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)

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.

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.

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

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

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

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.)

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,O

Metallacyclobutane substitution and its effect on alkene metathesis for propylene production over W-H/Al2O3: Case of isobutene/2-butene cross-metathesis

KAUST Repository

Szeto, Kaï Chung; Mazoyer, Etienne; Merle, Nicolas; Norsic, Sé bastien; Basset, Jean-Marie; Nicholas, Christopher P.; Taoufik, Mostafa

2013-01-01

Cross metathesis between 2-butenes and isobutene yielding the valuable products propylene and 2-methyl-2-butene has been investigated at low pressure and temperature using WH3/Al2O3, a highly active and selective catalyst. Two parallel catalytic cycles for this reaction have been proposed where the cycle involving the less sterically hindered tungstacyclobutane intermediates is most likely favored. Moreover, it has been found that the arrangement of substituents on the least thermodynamically favored tungstacyclobutane governs the conversion rate of the cross metathesis reaction for propylene production from butenes and/or ethylene. © 2013 American Chemical Society.

Metallacyclobutane substitution and its effect on alkene metathesis for propylene production over W-H/Al2O3: Case of isobutene/2-butene cross-metathesis

KAUST Repository

Szeto, Kaï Chung

2013-09-06

Cross metathesis between 2-butenes and isobutene yielding the valuable products propylene and 2-methyl-2-butene has been investigated at low pressure and temperature using WH3/Al2O3, a highly active and selective catalyst. Two parallel catalytic cycles for this reaction have been proposed where the cycle involving the less sterically hindered tungstacyclobutane intermediates is most likely favored. Moreover, it has been found that the arrangement of substituents on the least thermodynamically favored tungstacyclobutane governs the conversion rate of the cross metathesis reaction for propylene production from butenes and/or ethylene. © 2013 American Chemical Society.

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.

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)

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)

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°.

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

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.

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

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.

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.

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.

Cp*Co(III) Catalyzed Site-Selective C-H Activation of Unsymmetrical O-Acyl Oximes: Synthesis of Multisubstituted Isoquinolines from Terminal and Internal Alkynes.

Science.gov (United States)

Sun, Bo; Yoshino, Tatsuhiko; Kanai, Motomu; Matsunaga, Shigeki

2015-10-26

The synthesis of isoquinolines by site-selective C-H activation of O-acyl oximes with a Cp*Co(III) catalyst is described. In the presence of this catalyst, the C-H activation of various unsymmetrically substituted O-acyl oximes selectively occurred at the sterically less hindered site, and reactions with terminal as well as internal alkynes afforded the corresponding products in up to 98 % yield. Whereas the reactions catalyzed by the Cp*Co(III) system proceeded with high site selectivity (15:1 to 20:1), use of the corresponding Cp*Rh(III) catalysts led to low selectivities and/or yields when unsymmetrical O-acyl oximes and terminal alkynes were used. Deuterium labeling studies indicate a clear difference in the site selectivity of the C-H activation step under Cp*Co(III) and Cp*Rh(III) catalysis. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

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.

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.

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.

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

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.

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.

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.

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."

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.

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.

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

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.

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.

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

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.

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.

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.

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.

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

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

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

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

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.

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.

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.

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.

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

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.

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…

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…

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.

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.

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...

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

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.

Factors Motivating and Hindering Information and Communication Technologies Action Competence

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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

Di-tert-butyl 2,2′-(biphenyl-2,2′-diyldioxydiacetate

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Qamar Ali

2008-08-01

Full Text Available The title compound, C24H30O6, does not exhibit π–π interactions due to the steric effect of the bulky tert-butyl groups present in the molecule. The presence of these groups at the 2 and 2′ positions hinders the free motion of the benzene rings relative to each other, causing them to adopt an antiperiplanar arrangement. The benzene rings are twisted by just under 50.96 (17° with respect to each other. The carbonyl groups within the molecule are directed in different directions, one towards the biphenyl group and the other away from it. The molecules are linked together by C=O...H—C hydrogen bonds.

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.

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.

Nanoparticle dispersion in environmentally relevant culture media: a TiO2 case study and considerations for a general approach

International Nuclear Information System (INIS)

Horst, Allison M.; Ji, Zhaoxia; Holden, Patricia A.

