social media is associated with better social and community integration in people with TBI. Direct instruction on how to use smartphone apps is more important for people with TBI than for non-injured individuals. Developers of apps designed for this population should prioritize ease of app use, large displays, and availability of technical support, while maintaining an engaging design and interface.

  7. Did a skillful prediction of sea surface temperatures help or hinder forecasting of the 2012 Midwestern US drought?

    International Nuclear Information System (INIS)

    Kam, Jonghun; Sheffield, Justin; Yuan, Xing; Wood, Eric F

    2014-01-01

    The latest drought to hit the Midwestern (MW) US region, in 2012, was driven by the least summer precipitation for the last three decades with $20 billion in agriculture losses. For 2012, the summer forecast skill for Pacific and Atlantic sea surface temperature (SST) anomalies and low MW precipitation is remarkably good for some National Multi-Model Ensemble (NMME) models, but this is not generally repeated for other drought years, with some models predicting extreme wet anomalies, despite skill in predicting Pacific and Atlantic SST anomalies. In order to diagnose the origins of the limited skill of the NMME models, we use singular value decomposition (SVD) for global SSTs and continental US (CONUS) precipitation from observational data and NMME hindcasts (1982–2012). Observational data indicate that there is an insignificant coupling between global SSTs and MW precipitation during summer over the last 30 years. However, the NMME climate forecast models show strong coupling and therefore predicted the 2012 drought fortuitously for the wrong reason (a strong pan-Pacific El Niño–Southern Oscillation (ENSO)-like pattern). The observational data indicate that the strength of ENSO teleconnections with CONUS precipitation has weakened and the precipitation footprint has shifted over the past decades, suggesting that the transient nature of teleconnections may play a role in poor model skill. (paper)

  8. Rescue therapy with Tanshinone IIA hinders transition of acute kidney injury to chronic kidney disease via targeting GSK3β

    Science.gov (United States)

    Jiang, Chunming; Zhu, Wei; Yan, Xiang; Shao, Qiuyuan; Xu, Biao; Zhang, Miao; Gong, Rujun

    2016-01-01

    Acute kidney injury (AKI) remains challenging for clinical practice and poses a risk of developing progressive chronic kidney disease (CKD) with no definitive treatment available yet. Tanshinone IIA, an active ingredient of Chinese herbal Salvia miltiorrhiza, has been widely used in Asia for the remarkable organoprotective activities. Its effect on established AKI, however, remains unknown. In mice with folic acid-induced AKI, delayed treatment with Tanshinone IIA, commenced early or late after injury, diminished renal expression of kidney injury markers, reduced apoptosis and improved kidney dysfunction, concomitant with mitigated histologic signs of AKI to CKD transition, including interstitial fibrosis and tubular atrophy, and with an ameliorated inflammatory infiltration in tubulointerstitium and a favored M2-skewed macrophage polarization. Mechanistically, Tanshinone IIA blunted glycogen synthase kinase (GSK)3β overactivity and hyperactivation of its downstream mitogen-activated protein kinases that are centrally implicated in renal fibrogenesis and inflammation. Inhibition of GSK3β is likely a key mechanism mediating the therapeutic activity of Tanshinone IIA, because sodium nitroprusside, a GSK3β activator, largely offset its renoprotective effect. In confirmatory studies, rescue treatment with Tanshinone IIA likewise ameliorated ischemia/reperfusion-induced kidney destruction in mice. Our data suggest that Tanshinone IIA represents a valuable treatment that improves post-AKI kidney salvage via targeting GSK3β. PMID:27857162

  9. The New Juan Crow in Education: Revealing Panoptic Measures and Inequitable Resources That Hinder Latina/o Postsecondary Pathways

    Science.gov (United States)

    Madrigal-Garcia, Yanira I.; Acevedo-Gil, Nancy

    2016-01-01

    This qualitative study examined the distribution of inequitable resources, a culture of control, and implications for postsecondary pathways for Latinas/os in five California high schools. This study integrated critical race theory in education, school culture, and the concept of "panopticon" to examine school structures, climate, and…

  10. Mechanistic Evaluation of Motion in Redox-Driven Rotaxanes Reveals Longer Linkers Hasten Forward Escape's and Hinder Backward Translations

    DEFF Research Database (Denmark)

    Andersen, S. S.; Share, A. I.; Poulsen, B. L.

    2014-01-01

    temperatures to provide activation enthalpies (Delta H-double dagger) and entropies (Delta S-double dagger). Longer glycol linkers led to modest increases in the forward escape (t(1/2) = 60 to 69 s); though not because of a diffusive walk. The reduced rate of motion backward depended on folded structures...

  11. Macrophage-derived osteopontin is fragmented by MMP-9 to hinder angiogenesis in the post-myocardial infarction left ventricle

    DEFF Research Database (Denmark)

    Nielsen, Signe Holm; Flynn, E.R.; Lindsey, M.

    2017-01-01

    Extracellular matrix (ECM) turnover is a key event during remodeling of the left ventricle (LV) following myocardial infarction (MI). Turnover includes ECM degradation of existing ECM to remove necrotic myocytes and synthesis to produce new ECM to form the infarct scar. Matrix metalloproteinases...

  12. Strong compensation hinders the p-type doping of ZnO: a glance over surface defect levels

    Science.gov (United States)

    Huang, B.

    2016-07-01

    We propose a surface doping model of ZnO to elucidate the p-type doping and compensations in ZnO nanomaterials. With an N-dopant, the effects of N on the ZnO surface demonstrate a relatively shallow acceptor level in the band gap. As the dimension of the ZnO materials decreases, the quantum confinement effects will increase and render the charge transfer on surface to influence the shifting of Fermi level, by evidence of transition level changes of the N-dopant. We report that this can overwhelm the intrinsic p-type conductivity and transport of the ZnO bulk system. This may provide a possible route of using surface doping to modify the electronic transport and conductivity of ZnO nanomaterials.

  13. The importance of strengthening competence and control beliefs in patients with psychosis to reduce treatment hindering self-stigmatization.

    Science.gov (United States)

    Surmann, Marian; Gruchalla, Lara von; Falke, Sebastian; Maisch, Birgit; Uhlmann, Christina; Bock, Eva; Arolt, Volker; Lencer, Rebekka

    2017-09-01

    Different aspects of self-stigmatization represent barriers for recovery in patients with psychosis disorders. It is unclear whether addressing patient's competence and control beliefs could attenuate the extent of self-stigmatization. The major aim of this study was to identify predictors of self-stigmatization derived from competence and control beliefs in patients (N = 80). Sociodemographic characteristics, clinical variables, competence and control beliefs and self-stigmatization were assessed among 80 patients with psychosis disorders. The cross-sectional data was analyzed by correlation and regression analyses. Results indicate deficits in self-concept of own competences, i.e. the capability of acting in new, difficult or ambiguous situations, resulting in also impaired self-efficacy and relatively increased externality in patients compared to a general population sample. Subjective well-being under neuroleptics, trait-anxiety and defining oneself as religious were the most influential predictors of competence and control beliefs. A weaker self-concept of own competences was also revealed as the strongest predictor of overall high self-stigmatization. Our results stress the importance of orienting treatment strategies towards strengthening the self-concept of own competences in patients in order to reduce self-stigmatization and enhance resilience. Copyright © 2017 Elsevier Ireland Ltd. All rights reserved.

  14. How do postgraduate GP trainees regulate their learning and what helps and hinders them? A qualitative study

    NARCIS (Netherlands)

    Sagasser, M.H.; Kramer, A.W.M.; Vleuten, C.P.M. van der

    2012-01-01

    ABSTRACT: BACKGROUND: Self-regulation is essential for professional development. It involves monitoring of performance, identifying domains for improvement, undertaking learning activities, applying newly learned knowledge and skills and self-assessing performance. Since self-assessment alone is

  15. Spatial profiling of degradation processes in hindered-amine-stabilized polymers by electron spin resonance imaging of nitroxides

    Czech Academy of Sciences Publication Activity Database

    Marek, Antonín; Kaprálková, Ludmila; Pfleger, Jiří; Pospíšil, Jan; Pilař, Jan

    2005-01-01

    Roč. 99, S (2005), s. 195-198 ISSN 0009-2770. [Meeting on Chemistry and Life /3./. Brno, 20.9.2005-22.9.2005] Institutional research plan: CEZ:AV0Z40500505 Keywords : polymer degradation * nitroxides * electron spin resonance imaging Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 0.445, year: 2005

  16. How do postgraduate GP trainees regulate their learning and what helps and hinders them? A qualitative study

    Directory of Open Access Journals (Sweden)