2012-01-01

Nanoparticle exposure in toxicity studies requires that nanoparticles are bioavailable by remaining highly dispersed in culture media. However, reported dispersion approaches are variable, mostly study-specific, and not transferable owing to their empirical basis. Furthermore, many published approaches employ proteinaceous dispersants in rich laboratory media, both of which represent end members in environmental scenarios. Here, a systematic approach was developed to disperse initially agglomerated TiO 2 nanoparticles (Aeroxide® TiO 2 P25, Evonik, NJ; primary particle size range 6.4–73.8 nm) in oligotrophic culture medium for environmentally relevant bacterial toxicity studies. Based on understanding particle–particle interactions in aqueous media and maintaining environmental relevance, the approach involves (1) quantifying the relationship between pH and zeta potential to determine the point of zero charge of select nanoparticles in water; (2) nominating, then testing and selecting, environmentally relevant stabilizing agents; and (3) dispersing via “condition and capture” whereby stock dry powder nanoparticles are sonicated in pre-conditioned (with base, or acid, plus stabilizing agent) water, then diluted into culture media. The “condition and capture” principle is transferable to other nanoparticle and media chemistries: simultaneously, mechanically and electrostatically, nanoparticles can be dispersed with surrounding stabilizers that coat and sterically hinder reagglomeration in the culture medium.

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

Teamwork in a coronary care unit: facilitating and hindering aspects

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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.

Targeted Sterically Stabilized Phospholipid siRNA Nanomedicine for Hepatic and Renal Fibrosis

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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.

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 ...

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.

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.

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

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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

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.

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...

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.

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.

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.

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.

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

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

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.

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...

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....

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.

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.

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...

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.

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

The structure and dynamics of the Fe-CO bond in myoglobin

International Nuclear Information System (INIS)

Rovira, Carme

2003-01-01

This paper is a review of our recent work on the structure and dynamics of the Fe-CO bond in carbonmonoxy myoglobin (MbCO), performed using density functional theory, Car-Parrinello molecular dynamics and hybrid quantum mechanics/molecular mechanics approaches. The results of these investigations have served to shed light onto one of the long standing questions in myoglobin research: whether the protein discriminates the CO ligand with respect to O 2 by distorting the FeCO bond. The calculations show that both in the gas phase and in the protein the Fe-CO bond is essentially linear and therefore exclude the hypothesis that the CO in MbCO is sterically hindered. In contrast, hydrogen bonding between the O 2 ligand and the His64 residue easily explains the protein discrimination for CO

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

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.

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

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 ...

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

Matrix Isolation Spectroscopy of H2O2, D2O, and HDO in Solid Parahydrogen

National Research Council Canada - National Science Library

Fajardo, Mario

2003-01-01

...) solids doped with H2O, D2O and HDO molecules. Analysis of the rovibrational spectra of the isolated H20, D2O and HDO monomers reveals their existence as very slightly hindered rotors, typically showing only 2 to 5...

Electronic-state-driven adsorption of O2 on a nanocrystalline TiO2 under 'dark' and UV-irradiation conditions: Ab initio study

Science.gov (United States)

Kevorkyants, R.; Sboev, M. N.; Chizhov, Yu. V.

2018-04-01

DFT study on O2 adsorption on a nanocrystalline titania is presented for the first time. The dioxide's nanoparticle is modeled via the nanocluster Ti8O16. According to the calculations, O2 physisorbs on the nanocluster Ti8O16 in S0 and T0 states and chemisorbs on the nanocluster in S1 state. The computed adsorption enthalpies, O2 vibrational frequencies, and O2-g-tensor agree well with available data. In contrast to the axial O2 orientation on a surface of titania with oxygen vacancies, in the chemisorption complex O2 is oriented laterally. We explain this by the sterical hindrance of the Ti3+ centers in the former case.

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.

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.

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.

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...

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.

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

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

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.

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.

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

Full Text Available O enfermeiro depara-se com fatores que favorecem e dificultam a realização do seu trabalho e que interferem nos sentimentos em relação ao trabalho. Este estudo é do tipo exploratório-descritivo, com abordagem qualitativa. Teve como objetivos caracterizar sociodemograficamente os enfermeiros dos Serviços de Atenção à Saúde de um município do Estado do Rio Grande do Sul e identificar os fatores que favorecem e dificultam a realização do trabalho. Os dados foram coletados de março a julho de 2007 por meio de um questionário. A amostra foi composta por 24 enfermeiros. A análise dos dados possibilitou construir dois eixos temáticos: fatores que favorecem e que dificultam a realização do trabalho do enfermeiro. Os resultados sugerem que os enfermeiros percebem satisfação no trabalho. No entanto, é necessário repensar o processo de trabalho desse profissional para fortalecer as ações perante o usuário do Sistema Único de Saúde e buscar resolutividade diante das necessidades da comunidade.RESUMEN El enfermero se depara con factores que favorecen y dificultan la realización de sus actividades laborales y que interfieren en los sentimientos relacionados al trabajo. Este estudio es de tipo exploratorio-descriptivo, con un abordaje cualitativo. Sus objetivos fueron caracterizar socio-demográficamente los enfermeros de los Servicios de Atención a la Salud de una ciudad de la provincia de Rio Grande do Sul e identificar los factores que favorecen y dificultan la realización del trabajo. La recolección de los datos se hizo de marzo hasta julio de 2007, por medio de un cuestionario. Compusieron la muestra 24 enfermeros. El análisis de los datos posibilitó construir ejes temáticos: factores que favorecen y que dificultan la realización del trabajo del enfermero. Los resultados indican que los enfermeros perciben la satisfacción en el trabajo. Sin embargo, es necesario repensar el proceso de trabajo de ese profesional para

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.

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.

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...

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...

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.

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…

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

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).

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.

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.

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%.

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.

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.

Effect of silver on the phase transition and wettability of titanium oxide films

Science.gov (United States)

Mosquera, Adolfo A.; Albella, Jose M.; Navarro, Violeta; Bhattacharyya, Debabrata; Endrino, Jose L.

2016-01-01

The effect of silver on the phase transition and microstructure of titanium oxide films grown by pulsed cathodic arc had been investigated by XRD, SEM and Raman spectroscopy. Following successive thermal annealing up to 1000 °C, microstructural analysis of annealed Ag-TiO2 films reveals that the incorporation of Ag nanoparticles strongly affects the transition temperature from the initial metastable amorphous phase to anatase and stable rutile phase. An increase of silver content into TiO2 matrix inhibits the amorphous to anatase phase transition, raising its temperature boundary and, simultaneously reduces the transition temperature to promote rutile structure at lower value of 600 °C. The results are interpreted in terms of the steric effects produced by agglomeration of Ag atoms into larger clusters following annealing which hinders diffusion of Ti and O ions for anatase formation and constrains the volume available for the anatase lattice, thus disrupting its structure to form rutile phase. The effect of silver on the optical and wetting properties of TiO2 was evaluated to demonstrate its improved photocatalytic performance. PMID:27571937

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.

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.

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

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

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.

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.

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.

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.

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

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.

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.

o-Iminobenzosemiquinonate and o-imino-p-methylbenzosemiquinonate anion radicals coupled VO2+ stabilization.

Science.gov (United States)

Roy, Amit Saha; Saha, Pinaki; Adhikary, Nirmal Das; Ghosh, Prasanta

2011-03-21

complexes are unstable with respect to triplet perturbations. But BS (1,1) M(s) = 0 (VO(2+)-iminobenzosemiquinonate anion radical (L(R)(IS)(•-)) coordination) solutions of these species are stable and reproduce the experimental bond parameters well. Spin density distributions of one electron oxidized cations are consistent with the [(L(-))(VO(2+))(L(R)(IQ))](+) descriptions [VO(2+)-o-iminobenzoquinone (L(R)(IQ)) coordination], and one electron reduced anions are consistent with the [(L(•2-))(VO(3+))(L(R)(AP)(2-))](-) descriptions [VO(3+)-amidophenolato (L(R)(AP)(2-)) coordination], incorporating the diimine anion radical (L(1)(•2-)) or azo anion radical (L(2)(3-)). Although, cations and anions are not isolable, but electro-and spectro-electrochemical experiments have shown that 3(+) and 3(-) ions are more stable than 1(+), 2(+) and 1(-), 2(-) ions. In all cases, the reductions occur with simultaneous two electron transfer, may be due to formation of coupled diimine/azo anion radical-VO(2+) species as in [(L(•2-))(VO(2+))(L(R)(AP)(2-))](2-).

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.

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.

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.

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.

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.