    Sagasser Margaretha H

    2012-08-01

    Full Text Available Abstract Background Self-regulation is essential for professional development. It involves monitoring of performance, identifying domains for improvement, undertaking learning activities, applying newly learned knowledge and skills and self-assessing performance. Since self-assessment alone is ineffective in identifying weaknesses, learners should seek external feedback too. Externally regulated educational interventions, like reflection, learning portfolios, assessments and progress meetings, are increasingly used to scaffold self-regulation. The aim of this study is to explore how postgraduate trainees regulate their learning in the workplace, how external regulation promotes self-regulation and which elements facilitate or impede self-regulation and learning. Methods In a qualitative study with a phenomenologic approach we interviewed first- and third-year GP trainees from two universities in the Netherlands. Twenty-one verbatim transcripts were coded. Through iterative discussion the researchers agreed on the interpretation of the data and saturation was reached. Results Trainees used a short and a long self-regulation loop. The short loop took one week at most and was focused on problems that were easy to resolve and needed minor learning activities. The long loop was focused on complex or recurring problems needing multiple and planned longitudinal learning activities. External assessments and formal training affected the long but not the short loop. The supervisor had a facilitating role in both loops. Self-confidence was used to gauge competence.Elements influencing self-regulation were classified into three dimensions: personal (strong motivation to become a good doctor, interpersonal (stimulation from others and contextual (organizational and educational features. Conclusions Trainees did purposefully self-regulate their learning. Learning in the short loop may not be visible to others. Trainees should be encouraged to actively seek and use external feedback in both loops. An important question for further research is which educational interventions might be used to scaffold learning in the short loop. Investing in supervisor quality remains important, since they are close to trainee learning in both loops.

  17. Lattice vibrations and barrier to hindered rotation in lithium tetradeuteroaluminate by 2H, 7Li and 27Al NMR

    International Nuclear Information System (INIS)

    Tarasov, V.P.; Kirakosyan, G.A.

    1996-01-01

    Temperature dependences of 2 H, 7 Li, 27 Al NMR line shape in LiAlD 4 lithium polycrystal tetradeuteroaluminate in the range of 103-420 K have been studied. The quadrupole bond constants and asymmetry parameters of electric field gradient tensor have been measured. The frequencies of lattice vibrations have been evaluated in the framework of the Buyer model. From temperature dependences of spin-lattice relaxation time and 2 H NMR line shape the activation energies of AlD 4 anion decelerated rotation, amounting to 74 and 62 k J/mol respectively, have been determined. 15 refs.; 5 figs.; 2 tabs

  18. Aromatic inhibitors derived from ammonia-pretreated lignocellulose hinder bacterial ethanologenesis by activating regulatory circuits controlling inhibitor efflux and detoxification

    Directory of Open Access Journals (Sweden)

    David H. Keating

    2014-08-01

    Full Text Available Efficient microbial conversion of lignocellulosic hydrolysates to biofuels is a key barrier to the economically viable deployment of lignocellulosic biofuels. A chief contributor to this barrier is the impact on microbial processes and energy metabolism of lignocellulose-derived inhibitors, including phenolic carboxylates, phenolic amides (for ammonia-pretreated biomass, phenolic aldehydes, and furfurals. To understand the bacterial pathways induced by inhibitors present in ammonia-pretreated biomass hydrolysates, which are less well studied than acid-pretreated biomass hydrolysates, we developed and exploited synthetic mimics of ammonia-pretreated corn stover hydrolysate (ACSH. To determine regulatory responses to the inhibitors normally present in ACSH, we measured transcript and protein levels in an Escherichia coli ethanologen using RNA-seq and quantitative proteomics during fermentation to ethanol of synthetic hydrolysates containing or lacking the inhibitors. Our study identified four major regulators mediating these responses, the MarA/SoxS/Rob network, AaeR, FrmR, and YqhC. Induction of these regulons was correlated with a reduced rate of ethanol production, buildup of pyruvate, depletion of ATP and NAD(PH, and an inhibition of xylose conversion. The aromatic aldehyde inhibitor 5-hydroxymethylfurfural appeared to be reduced to its alcohol form by the ethanologen during fermentation, whereas phenolic acid and amide inhibitors were not metabolized. Together, our findings establish that the major regulatory responses to lignocellulose-derived inhibitors are mediated by transcriptional rather than translational regulators, suggest that energy consumed for inhibitor efflux and detoxification may limit biofuel production, and identify a network of regulators for future synthetic biology efforts.

  19. Broadening the regulated-river management paradigm: A case study of the forgotten dead zone hindering Pallid Sturgeon recovery

    Science.gov (United States)

    Guy, Christopher S.; Treanor, Hilary B.; Kappenman, Kevin M.; Scholl, Eric A.; Ilgen, Jason E.; Webb, Molly A. H.

    2015-01-01

    The global proliferation of dams within the last half century has prompted ecologists to understand the effects of regulated rivers on large-river fishes. Currently, much of the effort to mitigate the influence of dams on large-river fishes has been focused on downriver effects, and little attention has been given to upriver effects. Through a combination of field observations and laboratory experiments, we tested the hypothesis that abiotic conditions upriver of the dam are the mechanism for the lack of recruitment in Pallid Sturgeon (Scaphirhynchus albus), an iconic large-river endangered species. Here we show for the first time that anoxic upriver habitat in reservoirs (i.e., the transition zone between the river and reservoir) is responsible for the lack of recruitment in Pallid Sturgeon. The anoxic condition in the transition zone is a function of reduced river velocities and the concentration of fine particulate organic material with high microbial respiration. As predicted, the river upstream of the transition zone was oxic at all sampling locations. Our results indicate that transition zones are an ecological sink for Pallid Sturgeon. We argue that ecologists, engineers, and policy makers need to broaden the regulated-river paradigm to consider upriver and downriver effects of dams equally to comprehensively mitigate altered ecosystems for the benefit of large-river fishes, especially for the Pallid Sturgeon.

  20. Challenges that Hinder Parturients to Deliver in Health Facilities: A Qualitative Analysis in Two Districts of Indonesia

    Directory of Open Access Journals (Sweden)

    Sudirman Nasir

    2016-12-01

    Full Text Available Background: There are many challenges women face to be able to give birth in health facilities in many parts of Indonesia. This study explores the roles and observations of close-to-community maternal health providers and other community members on potential barriers faced by women to deliver in health facilities in two districts within The Archipelago. Methods: Employing an explorative qualitative approach, 110 semi-structured interviews and 7 focus group discussions were conducted in 8 villages in Southwest Sumba, in the East Nusa Tenggara province, and in 8 villages in Cianjur, in the West Java province. The participants included village midwives, Posyandu kader (village health volunteers, traditional birth attendants (TBAs, mothers, men, village heads and district health officials. Results: The main findings were mostly similar in the two study areas. However, there were some key differences. Preference for TBA care, traditional beliefs, a lack of responsiveness of health providers to local traditions, distance, cost of travel and indirect costs of accompanying family members were all barriers to patients attending health facilities for the birth of their child. TBAs were the preferred health providers in most cases due to their close proximity at the time of childbirth and their adherence to traditional practices during pregnancy and delivery. Conclusions: Improving collaborations between midwives and TBAs, and responsiveness to traditional practices within health facilities and effective health promotion campaigns about the benefits of giving birth in health facilities may increase the use of health facilities in both study areas.

  1. "Yes, I Can": the protective role of personal self-efficacy in hindering counterproductive work behavior under stressful conditions.

    Science.gov (United States)

    Fida, Roberta; Paciello, Marinella; Tramontano, Carlo; Barbaranelli, Claudio; Farnese, Maria Luisa

    2015-01-01

    Within the stressor-emotion model, counterproductive work behavior (CWB) is considered a possible result of stress. It is well-known that self-efficacy mitigates the detrimental effects of stress and the stressor-strain relation. We aim to extend the stressor-emotion model of CWB by examining the additive and moderating role of work and regulatory emotional self-efficacy dimensions. A structural equation model and a set of hierarchical regressions were conducted on a convenience sample of 1147 Italian workers. Individuals who believed in their capabilities to manage work activities had a lower propensity to act counterproductively. Workers who believed in their capabilities to cope with negative feelings had a lower propensity to react with negative emotions under stressful conditions. Finally, results showed that self-efficacy moderates at least some of the relationships between stressors and negative emotions, and also between stressors and CWB, but did not moderate the relationship between negative emotions and these types of conduct. Self-efficacy beliefs proved to be a protective factor that can reduce the impact of stressful working conditions.

  2. Promoting universal financial protection: evidence from seven low- and middle-income countries on factors facilitating or hindering progress.