Enhanced stability and dissolution of CuO nanoparticles by extracellular polymeric substances in aqueous environment

International Nuclear Information System (INIS)

Miao, Lingzhan; Wang, Chao; Hou, Jun; Wang, Peifang; Ao, Yanhui; Li, Yi; Lv, Bowen; Yang, Yangyang; You, Guoxiang; Xu, Yi

2015-01-01

Stability of engineered nanoparticles in aquatic environment is an essential parameter to evaluate their fate, bioavailability, and potential toxic effects toward living organisms. As CuO NPs enter the wastewater systems, they will encounter extracellular polymeric substances (EPS) from microbial community before directly interacting with bacterial cells. EPS may play an important role in affecting the stability and the toxicity of CuO NPs in aquatic environment. In this study, the influences of flocculent sludge-derived EPS, as well as model protein (BSA) and natural polysaccharides (alginate) on the dissolution kinetics and colloidal stability of CuO NPs were investigated. Results showed that the presence of NOMs strongly suppressed CuO NPs aggregation, confirmed by DLS, zeta potentials, and TEM analysis. The enhanced stability of CuO NPs in the presence of EPS and alginate were attributed to the electrostatic combined with steric repulsion, while the steric-hindrance effect may be the predominant mechanism retarding nano-CuO aggregation for BSA. Higher degrees of copper release were achieved with the increasing concentrations of NOMs. EPS are more effective than alginate and BSA in releasing copper, probably due to the abundant functional groups and the excellent metal-binding capacity. The ratio of free-Cu 2+ /total dissolved Cu significantly decreased in the presence of EPS, indicating that EPS may affect the speciation and Cu bioavailability in aqueous environment. These results may be important for assessing the fate and transport behaviors of CuO NPs in the environment as well as for setting up usage regulation and treatment strategy.

Enhanced stability and dissolution of CuO nanoparticles by extracellular polymeric substances in aqueous environment

Energy Technology Data Exchange (ETDEWEB)

Miao, Lingzhan; Wang, Chao; Hou, Jun, E-mail: hhuhjyhj@126.com; Wang, Peifang; Ao, Yanhui; Li, Yi; Lv, Bowen; Yang, Yangyang; You, Guoxiang; Xu, Yi [Hohai University, Key Laboratory of Integrated Regulation and Resources Development on Shallow Lakes, Ministry of Education (China)

2015-10-15

Stability of engineered nanoparticles in aquatic environment is an essential parameter to evaluate their fate, bioavailability, and potential toxic effects toward living organisms. As CuO NPs enter the wastewater systems, they will encounter extracellular polymeric substances (EPS) from microbial community before directly interacting with bacterial cells. EPS may play an important role in affecting the stability and the toxicity of CuO NPs in aquatic environment. In this study, the influences of flocculent sludge-derived EPS, as well as model protein (BSA) and natural polysaccharides (alginate) on the dissolution kinetics and colloidal stability of CuO NPs were investigated. Results showed that the presence of NOMs strongly suppressed CuO NPs aggregation, confirmed by DLS, zeta potentials, and TEM analysis. The enhanced stability of CuO NPs in the presence of EPS and alginate were attributed to the electrostatic combined with steric repulsion, while the steric-hindrance effect may be the predominant mechanism retarding nano-CuO aggregation for BSA. Higher degrees of copper release were achieved with the increasing concentrations of NOMs. EPS are more effective than alginate and BSA in releasing copper, probably due to the abundant functional groups and the excellent metal-binding capacity. The ratio of free-Cu{sup 2+}/total dissolved Cu significantly decreased in the presence of EPS, indicating that EPS may affect the speciation and Cu bioavailability in aqueous environment. These results may be important for assessing the fate and transport behaviors of CuO NPs in the environment as well as for setting up usage regulation and treatment strategy.

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.

Solution 1H NMR investigation of the active site molecular and electronic structures of substrate-bound, cyanide-inhibited HmuO, a bacterial heme oxygenase from Corynebacterium diphtheriae.

Science.gov (United States)

Li, Yiming; Syvitski, Ray T; Chu, Grace C; Ikeda-Saito, Masao; Mar, Gerd N La

2003-02-28

The molecular structure and dynamic properties of the active site environment of HmuO, a heme oxygenase (HO) from the pathogenic bacterium Corynebacterium diphtheriae, have been investigated by (1)H NMR spectroscopy using the human HO (hHO) complex as a homology model. It is demonstrated that not only the spatial contacts among residues and between residues and heme, but the magnetic axes that can be related to the direction and magnitude of the steric tilt of the FeCN unit are strongly conserved in the two HO complexes. The results indicate that very similar contributions of steric blockage of several meso positions and steric tilt of the attacking ligand are operative. A distal H-bond network that involves numerous very strong H-bonds and immobilized water molecules is identified in HmuO that is analogous to that previously identified in hHO (Li, Y., Syvitski, R. T., Auclair, K., Wilks, A., Ortiz de Montellano, P. R., and La Mar, G. N. (2002) J. Biol. Chem. 277, 33018-33031). The NMR results are completely consistent with the very recent crystal structure of the HmuO.substrate complex. The H-bond network/ordered water molecules are proposed to orient the distal water molecule near the catalytically key Asp(136) (Asp(140) in hHO) that stabilizes the hydroperoxy intermediate. The dynamic stability of this H-bond network in HmuO is significantly greater than in hHO and may account for the slower catalytic rate in bacterial HO compared with mammalian HO.

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.

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…

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...

Enhanced antifouling behaviours of polyvinylidene fluoride membrane modified through blending with nano-TiO2/polyethylene glycol mixture

International Nuclear Information System (INIS)

Zhang, Jie; Wang, Zhiwei; Zhang, Xingran; Zheng, Xiang; Wu, Zhichao

2015-01-01

Graphical abstract: - Highlights: • Nano-TiO 2 /polyethylene glycol (PEG) mixture was used to modify PVDF membranes. • The steric hindrance effects of PEG enabled the dispersion of nanoparticles. • The energy barrier between SMP and modified membranes was increased. • The modification by nano-TiO 2 /PEG well improved the anti-fouling ability. - Abstract: Titanium dioxide (TiO 2 ) nanoparticles/polyethylene glycol (PEG) mixture was used to modify polyvinylidene fluoride (PVDF) membranes aiming to improve their antifouling ability. The use of PEG could improve the dispersion of nanoparticles thanks to steric hindrance effects. Test results showed that compared to the original PVDF membrane, the modified membranes had higher hydrophilicity and lower negative Zeta potential, facilitating membrane fouling control. The extended Derjaguin-Landau-Verwey-Overbeek (XDLVO) analysis indicated that the addition of TiO 2 nanoparticles improved their electron donor monopolarity, i.e., enhanced electron-donating ability. The interaction energy barrier between soluble microbial products (SMP) and membrane surfaces was also improved, indicating that anti-fouling ability of the modified membrane was elevated. The optimal dosage of nano-TiO 2 was found to be 0.15%, and further increase of dosage resulted in the aggregation of nanoparticles which consequently impaired the modification efficiency. Quartz crystal microbalance with dissipation (QCM-D) monitoring and SMP filtration tests confirmed the antifouling ability of the modified membrane

Enhanced antifouling behaviours of polyvinylidene fluoride membrane modified through blending with nano-TiO{sub 2}/polyethylene glycol mixture

Energy Technology Data Exchange (ETDEWEB)

Zhang, Jie [State Key Laboratory of Pollution Control and Resource Reuse, School of Environmental Science and Engineering, Tongji University, Shanghai, 200092 (China); Wang, Zhiwei, E-mail: zwwang@tongji.edu.cn [State Key Laboratory of Pollution Control and Resource Reuse, School of Environmental Science and Engineering, Tongji University, Shanghai, 200092 (China); Zhang, Xingran [State Key Laboratory of Pollution Control and Resource Reuse, School of Environmental Science and Engineering, Tongji University, Shanghai, 200092 (China); Zheng, Xiang, E-mail: zhengxiang7825@163.com [School of Environment and Natural Resources, Renmin University of China, Beijing, 100872 (China); Wu, Zhichao [State Key Laboratory of Pollution Control and Resource Reuse, School of Environmental Science and Engineering, Tongji University, Shanghai, 200092 (China)