    Science.gov (United States)

    McIntyre, Di; Ranson, Michael K; Aulakh, Bhupinder K; Honda, Ayako

    2013-09-24

    Although universal health coverage (UHC) is a global health policy priority, there remains limited evidence on UHC reforms in low- and middle-income countries (LMICs). This paper provides an overview of key insights from case studies in this thematic series, undertaken in seven LMICs (Costa Rica, Georgia, India, Malawi, Nigeria, Tanzania, and Thailand) at very different stages in the transition to UHC.These studies highlight the importance of increasing pre-payment funding through tax funding and sometimes mandatory insurance contributions when trying to improve financial protection by reducing out-of-pocket payments. Increased tax funding is particularly important if efforts are being made to extend financial protection to those outside formal-sector employment, raising questions about the value of pursuing contributory insurance schemes for this group. The prioritisation of insurance scheme coverage for civil servants in the first instance in some LMICs also raises questions about the most appropriate use of limited government funds.The diverse reforms in these countries provide some insights into experiences with policies targeted at the poor compared with universalist reform approaches. Countries that have made the greatest progress to UHC, such as Costa Rica and Thailand, made an explicit commitment to ensuring financial protection and access to needed care for the entire population as soon as possible, while this was not necessarily the case in countries adopting targeted reforms. There also tends to be less fragmentation in funding pools in countries adopting a universalist rather than targeting approach. Apart from limiting cross-subsidies, fragmentation of pools has contributed to differential benefit packages, leading to inequities in access to needed care and financial protection across population groups; once such differentials are entrenched, they are difficult to overcome. Capacity constraints, particularly in purchasing organisations, are a pervasive problem in LMICs. The case studies also highlighted the critical role of high-level political leadership in pursuing UHC policies and citizen support in sustaining these policies.This series demonstrates the value of promoting greater sharing of experiences on UHC reforms across LMICs. It also identifies key areas of future research on health care financing in LMICs that would support progress towards UHC.

  3. Hybridization of two biotypes of Lilioceris cheni will not hinder biological control of air potato, Dioscorea bulbifera

    Science.gov (United States)

    Dioscorea bulbifera L. (Dioscoreales: Dioscoreaceae), air potato, is a perennial vine native to Asia and Africa that is invasive in Florida and other parts of the southeastern United States. Air potato vines can grow more than 20 meters long and outcompete native vegetation in a variety of habitats....

  4. Gender as a Hindering Factor for Women Operation in the Leading Positions in the Public Administration of Latvia

    OpenAIRE

    Zaķe, Agate

    2012-01-01

    ANNOTATION The dissertation provides an analysis of scientific theories related to a woman’s role in public administration, including interaction of equality, feminism and public administration theories and women’s career development, discusses management vs. leadership in gender perspective, decision-making mechanisms, team role theories and gives theoretical analysis of gender stereotypes and prejudice and a comparison of discrimination theories. The practice of solving ge...

  5. Structure and hindered vibration of Bi2+ in the red-orange phosphor SrB4O7:Bi

    NARCIS (Netherlands)

    De Jong, Mathijs; Meijerink, A; Barandiarán, Zoila; Seijo, Luis

    2014-01-01

    The emission band profile of bismuth-doped SrB4O7 is measured with high resolution, and distinct vibronic features are observed at 4.2 K. The energy intervals show an irregular distribution. It is interpreted in the light of ab initio calculations as due to two off-center totally symmetric normal

  6. Hindering the illegal trade in dog and cat furs through a DNA-based protocol for species identification

    Directory of Open Access Journals (Sweden)

    Luisa Garofalo

    2018-06-01

    Full Text Available In Western countries dogs and cats are the most popular pets, and people are increasingly opposed to their rearing for the fur industry. In 2007, a Regulation of the European Union (EU banned the use and trade of dog and cat furs, but an official analytical protocol to identify them as source species was not provided, and violations of law are still frequent in all Member States. In this paper we report on the development and validation of a simple and affordable DNA method for species detection in furs to use as an effective tool to combat illegal trade in fur products. A set of mitochondrial primers was designed for amplification of partial cytochrome b, control region and ND1 gene in highly degraded samples, like furs and pelts. Our amplification workflow involved the use of a non-specific primer pair to perform a first test to identify the species through sequencing, then the application of species-specific primer pairs to use in singleplex end-point PCRs as confirmation tests. The advantage of this two-step procedure is twofold: on the one hand it minimises the possibility of negative test results from degraded samples, since failure of amplification with a first set of primers can be offset by successful amplification of the second, and on the other it adds confidence and reliability to final authentication of species. All designed primers were validated on a reference collection of tissue samples, obtaining solid results in terms of specificity, sensitivity, repeatability and reproducibility. Application of the protocol on real caseworks from seized furs yielded successful results also from old and dyed furs, suggesting that age and chemical staining do not necessarily affect positive amplifications. Major pros of this approach are: (1 sensitive and informative primer sets for detection of species; (2 short PCR amplicons for the analysis of poor quality DNA; (3 binding primers that avoid contamination from human DNA; (4 user-friendly protocol for any laboratory equipped for analysis of low-copy-number DNA. Our molecular procedure proved to be a good starting point for enforcing the EU Regulation against dog and cat fur trade in forensic contexts where source attribution is essential to the assignment of responsibilities.

  7. Diastereoselectivity in the reduction of bicyclic enones with hindered hydrides; Diastereosseletividade na reducao de enonas biciclicas com hidretos volumosos

    Energy Technology Data Exchange (ETDEWEB)

    Camozzato, Andreza C.; Tenius, Beatriz S. M.; Oliveira, Eduardo R. de [Universidade Federal do Rio Grande do Sul (UFRGS), Porto Alegre, RS (Brazil). Inst. de Quimica. Dept. de Quimica Organica]. E-mail: eroliv@iq.ufrgs.br; Viegas Junior, Claudio [Universidade Federal de Alfenas (UFAL), MG (Brazil). Dept. de Farmacia; Victor, Mauricio M. [Universidade Federal da Bahia (UFBA), Salvador, BA (Brazil). Inst. de Quimica. Dept. de Quimica Organica; Silveira, Leandro G. da [Universidade Regional Integrada do Alto Uruguai e das Missoes, Frederico Westphalen, RS (Brazil). Curso de Quimica. Dept. de Ciencias Exatas e da Terra

    2008-07-01

    Reduction of five substituted octalones employing lithium tri-sec-butylborohydride (L-selectride{sup R}) in THF and ethyl ether led to allylic alcohols with moderate diastereoselectivity. The stereoselectivity of addition of bulky hydrides showed to be different from most examples in the literature and was strongly influenced by substitution on the octalone ring. (author)

  8. Lack of knowledge and availability of diagnostic equipment could hinder the diagnosis of sarcopenia and its management

    NARCIS (Netherlands)

    Reijnierse, Esmee M.; De Van Der Schueren, Marian A.E.; Trappenburg, Marijke C.; Doves, Marjan; Meskers, Carel G.M.; Maier, Andrea B.

    2017-01-01

    Objectives: Sarcopenia is an emerging clinical challenge in an ageing population and is associated with serious negative health outcomes. This study aimed to assess the current state of the art regarding the knowledge about the concept of sarcopenia and practice of the diagnostic strategy and

  9. Factors that may Facilitate or Hinder a Family-Focus in the Treatment of Parents with a Mental Illness.

    Science.gov (United States)

    Lauritzen, Camilla; Reedtz, Charlotte; Van Doesum, Karin; Martinussen, Monica

    Children with mentally ill parents are at risk of developing mental health problems themselves. To enhance early support for these children may prevent mental health problems from being transmitted from one generation to the next. The sample ( N  = 219) included health professionals in a large university hospital, who responded to a web-based survey on the routines of the mental health services, attitudes within the workforce capacity, worker's knowledge on the impact of parental mental illness on children, knowledge on legislation concerning children of patients, experience, expectations for possible outcomes of change in current clinical practice and demographic variables. A total of 56 % reported that they did not identify whether or not patients had children. There were no significant differences between the groups (identifiers and non-identifiers) except for the two scales measuring aspects of knowledge, i.e., Knowledge Children and Knowledge Legislation where workers who identified children had higher scores. The results also showed that younger workers with a medium level of education scored higher on Positive Attitudes. Furthermore, workers who reported to have more knowledge about children and the impact of mental illness on the parenting role were less concerned about a child-focussed approach interfering with the patient-therapist relation.

  10. Factors that may Facilitate or Hinder a Family-Focus in the Treatment of Parents with a Mental Illness

    NARCIS (Netherlands)

    Lauritzen, C.; Reedtz, C.; Doesum, K.T.M. van; Martinussen, M.