2015-08-01

Graphical abstract: - Highlights: • Nano-TiO{sub 2}/polyethylene glycol (PEG) mixture was used to modify PVDF membranes. • The steric hindrance effects of PEG enabled the dispersion of nanoparticles. • The energy barrier between SMP and modified membranes was increased. • The modification by nano-TiO{sub 2}/PEG well improved the anti-fouling ability. - Abstract: Titanium dioxide (TiO{sub 2}) nanoparticles/polyethylene glycol (PEG) mixture was used to modify polyvinylidene fluoride (PVDF) membranes aiming to improve their antifouling ability. The use of PEG could improve the dispersion of nanoparticles thanks to steric hindrance effects. Test results showed that compared to the original PVDF membrane, the modified membranes had higher hydrophilicity and lower negative Zeta potential, facilitating membrane fouling control. The extended Derjaguin-Landau-Verwey-Overbeek (XDLVO) analysis indicated that the addition of TiO{sub 2} nanoparticles improved their electron donor monopolarity, i.e., enhanced electron-donating ability. The interaction energy barrier between soluble microbial products (SMP) and membrane surfaces was also improved, indicating that anti-fouling ability of the modified membrane was elevated. The optimal dosage of nano-TiO{sub 2} was found to be 0.15%, and further increase of dosage resulted in the aggregation of nanoparticles which consequently impaired the modification efficiency. Quartz crystal microbalance with dissipation (QCM-D) monitoring and SMP filtration tests confirmed the antifouling ability of the modified membrane.

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.

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.

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

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.

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

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

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.

HRTEM analysis on nanocrystalline BaTiO3 and PbTiO3: size effects on ferroelectric phase transition temperature

International Nuclear Information System (INIS)

Bursill, L.A.; Jiang, B.; Peng, J.L.; Zhong, W.L.; Zhang, P.L.

1997-01-01

High-Resolution Transmission Electron Microscopic studies of nanocrystaline particles of BaTiO 3 and PbTiO 3 are reported. There are characteristic differences observed for BaTiO 3 prepared using sol gel (SG) and steric acid gel (SAG) methods. The former exhibit a critical size below which there is no paraelectric/ferroelectric phase transition, whereas BaTiO 3 prepared via the SAG route remained cubic for all conditions. The SAG preparations always showed chemical intergrowth defects whereas the SG preparations were single phase. Atomic resolution images of both varieties showed interesting surface steps and surface relaxations/reconstructions of some facets. Nanocrystalline PbTiO 3 prepared by the SG route remains tetragonal, albeit with decreasing c/a ratio, down to 25nm diameter. HRTEM observations of nanocrystalline PbTiO 3 are also presented. X-ray diffraction, dielectric and Raman scattering measurements also demonstrate pronounced size effects. The relationship between the observed nanostructures and size effects on the physical properties is discussed. 6 refs., 1 tab., 6 figs

Effects of glycosylation on the conformation and dynamics of O-linked glycoproteins: Carbon-13 NMR studies of ovine submaxillary mucin

International Nuclear Information System (INIS)

Gerken, T.A.; Butenhof, K.J.; Shogren, R.

1989-01-01

Carbon-13 NMR spectroscopic studies of native and sequentially deglycosylated ovine submaxillary mucin (OSM) have been performed to examine the effects of glycosylation on the conformation and dynamics of the peptide core of O-linked glycoproteins. OSM is a large nonglobular glycoprotein in which nearly one-third of the amino acid residues are Ser and Thr which are glycosylated by the α-Neu-NAc(2-6)α-Ga1NAc- disaccharide. The β-carbon resonances of glycosylated Ser and Thr residues in intact and asialo mucin display considerable chemical shift heterogeneity which, upon the complete removal of carbohydrate, coalesces to single sharp resonances. This chemical shift heterogeneity is due to peptide sequence variability and is proposed to reflect the presence of sequence-dependent conformations of the peptide core. These different conformations are thought to be determined by steric interactions of the Ga1NAc residue with adjacent peptide residues. The absence of chemical shift heterogeneity in apo mucin is taken to indicate a loss in the peptide-carbohydrate steric interactions, consistent with a more relaxed random coiled structure. On the basis of the 13 C relaxation behavior the dynamics of the α-carbons appear to be unique to each amino acid type and glycosylation state. These results are consistent with the changes in molecular dimensions determined by light-scattering techniques for the same series of modified mucins. Taken together, these results further demonstrate that mucins possess a highly expanded conformation that is dominated by steric interactions between the peptide core and the O-linked Ga1NAc residue

Computational Replication of the Primary Isotope Dependence of Secondary Kinetic Isotope Effects in Solution Hydride-Transfer Reactions: Supporting the Isotopically Different Tunneling Ready State Conformations.

Science.gov (United States)

Derakhshani-Molayousefi, Mortaza; Kashefolgheta, Sadra; Eilers, James E; Lu, Yun

2016-06-30

We recently reported a study of the steric effect on the 1° isotope dependence of 2° KIEs for several hydride-transfer reactions in solution (J. Am. Chem. Soc. 2015, 137, 6653). The unusual 2° KIEs decrease as the 1° isotope changes from H to D, and more in the sterically hindered systems. These were explained in terms of a more crowded tunneling ready state (TRS) conformation in D-tunneling, which has a shorter donor-acceptor distance (DAD) than in H-tunneling. To examine the isotopic DAD difference explanation, in this paper, following an activated motion-assisted H-tunneling model that requires a shorter DAD in a heavier isotope transfer process, we computed the 2° KIEs at various H/D positions at different DADs (2.9 Å to 3.5 Å) for the hydride-transfer reactions from 2-propanol to the xanthylium and thioxanthylium ions (Xn(+) and TXn(+)) and their 9-phenyl substituted derivatives (Ph(T)Xn(+)). The calculated 2° KIEs match the experiments and the calculated DAD effect on the 2° KIEs fits the observed 1° isotope effect on the 2° KIEs. These support the motion-assisted H-tunneling model and the isotopically different TRS conformations. Furthermore, it was found that the TRS of the sterically hindered Ph(T)Xn(+) system does not possess a longer DAD than that of the (T)Xn(+) system. This predicts a no larger 1° KIE in the former system than in the latter. The observed 1° KIE order is, however, contrary to the prediction. This implicates the stronger DAD-compression vibrations coupled to the bulky Ph(T)Xn(+) reaction coordinate.

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

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.

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. ...

A Novel MgO-CaO-SiO2 System for Fabricating Bone Scaffolds with Improved Overall Performance

Directory of Open Access Journals (Sweden)

Hang Sun

2016-04-01

Full Text Available Although forsterite (Mg2SiO4 possesses good biocompatibility and suitable mechanical properties, the insufficient bioactivity and degradability hinders its further application. In this study, a novel MgO-CaO-SiO2 system was developed by adding wollastonite (CaSiO3 into Mg2SiO4 to fabricate bone scaffolds via selective laser sintering (SLS. The apatite-forming ability and degradability of the scaffolds were enhanced because the degradation of CaSiO3 could form silanol groups, which could offer nucleation sites for apatite. Meanwhile, the mechanical properties of the scaffolds grew with increasing CaSiO3 to 20 wt %. It was explained that the liquid phase of CaSiO3 promoted the densification during sintering due to its low melting point. With the further increase in CaSiO3, the mechanical properties decreased due to the formation of the continuous filling phase. Furthermore, the scaffolds possessed a well-interconnected porous structure and exhibited an ability to support cell adhesion and proliferation.

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…

Interaction of actinide ions with [NaP5W30O110]14- and [P2W18O62]6-

International Nuclear Information System (INIS)

Choppin, G.R.; Wall, D.E.

2003-01-01

Stability constants (log β 101 ) of Th 4+ , UO 2 2+ , NpO 2 + and Am 3+ with [NaP 5 W 30 O 110 ] 14- were determined by solvent extraction (μ = 0.1M NaCl) and found to be 6.18 ± 0.07, 3.80 ± 0.06, 2.98 ± 0.04, and 5.85 ± 0.05, respectively. The order of stability constants: Th 4+ > Am 3+ > UO 2 2+ > NpO 2 + is due to electrostatic repulsion between the actinyl oxygens and oxygens on the polyoxometalate surface. The order of stability constants for metal complexes with [P 2 W 18 O 62 ] 6- is Th 4+ > UO 2 2+ > Eu 3+ >NpO 2 + because the steric repulsion between actinyl oxygens and oxygens on polyoxometalate are less important. Enthalpies of complexation were measured by calorimetric titration of Th 4+ , UO 2 2+ , Nd 3+ with [NaP 5 W 30 O 110 ] 14- and [P 2 W 18 O 62 ] 6- . The results indicate that the conformation and charge distribution of the microscopic surface structures are important factors in the formation of pseudocolloids. (author)

Aqueous suspensions of {alpha}Al{sub 2}O{sub 3}/SiC mixed systems

Energy Technology Data Exchange (ETDEWEB)

Pagnoux, C.; Baklouti, S.; Chartier, T.; Baumard, J.F. [ENSCI, Limoges (France). LMCTS