    2015-01-01

    Children with mentally ill parents are at risk of developing mental health problems themselves. To enhance early support for these children may prevent mental health problems from being transmitted from one generation to the next. The sample (N = 219) included health professionals in a large

  11. How do postgraduate GP trainees regulate their learning and what helps and hinders them? A qualitative study.

    Science.gov (United States)

    Sagasser, Margaretha H; Kramer, Anneke W M; van der Vleuten, Cees P M

    2012-08-06

    Self-regulation is essential for professional development. It involves monitoring of performance, identifying domains for improvement, undertaking learning activities, applying newly learned knowledge and skills and self-assessing performance. Since self-assessment alone is ineffective in identifying weaknesses, learners should seek external feedback too. Externally regulated educational interventions, like reflection, learning portfolios, assessments and progress meetings, are increasingly used to scaffold self-regulation.The aim of this study is to explore how postgraduate trainees regulate their learning in the workplace, how external regulation promotes self-regulation and which elements facilitate or impede self-regulation and learning. In a qualitative study with a phenomenologic approach we interviewed first- and third-year GP trainees from two universities in the Netherlands. Twenty-one verbatim transcripts were coded. Through iterative discussion the researchers agreed on the interpretation of the data and saturation was reached. Trainees used a short and a long self-regulation loop. The short loop took one week at most and was focused on problems that were easy to resolve and needed minor learning activities. The long loop was focused on complex or recurring problems needing multiple and planned longitudinal learning activities. External assessments and formal training affected the long but not the short loop. The supervisor had a facilitating role in both loops. Self-confidence was used to gauge competence.Elements influencing self-regulation were classified into three dimensions: personal (strong motivation to become a good doctor), interpersonal (stimulation from others) and contextual (organizational and educational features). Trainees did purposefully self-regulate their learning. Learning in the short loop may not be visible to others. Trainees should be encouraged to actively seek and use external feedback in both loops. An important question for further research is which educational interventions might be used to scaffold learning in the short loop. Investing in supervisor quality remains important, since they are close to trainee learning in both loops.

  12. Expression of RNA virus proteins by RNA polymerase II dependent expression plasmids is hindered at multiple steps

    Directory of Open Access Journals (Sweden)

    Überla Klaus

    2007-06-01

    Full Text Available Abstract Background Proteins of human and animal viruses are frequently expressed from RNA polymerase II dependent expression cassettes to study protein function and to develop gene-based vaccines. Initial attempts to express the G protein of vesicular stomatitis virus (VSV and the F protein of respiratory syncytial virus (RSV by eukaryotic promoters revealed restrictions at several steps of gene expression. Results Insertion of an intron flanked by exonic sequences 5'-terminal to the open reading frames (ORF of VSV-G and RSV-F led to detectable cytoplasmic mRNA levels of both genes. While the exonic sequences were sufficient to stabilise the VSV-G mRNA, cytoplasmic mRNA levels of RSV-F were dependent on the presence of a functional intron. Cytoplasmic VSV-G mRNA levels led to readily detectable levels of VSV-G protein, whereas RSV-F protein expression remained undetectable. However, RSV-F expression was observed after mutating two of four consensus sites for polyadenylation present in the RSV-F ORF. Expression levels could be further enhanced by codon optimisation. Conclusion Insufficient cytoplasmic mRNA levels and premature polyadenylation prevent expression of RSV-F by RNA polymerase II dependent expression plasmids. Since RSV replicates in the cytoplasm, the presence of premature polyadenylation sites and elements leading to nuclear instability should not interfere with RSV-F expression during virus replication. The molecular mechanisms responsible for the destabilisation of the RSV-F and VSV-G mRNAs and the different requirements for their rescue by insertion of an intron remain to be defined.

  13. Host-adaptation of Francisella tularensis alters the bacterium's surface-carbohydrates to hinder effectors of innate and adaptive immunity.

    Directory of Open Access Journals (Sweden)

    Tiffany M Zarrella

    Full Text Available The gram-negative bacterium Francisella tularensis survives in arthropods, fresh water amoeba, and mammals with both intracellular and extracellular phases and could reasonably be expected to express distinct phenotypes in these environments. The presence of a capsule on this bacterium has been controversial with some groups finding such a structure while other groups report that no capsule could be identified. Previously we reported in vitro culture conditions for this bacterium which, in contrast to typical methods, yielded a bacterial phenotype that mimics that of the bacterium's mammalian, extracellular phase.SDS-PAGE and carbohydrate analysis of differentially-cultivated F. tularensis LVS revealed that bacteria displaying the host-adapted phenotype produce both longer polymers of LPS O-antigen (OAg and additional HMW carbohydrates/glycoproteins that are reduced/absent in non-host-adapted bacteria. Analysis of wildtype and OAg-mutant bacteria indicated that the induced changes in surface carbohydrates involved both OAg and non-OAg species. To assess the impact of these HMW carbohydrates on the access of outer membrane constituents to antibody we used differentially-cultivated bacteria in vitro to immunoprecipitate antibodies directed against outer membrane moieties. We observed that the surface-carbohydrates induced during host-adaptation shield many outer membrane antigens from binding by antibody. Similar assays with normal mouse serum indicate that the induced HMW carbohydrates also impede complement deposition. Using an in vitro macrophage infection assay, we find that the bacterial HMW carbohydrate impedes TLR2-dependent, pro-inflammatory cytokine production by macrophages. Lastly we show that upon host-adaptation, the human-virulent strain, F. tularensis SchuS4 also induces capsule production with the effect of reducing macrophage-activation and accelerating tularemia pathogenesis in mice.F. tularensis undergoes host-adaptation which includes production of multiple capsular materials. These capsules impede recognition of bacterial outer membrane constituents by antibody, complement, and Toll-Like Receptor 2. These changes in the host-pathogen interface have profound implications for pathogenesis and vaccine development.

  14. What Helps and Hinders Indigenous Student Success in Higher Education Health Programmes: A Qualitative Study Using the Critical Incident Technique

    Science.gov (United States)

    Curtis, Elana; Wikaire, Erena; Kool, Bridget; Honey, Michelle; Kelly, Fiona; Poole, Phillippa; Barrow, Mark; Airini; Ewen, Shaun; Reid, Papaarangi

    2015-01-01

    Tertiary institutions aim to provide high quality teaching and learning that meet the academic needs for an increasingly diverse student body including indigenous students. "Tatou Tatou" is a qualitative research project utilising Kaupapa "Maori" research methodology and the Critical Incident Technique interview method to…

  15. Electronic Waste: DOD Is Recovering Materials, but Several Factors May Hinder Near-Term Expansion of These Efforts

    Science.gov (United States)

    2016-06-01

    non-ferrous metals include aluminum, copper , lead, zinc, and tin, as well as precious metals like gold and silver. 31DLA’s operations are funded...36The rates the recyclers are paying to buy DOD’s electronic waste are based on a percentage of the American Metal Market #1 copper and...after which lighter weight and combustible materials, such as plastic and paper, are removed by burning or flotation . The remaining solids are heated

  16. The impact of mobility scooters on their users. Does their usage help or hinder?: A state of the art review.

    Science.gov (United States)

    Thoreau, Roselle

    2015-06-01

    As older people start to have difficulty in walking many choose to use a mobility scooter to help them move around. Benefitting from improved design, mobility scooters are becoming an increasingly popular mobility device and are a common sight on many streets. However, very little is known about their usage or their impact in terms of either quality of life or functional health. Whilst mobility scooters may help to improve the quality of life of their users, it is also possible that the sedentary nature of their usage results in a decline of physical functionality and therefore reduced capabilities. Before any substantial research can be carried out it is crucial to understand the importance of a mobility scooter on the lives of the people that use them and to review the initial research published on the effect of scooter use on physical health. This paper is a state-of-the-art review. It describes the current research knowledge on mobility scooters, shows where gaps in knowledge exist and where future research needs to focus.

  17. What hinders the uptake of computerized decision support systems in hospitals? A qualitative study and framework for implementation.

    Science.gov (United States)

    Liberati, Elisa G; Ruggiero, Francesca; Galuppo, Laura; Gorli, Mara; González-Lorenzo, Marien; Maraldi, Marco; Ruggieri, Pietro; Polo Friz, Hernan; Scaratti, Giuseppe; Kwag, Koren H; Vespignani, Roberto; Moja, Lorenzo

    2017-09-15

    Advanced Computerized Decision Support Systems (CDSSs) assist clinicians in their decision-making process, generating recommendations based on up-to-date scientific evidence. Although this technology has the potential to improve the quality of patient care, its mere provision does not guarantee uptake: even where CDSSs are available, clinicians often fail to adopt their recommendations. This study examines the barriers and facilitators to the uptake of an evidence-based CDSS as perceived by diverse health professionals in hospitals at different stages of CDSS adoption. Qualitative study conducted as part of a series of randomized controlled trials of CDSSs. The sample includes two hospitals using a CDSS and two hospitals that aim to adopt a CDSS in the future. We interviewed physicians, nurses, information technology staff, and members of the boards of directors (n = 30). We used a constant comparative approach to develop a framework for guiding implementation. We identified six clusters of experiences of, and attitudes towards CDSSs, which we label as "positions." The six positions represent a gradient of acquisition of control over CDSSs (from low to high) and are characterized by different types of barriers to CDSS uptake. The most severe barriers (prevalent in the first positions) include clinicians' perception that the CDSSs may reduce their professional autonomy or may be used against them in the event of medical-legal controversies. Moving towards the last positions, these barriers are substituted by technical and usability problems related to the technology interface. When all barriers are overcome, CDSSs are perceived as a working tool at the service of its users, integrating clinicians' reasoning and fostering organizational learning. Barriers and facilitators to the use of CDSSs are dynamic and may exist prior to their introduction in clinical contexts; providing a static list of obstacles and facilitators, irrespective of the specific implementation phase and context, may not be sufficient or useful to facilitate uptake. Factors such as clinicians' attitudes towards scientific evidences and guidelines, the quality of inter-disciplinary relationships, and an organizational ethos of transparency and accountability need to be considered when exploring the readiness of a hospital to adopt CDSSs.

  18. Contextual attributes promote or hinder self-regulated learning: A qualitative study contrasting rural physicians with undergraduate learners in Japan.

    Science.gov (United States)

    Matsuyama, Yasushi; Nakaya, Motoyuki; Okazaki, Hitoaki; Leppink, Jimmie; van der Vleuten, Cees

    2018-03-01

    Previous studies support the notion that East Asian medical students do not possess sufficient self-regulation for postgraduate clinical training. However, some East Asian physicians who are employed in geographically isolated and educationally underserved rural settings can self-regulate their study during the early phase of their postgraduate career. To explore the contextual attributes that contribute to self-regulated learning (SRL), we examined the differences in self-regulation between learning as an undergraduate and in a rural context in East Asia. We conducted interviews and diary data collection among rural physicians (n = 10) and undergraduates (n = 11) in Japan who undertook self-study of unfamiliar diseases. We analyzed three domains of Zimmerman's definition of SRL: learning behaviors, motivation, and metacognition using constructivist grounded theory. Rural physicians recognized their identity as unique, and as professionals with a central role of handling diseases in the local community by conducting self-study. They simultaneously found themselves being at risk of providing inappropriate aid if their self-study was insufficient. They developed strategic learning strategies to cope with this high-stakes task. Undergraduates had a fear of being left behind and preferred to remain as one of the crowd with students in the same school year. Accordingly, they copied the methods of other students for self-study and used monotonous and homogeneous strategies. Different learning contexts do not keep East Asian learners from being self-regulated. Awareness of their unique identity leads them to view learning tasks as high-stakes, and to initiate learning strategies in a self-regulated manner. Teacher-centered education systems cause students to identify themselves as one of the crowd, and tasks as low-stakes, and to accordingly employ non-self-regulated strategies.

  19. Emotional eating behavior hinders body weight loss in women after Roux-en-Y gastric bypass surgery.

    Science.gov (United States)

    Novelli, Isabelle Romero; Fonseca, Laís Gomes; Gomes, Daniela Lopes; Dutra, Eliane Said; Baiocchi de Carvalho, Kênia Mara

    2018-05-01

    Successful weight loss and maintenance after Roux-en-Y gastric bypass (RYGB) may be related to eating behavior. The aim of this study was to assess the eating behavior domains that prevail in women during the RYGB postoperative period and their associations with surgery outcome. This cross-sectional study investigated eating behavior in 95 women (47.3 ± 9.8 y old)  ≥ 2 y after Roux-en-Y gastric bypass. Patients were grouped according to surgery outcome: successful group (SG; n = 67), defined as having lost ≥ 50% of the preoperative excess weight loss (EWL), and an unsuccessful group (UG; n = 28). Mean postoperative time was 59.5 ± 21.2 mo (55.7 ± 19.9 in the SG and 68.6 ± 21.9 in the UG). The short version of the Three-Factor Eating Questionnaire was used to assess cognitive restraint, emotional eating, and uncontrolled eating behaviors. Multivariate analysis was used to investigate associations between eating behavior scores and EWL. The highest score in both groups was for the cognitive restraint domain, followed by emotional and uncontrolled eating. Emotional eating was negatively associated with percentage of EWL (β = -0.286; P = 0.033), regardless of age, educational attainment, and postoperative time. The cognitive restraint domain was the main type of eating behavior observed, and patients with higher emotional eating score were at a higher risk for having insufficient weight loss after RYGB. These results indicate the relevance of monitoring emotional components during the long-term nutritional follow-up of bariatric patients to achieve better surgery outcomes. Copyright © 2017 Elsevier Inc. All rights reserved.

  20. Australian regulatory framework and reporting entities are hindering the lessons to be learned from adverse radiation events

    International Nuclear Information System (INIS)

    Denham, G.

    2016-01-01

    When adverse radiation events occur in the medical radiation science profession in Australia they are reported to the relevant state or territory authority. The details and cause of the incident are forwarded to the Australian Radiation Protection and Nuclear Safety Agency (ARPANSA) to be included in the Australian Radiation Incident Register. The aim of any error reporting system is to learn from previous errors and to prevent them occurring again. The information obtained from past errors is one of the most invaluable tools to prevent future adverse events. This article examines the current regulatory framework, reporting systems and radiation protection authorities in Australia and their effectiveness at improving patient safety. Several obstacles must be overcome if the systems and organisations responsible for radiation safety are to meet the expectations of both the community and the medical radiation science profession. - Highlights: • Adverse radiation events in Australia are reported to state and territory authorities. • Adverse radiation events are included in the Australian Radiation Incident Register State and territory radiation authorities have failed to implement changes agreed upon in 1999. • The Australian Radiation Incident Register requires reforms if it is to operate as an effective learning system.

  1. 9,10-Anthraquinone hinders β-aggregation: How does a small molecule interfere with Aβ-peptide amyloid fibrillation?

    Science.gov (United States)

    Convertino, Marino; Pellarin, Riccardo; Catto, Marco; Carotti, Angelo; Caflisch, Amedeo

    2009-01-01

    Amyloid aggregation is linked to a number of neurodegenerative syndromes, the most prevalent one being Alzheimer's disease. In this pathology, the β-amyloid peptides (Aβ) aggregate into oligomers, protofibrils, and fibrils and eventually into plaques, which constitute the characteristic hallmark of Alzheimer's disease. Several low-molecular-weight compounds able to impair the Aβ aggregation process have been recently discovered; yet, a detailed description of their interactions with oligomers and fibrils is hitherto missing. Here, molecular dynamics simulations are used to investigate the influence of two relatively similar tricyclic, planar compounds, that is, 9, 10-anthraquinone (AQ) and anthracene (AC), on the early phase of the aggregation of the Aβ heptapeptide segment H14QKLVFF20, the hydrophobic stretch that promotes the Aβ self-assembly. The simulations show that AQ interferes with β-sheet formation more than AC. In particular, AQ intercalates into the β-sheet because polar interactions between the compound and the peptide backbone destabilize the interstrand hydrogen bonds, thereby favoring disorder. The thioflavin T-binding assay indicates that AQ, but not AC, sensibly reduces the amount of aggregated Aβ1–40 peptide. Taken together, the in silico and in vitro results provide evidence that structural perturbations by AQ can remarkably affect ordered oligomerization. Moreover, the simulations shed light at the atomic level on the interactions between AQ and Aβ oligomers, providing useful insights for the design of small-molecule inhibitors of aggregation with therapeutic potential in Alzheimer's disease. PMID:19309732

  2. How do postgraduate GP trainees regulate their learning and what helps and hinders them? A qualitative study

    Science.gov (United States)

    2012-01-01

    Background Self-regulation is essential for professional development. It involves monitoring of performance, identifying domains for improvement, undertaking learning activities, applying newly learned knowledge and skills and self-assessing performance. Since self-assessment alone is ineffective in identifying weaknesses, learners should seek external feedback too. Externally regulated educational interventions, like reflection, learning portfolios, assessments and progress meetings, are increasingly used to scaffold self-regulation. The aim of this study is to explore how postgraduate trainees regulate their learning in the workplace, how external regulation promotes self-regulation and which elements facilitate or impede self-regulation and learning. Methods In a qualitative study with a phenomenologic approach we interviewed first- and third-year GP trainees from two universities in the Netherlands. Twenty-one verbatim transcripts were coded. Through iterative discussion the researchers agreed on the interpretation of the data and saturation was reached. Results Trainees used a short and a long self-regulation loop. The short loop took one week at most and was focused on problems that were easy to resolve and needed minor learning activities. The long loop was focused on complex or recurring problems needing multiple and planned longitudinal learning activities. External assessments and formal training affected the long but not the short loop. The supervisor had a facilitating role in both loops. Self-confidence was used to gauge competence.Elements influencing self-regulation were classified into three dimensions: personal (strong motivation to become a good doctor), interpersonal (stimulation from others) and contextual (organizational and educational features). Conclusions Trainees did purposefully self-regulate their learning. Learning in the short loop may not be visible to others. Trainees should be encouraged to actively seek and use external feedback in both loops. An important question for further research is which educational interventions might be used to scaffold learning in the short loop. Investing in supervisor quality remains important, since they are close to trainee learning in both loops. PMID:22866981

  3. Contemporary temperature-driven divergence in a Nordic freshwater fish under conditions commonly thought to hinder adaptation

    Directory of Open Access Journals (Sweden)

    Gregersen Finn

    2010-11-01

    Full Text Available Abstract Background Evaluating the limits of adaptation to temperature is important given the IPCC-predicted rise in global temperatures. The rate and scope of evolutionary adaptation can be limited by low genetic diversity, gene flow, and costs associated with adaptive change. Freshwater organisms are physically confined to lakes and rivers, and must therefore deal directly with climate variation and change. In this study, we take advantage of a system characterised by low genetic variation, small population size, gene flow and between-trait trade-offs to study how such conditions affect the ability of a freshwater fish to adapt to climate change. We test for genetically-based differences in developmental traits indicating local adaptation, by conducting a common-garden experiment using embryos and larvae from replicate pairs of sympatric grayling demes that spawn and develop in natural cold and warm water, respectively. These demes have common ancestors from a colonization event 22 generations ago. Consequently, we explore if diversification may occur under severely constraining conditions. Results We found evidence for divergence in ontogenetic rates. The divergence pattern followed adaptation predictions as cold-deme individuals displayed higher growth rates and yolk conversion efficiency than warm-deme individuals at the same temperature. The cold-deme embryos had a higher rate of muscle mass development. Most of the growth- and development differences occurred prior to hatch. The divergence was probably not caused by genetic drift as there was a strong degree of parallelism in the divergence pattern and because phenotypic differentiation (QST was larger than estimated genetic drift levels (microsatellite FST between demes from different temperature groups. We also document that these particular grayling populations cannot develop successfully at temperatures above 12°C, whereas other European populations can, and that increasing the muscle mass development rate comes at the cost of some skeletal trait development rates. Conclusions This study shows that genetically based phenotypic divergence can prevail even under conditions of low genetic variation and ongoing gene flow. Furthermore, population-specific maximum development temperatures along with musculoskeletal developmental trade-offs may constrain adaptation.

  4. Organizational Cultural Factors Hindering Women Ascending to Top Management Positions in Public Universities in Kenya: A Case of Moi University

    Science.gov (United States)

    Makori, Rebecca S.; Onyango, Maria; Attyang, Judith Miguda; Bantu, Edward; Onderi, Peter Omae

    2016-01-01

    It is observed that the major setback to economic development in Kenya is stagnation in industrial development. To overcome these, Kenya plans to be a middle level income nation by the year 2030. These plans are to be realized through "Vision 2030." To achieve these goals, Kenya requires gender mainstreamed team of highly skilled workers…

  5. The cytotoxic effect of palytoxin on Caco-2 cells hinders their use for in vitro absorption studies.

    Science.gov (United States)

    Pelin, M; Sosa, S; Della Loggia, R; Poli, M; Tubaro, A; Decorti, G; Florio, C

    2012-02-01

    Palytoxin (PLTX), found in Palythoa zoanthids and Ostreopsis dinoflagellates, has also been detected in crabs and fish, through which it can enter into the food chain. Indeed, PLTX is considered the causative agent of several cases of human seafood poisoning resulting in systemic symptoms. Available epidemiological data on PLTX human toxicity suggest that the intestinal tract may be one of its in vivo targets and its potential site of access into the bloodstream. Hence, the purpose of this study was to investigate the suitability of the human intestinal Caco-2 cell line for evaluating PLTX oral absorption. A detailed analysis of PLTX cytotoxicity revealed a high sensitivity of Caco-2 cells: 4h toxin exposure reduced mitochondrial activity (MTT assay, EC(50) of 8.9±3.7×10(-12)M), cell density (SRB assay, EC(50) of 2.0±0.6×10(-11)M) and membrane integrity (LDH release, EC(50) of 4.5±1.4×10(-9)M and PI uptake, EC(50) of 1.0±0.8×10(-8)M). After low PLTX concentration (1.0×10(-11)M) exposure for 1-8h, followed by 24h recovery time in toxin-free medium, cell density reduction was only partially reversible. These results indicate that, due to the high susceptibility to PLTX cytotoxic effects, Caco-2 cells do not represent an appropriate and reliable model for investigating intestinal barrier permeation by this toxin. Copyright © 2011 Elsevier Ltd. All rights reserved.

  6. Worked Examples with Errors: When Self-Explanation Prompts Hinder Learning of Teachers Diagnostic Competences on Problem-Based Learning

    Science.gov (United States)

    Heitzmann, Nicole; Fischer, Frank; Fischer, Martin R.

    2018-01-01

    To diagnose classroom situations is crucial for teachers' everyday practice. The approach of worked examples with errors seems promising to support the diagnosis of classroom situations in student teachers (Stark et al. in "Learn Instr" 21(1):22-33, 2011). To enhance that approach, error-explanation prompts and an adaptable feedback…

  7. 21st Century Changes in Precipitation Extremes Over the United States: Can Climate Analogues Help or Hinder?

    Science.gov (United States)

    Gao, X.; Schlosser, C. A.

    2013-12-01

    Global warming is expected to alter the frequency and/or magnitude of extreme precipitation events. Such changes could have substantial ecological, economic, and sociological consequences. However, climate models in general do not correctly reproduce the frequency and intensity distribution of precipitation, especially at the regional scale. In this study, gridded data from a dense network of surface precipitation gauges and a global atmospheric analysis at a coarser scale are combined to develop a diagnostic framework for the large-scale meteorological conditions (i.e. flow features, moisture supply) that dominate during extreme precipitation. Such diagnostic framework is first evaluated with the late 20th century simulations from an ensemble of climate models participating in the Coupled Model Intercomparison Project Phase 5 (CMIP5), and is found to produce more consistent (and less uncertain) total and interannaul number of extreme days with the observations than the model-based precipitation over the south-central United States and the Western United States examined in this study. The framework is then applied to the CMIP5 multi-model projections for two radiative forcing scenarios (Representative Concentration Pathways 4.5 and 8.5) to assess the potential future changes in the probability of precipitation extremes over the same study regions. We further analyze the accompanying circulation features and their changes that may be responsible for shifts in extreme precipitation in response to changed climate. The results from this study may guide hazardous weather watches and help society develop adaptive strategies for preventing catastrophic losses.

  8. Hydroalumination of Ketenimines and Subsequent Reactions with Heterocumulenes: Synthesis of Unsaturated Amide Derivatives and 1,3-Diimines.

    Science.gov (United States)

    Jin, Xing; Willeke, Matthias; Lucchesi, Ralph; Daniliuc, Constantin-Gabriel; Fröhlich, Roland; Wibbeling, Birgit; Uhl, Werner; Würthwein, Ernst-Ulrich

    2015-06-19

    The series of differently substituted ketenimines 1 was hydroluminated using di-iso-butyl aluminum hydride. For the sterically congested ketenimine 1a, preferred hydroalumination of the C═N-bond was proven by X-ray crystallography (compound 5a). In situ treatment of the hydroaluminated ketenimines 5 with various heterocumulenes like carbodiimides, isocycanates, isothiocyanates and ketenimines as electrophiles and subsequent hydrolytic workup resulted in novel enamine derived amide species in case of N-attack (sterically less hindered ketenimines) under formation of a new C-N-bond or in 1,3-diimines by C-C-bond-formation in case of bulky substituents at the ketenimine-nitrogen atom. Furthermore, domino reactions with more than 1 equiv of the electrophile or by subsequent addition of two different electrophiles are possible and lead to polyfunctional amide derivatives of the biuret type which are otherwise not easily accessible.

  9. Using the general-purpose reactivity indicator: challenging examples.

    Science.gov (United States)

    Anderson, James S M; Melin, Junia; Ayers, Paul W

    2016-03-01

    We elucidate the regioselectivity of nucleophilic attack on substituted benzenesulfonates, quinolines, and pyridines using a general-purpose reactivity indicator (GPRI) for electrophiles. We observe that the GPRI is most accurate when the incoming nucleophile resembles a point charge. We further observe that the GPRI often chooses reactive "dead ends" as the most reactive sites as well as sterically hindered reactive sites. This means that care must be taken to remove sites that are inherently unreactive. Generally, among sites where reactions actually occur, the GPRI identifies the sites in the molecule that lead to the kinetically favored product(s). Furthermore, the GPRI can discern which sites react with hard reagents and which sites react with soft reagents. Because it is currently impossible to use the mathematical framework of conceptual DFT to identify sterically inaccessible sites and reactive dead ends, the GPRI is primarily useful as an interpretative, not a predictive, tool.

  10. Influence of Bridgehead Substitution and Ring Annelation on the Photophysical Properties of Polycyclic DBO-Type Azoalkanes.

    Science.gov (United States)

    Adam, Waldemar; Nikolaus, Achim; Sauer, Jürgen

    1999-05-14

    The photophysical data for the polycyclic, bridgehead-substituted derivatives 1-10 of the photoreluctant diazabicyclo[2.2.2]oct-2-ene (DBO) are presented. Substitution on the bridgehead positions with radical-stabilizing substituents enhances the photoreactivity (Phi(r)) and decreases the fluorescence quantum yields (Phi(f)) and lifetimes (tau) compared to the parent DBO. The annelated rings have no influence on the photoreactivity, except when steric interactions with an alpha substituent hinder the optimal radical-stabilizing conformation. The fused rings and some of the bridgehead substituents reduce the solvent-induced quenching of the singlet-excited azo chromophore by steric shielding of the azo group and, thus, increase the fluorescence quantum yields and lifetimes.

  11. Importance of the Donor:Fullerene intermolecular arrangement for high-efficiency organic photovoltaics

    KAUST Repository

    Graham, Kenneth; Cabanetos, Clement; Jahnke, Justin P.; Idso, Matthew N.; El Labban, Abdulrahman; Ngongang Ndjawa, Guy Olivier; Heumueller, Thomas; Vandewal, Koen; Salleo, Alberto; Chmelka, Bradley F.; Amassian, Aram; Beaujuge, Pierre; McGehee, Michael D.

    2014-01-01

    The performance of organic photovoltaic (OPV) material systems are hypothesized to depend strongly on the intermolecular arrangements at the donor:fullerene interfaces. A review of some of the most efficient polymers utilized in polymer:fullerene PV devices, combined with an analysis of reported polymer donor materials wherein the same conjugated backbone was used with varying alkyl substituents, supports this hypothesis. Specifically, the literature shows that higher-performing donor-acceptor type polymers generally have acceptor moieties that are sterically accessible for interactions with the fullerene derivative, whereas the corresponding donor moieties tend to have branched alkyl substituents that sterically hinder interactions with the fullerene. To further explore the idea that the most beneficial polymer:fullerene arrangement involves the fullerene docking with the acceptor moiety, a family of benzo[1,2-b:4,5-b]dithiophene-thieno[3,4-c]pyrrole-4,6-dione polymers (PBDTTPD derivatives) was synthesized and tested in a variety of PV device types with vastly different aggregation states of the polymer. In agreement with our hypothesis, the PBDTTPD derivative with a more sterically accessible acceptor moiety and a more sterically hindered donor moiety shows the highest performance in bulk-heterojunction, bilayer, and low-polymer concentration PV devices where fullerene derivatives serve as the electron-accepting materials. Furthermore, external quantum efficiency measurements of the charge-transfer state and solid-state two-dimensional (2D) 13C{1H} heteronuclear correlation (HETCOR) NMR analyses support that a specific polymer:fullerene arrangement is present for the highest performing PBDTTPD derivative, in which the fullerene is in closer proximity to the acceptor moiety of the polymer. This work demonstrates that the polymer:fullerene arrangement and resulting intermolecular interactions may be key factors in determining the performance of OPV material systems

  12. Importance of the Donor:Fullerene intermolecular arrangement for high-efficiency organic photovoltaics

    KAUST Repository

    Graham, Kenneth

    2014-07-09

    The performance of organic photovoltaic (OPV) material systems are hypothesized to depend strongly on the intermolecular arrangements at the donor:fullerene interfaces. A review of some of the most efficient polymers utilized in polymer:fullerene PV devices, combined with an analysis of reported polymer donor materials wherein the same conjugated backbone was used with varying alkyl substituents, supports this hypothesis. Specifically, the literature shows that higher-performing donor-acceptor type polymers generally have acceptor moieties that are sterically accessible for interactions with the fullerene derivative, whereas the corresponding donor moieties tend to have branched alkyl substituents that sterically hinder interactions with the fullerene. To further explore the idea that the most beneficial polymer:fullerene arrangement involves the fullerene docking with the acceptor moiety, a family of benzo[1,2-b:4,5-b]dithiophene-thieno[3,4-c]pyrrole-4,6-dione polymers (PBDTTPD derivatives) was synthesized and tested in a variety of PV device types with vastly different aggregation states of the polymer. In agreement with our hypothesis, the PBDTTPD derivative with a more sterically accessible acceptor moiety and a more sterically hindered donor moiety shows the highest performance in bulk-heterojunction, bilayer, and low-polymer concentration PV devices where fullerene derivatives serve as the electron-accepting materials. Furthermore, external quantum efficiency measurements of the charge-transfer state and solid-state two-dimensional (2D) 13C{1H} heteronuclear correlation (HETCOR) NMR analyses support that a specific polymer:fullerene arrangement is present for the highest performing PBDTTPD derivative, in which the fullerene is in closer proximity to the acceptor moiety of the polymer. This work demonstrates that the polymer:fullerene arrangement and resulting intermolecular interactions may be key factors in determining the performance of OPV material systems

  13. Effect of carboxyl anchoring groups in asymmetric zinc phthalocyanine with large steric hindrance on the dye-sensitized solar cell performance

    Energy Technology Data Exchange (ETDEWEB)

    Shi, Wenye; Peng, Bosi; Lin, Li; Li, Renjie; Zhang, Jing, E-mail: jzhang03@whu.edu.cn; Peng, Tianyou, E-mail: typeng@whu.edu.cn

    2015-08-01

    Asymmetric zinc phthalocyanines containing tribenzonaphtho-condensed porphyrazine with six bulky diphenylphenoxy and one or two carboxyl groups are used as sensitizers for dye-sensitized solar cells (DSSCs). It is found that Zn-tri-PcNc-4 having two carboxyl groups shows a slight redshift in the Q-band absorption but a significantly decreased absorbance as compared with Zn-tri-PcNc-8 having one carboxyl group, and Zn-tri-PcNc-4 can be more stably and perpendicularly grafted onto the TiO{sub 2} surface than Zn-tri-PcNc-8, which further leads to the differences in the interfacial charge transfer dynamics and dye-loaded amount. Zn-tri-PcNc-4 with two carboxyl groups grafted onto the TiO{sub 2} electrode surface of DSSC results in a photovoltaic conversion efficiency of 3.22%, higher than that (3.01%) of the analog with one carboxyl group (Zn-tri-PcNc-8), which exhibits a lower short-circuit current but much higher open-circuit voltage. The additional carboxyl group in Zn-tri-PcNc-4 leads to the enhanced dye-loaded amount and the molecular orbital energy level shift toward positive direction, causing more efficient electron injection and higher short-circuit current than Zn-tri-PcNc-8; while the two carboxyl groups of Zn-tri-PcNc-4 would cause more protonation of TiO{sub 2} surface, which possibly leads to the downward shift of TiO{sub 2} conduction band edge, and then to the decreased open-circuit voltage. The present results demonstrate the molecular engineering aspect of ZnPc dyes in which the fine tuning of the energy levels and molecular structures is crucial for high conversion efficiency of DSSCs. - Highlights: • ZnPcs with six diphenylphenoxy and one/two carboxyl groups are used as dyes for DSSCs. • Effect of carboxyl group number on the ZnPc-sensitized cell property are scrutinized. • Grafting two carboxyl groups on ZnPc leads to the enhanced photocurrent and efficiency. • ZnPc with one COOH has a higher open-circuit voltage than its analog with two COOH.

  14. Variation of the Sterical Properties of the N-Heterocyclic Carbene Coligand in Thermally Triggerable Ruthenium-Based Olefin Metathesis Precatalysts/Initiators

    KAUST Repository

    Pump, Eva

    2015-11-09

    A series of ruthenium complexes based on the κ(C,N)-(2-(benzo[h]quinolin-10-yl)methylidene ruthenium dichloride fragment featuring different neutral coligands L (L = 1,3-bis(2,6-diisopropylphenyl)-4,5-dihydroimidazol-2-ylidene (SIPr), 1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidene (SIMes), 1,3-bis(2,4-dimethylphenyl)-4,5-dihydroimidazol-2-ylidene (SIXyl), and 1,3-bis(2-methylphenyl)-4,5-dihydroimidazol-2-ylidene (SITol)) was prepared, characterized, and tested in the thermally induced ring-opening metathesis polymerization of dicyclopentadiene. In addition, the corresponding tricyclohexylphosphine derivative was investigated for comparison. All compounds were isolated as their trans-dichloro isomers. NMR spectroscopic features as well as structural features are, particularly within the NHC-bearing complexes, very similar, but their polymerization activity at elevated temperatures is distinctly different. While the SIMes derivative shows the desired properties, i.e., latency at room temperature and pronounced polymerization activity at elevated temperature, all other preinitiators do not. The preinitiator featuring the SIPr coligand is the most latent one, needing temperatures > 140 °C to show moderate activity in the polymerization of dicyclopentadiene. Compounds bearing the smaller N-heterocyclic carbene congeners are stable and latent at room temperature, but decompose upon heating, diminishing the polymerization activity at elevated temperatures. Density functional calculations show that the SIMes derivative is the easiest to activate and yields the most stable 14-electron intermediate. Finally calculations reveal a distinct influence of the nature of the N-heterocyclic carbene ligand on the position of the equilibrium of cis- and trans-dichloro isomers of the complexes. While the SIPr and the SIMes derivatives prefer the cis-configuration, all other derivatives favor, at least in solvents with low dielectric constants, the trans-configuration. These computational findings were supported by the isolation and full characterization of the cis-dichloro isomer of the SIMes-bearing preinitiator obtained upon heating of its trans-isomer at 140 °C.

  15. Role of surface functionality on the formation of raspberry-like polymer/silica composite particles: Weak acid–base interaction and steric effect

    International Nuclear Information System (INIS)

    Wang, Lan; Song, LinYong; Chao, ZhiYin; Chen, PengPeng; Nie, WangYan; Zhou, YiFeng

    2015-01-01

    Graphical abstract: - Highlights: • Core–shell structured polymer/SiO 2 was obtained with carboxylic-functionalized templates. • Raspberry-like structure was observed with carboxylic and poly(ethylene glycol) hybrid-functionalized polymer microspheres. • Carboxylic groups contributed to the nucleation and the poly(ethylene glycol) chains was used to control the growth of silica particles. • Super-hydrophobic surface was obtained and the contact angle of water on the dual-sized structured surface was up to 160°. - Abstract: The surface functionality of polymer microspheres is the crucial factor to determine the nucleation and growth of silica particles and to construct the organic/inorganic hierarchical structures. The objective of this work was to evaluate the surface functionality and hierarchical morphology relationship via in situ sol–gel reaction. Carboxylic-functionalized poly (styrene-co-maleic anhydride) [P(S-co-MA)], poly(ethylene glycol)-functionalized poly(styrene-co-poly(ethylene glycol) methacrylate) [P(S-co-PEGMA)], and hybrid functionalized poly(styrene-co-maleic anhydride-co-poly(ethylene glycol) methacrylate) [P(S-co-MA-co-PEGMA)] microspheres were synthesized by emulsifier-free polymerization and used as templates. The morphologies of the composite particles were observed by transmission electron microscopy (TEM) and scanning electron microscopy (SEM). The results showed that core–shell structure was obtained with P(S-co-MA) as templates; raspberry-like structure was observed by using P(S-co-MA-co-PEGMA) as templates; and no silica particles were attached onto the surface of P(S-co-PEGMA) microspheres. These results indicated that the carboxylic groups on the surface formed by hydrolysis of anhydride groups were the determinate factor to control the nucleation of silica nanoparticles, and the PEG chains on the surface can affect the growth of silica particles. In addition, the particulate films were constructed by assembling these composite particles on glass substrates and modified with dodecyltrichlorosilane, the contact angles of water on the dual-sized structured surface were up to 160°

  16. Effect of canopy structures and their steric interactions on CO2 sorption behavior of liquid-like nanoparticle organic hybrid materials

    KAUST Repository

    Park, Youngjune; Petit, Camille; Han, Patrick; Alissa Park, Ah-Hyung

    2014-01-01

    Liquid-like NOHMs with different grafting densities of polymeric canopy were synthesized to evaluate their solvating properties as CO2 solvents. The in situ ATR FT-IR study of NOHMs with linear and branched canopies revealed distinct CO2 capture and corresponding swelling behaviors. These observations suggested that the entropic contribution for CO2 sorption in NOHMs can be tuned via the canopy design. © The Royal Society of Chemistry.

  17. Variation of the Sterical Properties of the N-Heterocyclic Carbene Coligand in Thermally Triggerable Ruthenium-Based Olefin Metathesis Precatalysts/Initiators

    KAUST Repository

    Pump, Eva; Leitgeb, Anita; Kozłowska, Anna; Torvisco, Ana; Falivene, Laura; Cavallo, Luigi; Grela, Karol; Slugovc, Christian

    2015-01-01

    A series of ruthenium complexes based on the κ(C,N)-(2-(benzo[h]quinolin-10-yl)methylidene ruthenium dichloride fragment featuring different neutral coligands L (L = 1,3-bis(2,6-diisopropylphenyl)-4,5-dihydroimidazol-2-ylidene (SIPr), 1,3-bis(2

  18. Precise Steric Control over 2D versus 3D Self-Assembly of Antimony(III) Alkoxide Cages through Strong Secondary Bonding Interactions.

    Science.gov (United States)

    Moaven, Shiva; Yu, Jingze; Yasin, Jason; Unruh, Daniel K; Cozzolino, Anthony F

    2017-07-17

    Antimony(III) alkoxide cages were designed as building blocks for predictable supramolecular self-assembly. Supramolecular synthons featuring two Sb···O secondary bonding interactions (SBIs), each SBI stronger than 30 kJ/mol, were used to drive the formation of the supramolecular architectures. Judicious choice of pendant groups provided predictable control over the formation of self-assembled 3D columnar helices, which crystallized with hollow morphologies, or a self-assembled 2D bilayer. The Sb-O stretching frequency provides a spectroscopic signature of Sb···O SBI formation.

  19. Adjusting the DNA Interaction and Anticancer Activity of Pt(II) N-Heterocyclic Carbene Complexes by Steric Shielding of the Trans Leaving Group

    Czech Academy of Sciences Publication Activity Database

    Muenzner, J.K.; Rehm, T.; Biersack, B.; Casini, A.; de Graaf, I.; Worawutputtapong, P.; Noor, A.; Kempe, R.; Brabec, Viktor; Kašpárková, Jana; Schobert, R.

    2015-01-01

    Roč. 58, č. 15 (2015), s. 6283-6292 ISSN 0022-2623 R&D Projects: GA ČR(CZ) GA14-21053S Institutional support: RVO:68081707 Keywords : PLATINUM COMPLEXES * CANCER-CELLS * CISPLATIN Subject RIV: BO - Biophysics Impact factor: 5.589, year: 2015

  20. Steric Effects on the Binding of Phosphate and Polyphosphate Anions by Zinc(II) and Copper(II) Dinuclear Complexes of m-Xylyl-bis-cyclen.

    Science.gov (United States)

    Esteves, Catarina V; Esteban-Gómez, David; Platas-Iglesias, Carlos; Tripier, Raphaël; Delgado, Rita

    2018-05-11

    The triethylbenzene-bis-cyclen (cyclen = 1,4,7,10-tetraazacyclododecane) compound (tbmce) was designed with an imposed structural rigidity at the m-xylyl spacer to be compared to a less restrained and known parent compound (bmce). The framework of both compounds differs only in the substituents of the m-xylyl spacer. The study was centered in the differences observed in the acid-base reactions of both compounds, their copper(II) and zinc(II) complexation behaviors, as well as in the uptake of phosphate and polyphosphate anions (HPPi 3- , ATP 4- , ADP 3- , AMP 2- , PhPO 4 2- , and HPO 4 2- ). On the one hand, the acid-base reactions showed lower values for the third and fourth protonation constants of tbmce than for bmce, suggesting that the ethyl groups of the spacer in tbmce force the two cyclen units to more conformational restricted positions. On the other hand, the stability constant values for copper(II) and zinc(II) complexes revealed that bmce is a better chelator than tbmce pointing out to additional conformational restraints imposed by the triethylbenzene spacer. The binding studies of phosphates by the dinuclear copper(II) and zinc(II) complexes showed much smaller effective association constants for the dicopper complexes. Single-crystal X-ray and computational (density functional theory) studies suggest that anion binding promotes the formation of tetranuclear entities in which anions are bridging the metal centers. Our studies also revealed the dinuclear zinc(II) complex of bmce as a promising receptor for phosphate anions, with the largest effective association constant of 5.94 log units being observed for the formation of [Zn 2 bmce(HPPi)] + . Accordingly, a colorimetric study via an indicator displacement assay to detect phosphates in aqueous solution found that the [Zn 2 bmce] 4+ complex acts as the best receptor for pyrophosphate displaying a detection limit of 2.5 nM by changes visible to naked eye.