1997-12-31

The preparation of aqueous {alpha}-Al{sub 2}O{sub 3}, {alpha}-SiO{sub 2} and {alpha}-SiC suspensions with polyelectrolytes, respectively the NH{sub 4}{sup +} salt of polymethacrylic acid (PMA-NH{sub 4}{sup +}) and acidic form polyethylene imine (PEI-H{sup +}) is investigated. It is based on the adsorption of these polyelectrolytes which in turn depends mainly on the nature of the polyelectrolyte, and the charge density which develops on the powder surface in water. Good dispersion and stability of dispersions are then obtained through electrostatic and steric stabilization. As an application, the preparation of an Al{sub 2}O{sub 3}-SiC aqueous mixed slurry was investigated as a preliminary step for processing of Al{sub 2}O{sub 3}/SiC nanocomposites. (orig.) 2 refs.

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.

The pH dependency of N-converting enzymatic processes, pathways and microbes: effect on net N₂O production

DEFF Research Database (Denmark)

Blum, Jan-Michael; Su, Qingxian; Ma, Yunjie

2018-01-01

causing steric changes in catalytic sites or proton/electron transfer routes that alter the enzymes' overall activity. Augmenting molecular information with, e.g., nitritation or denitrification rates yields explanations of changes in net N2 O production with pH. Ammonia oxidizing bacteria are of highest...... relevance for N2 O production, while heterotrophic denitrifiers are relevant for N2 O consumption at pH > 7.5. Net N2 O production in N-cycling water engineering systems is predicted to display a 'bell-shaped' curve in the range of pH 6.0-9.0 with a maximum at pH 7.0-7.5. Net N2 O production at acidic p...

Bond length effects during the dissociation of O2 on Ni(1 1 1)

International Nuclear Information System (INIS)

Shuttleworth, I.G.

2015-01-01

Graphical abstract: - Highlights: • The dissociation of O 2 on Ni(1 1 1) has been investigated using the Nudged Elastic Band (NEB) technique. • An exceptional correlation has been identified between the O/Ni bond order and the O 2 bond length for a series of sterically different reaction paths. • Direct magnetic phenomena accompany these processes suggesting further mechanisms for experimental control. - Abstract: The interaction between O 2 and Ni(1 1 1) has been investigated using spin-polarised density functional theory. A series of low activation energy (E A = 103–315 meV) reaction pathways corresponding to precursor and non-precursor mediated adsorption have been identified. It has been seen that a predominantly pathway-independent correlation exists between O−Ni bond order and the O 2 bond length. This correlation demonstrates that the O−O interaction predominantly determines the bonding of this system

survey of operators kn and maintenance o in ebonyi st vey

African Journals Online (AJOL)

eobe

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ZnO nanowires: Synthesis and charge transfer mechanism in the detection of ammonia vapour

Science.gov (United States)

Nancy Anna Anasthasiya, A.; Ramya, S.; Rai, P. K.; Jeyaprakash, B. G.

2018-01-01

ZnO nanowires with hexagonal wurtzite structure were grown on the glass substrate using Successive Ionic Layer Adsorption and Reaction (SILAR) method. Both experimental and theoretical studies demonstrated that NH3 chemisorbed and transferred the charge to the surface of the nanowire via its nitrogen site to the zinc site of ZnO nanowires, leading to the detection of NH3 vapour. The adsorbed ammonia dissociated into NH2 and H due to steric repulsion, and then into N2 and H2 gas. The formation of the N2 gas during the desorption process confirmed by observing peak at 14 and 28 m/z in the GC-MS spectrum.

Platinum(II Complexes with Tetradentate Schiff Bases as Ligands: Synthesis, Characterization and Detection of DNA Interaction by Differential Pulse Voltammetry

Directory of Open Access Journals (Sweden)

Lijun Li

2012-01-01

Full Text Available Five sterically hindered platinum(II complexes with tetradentate schiff bases as ligands, [Pt(L] (L= N,N′-bisalicylidene-1,2-ethylenediamine (L1, N,N′-bisalicylidene-1,2-cyclohexanediamine (L2, N,N′-bis(5-hydroxyl-salicylidene-1,2-cyclohexanediamine (L3, N,N′-bisalicylidene-1,2-diphenyl-ethylenediamine (L4 and N,N′-bis(3-tert-butyl-5-methyl-salicylidene-1,2-diphenylethylenediamine (L5 have been synthesized and characterized by IR spectroscopy and elemental analysis. The sterical hindrance of antitumor drug candidates potentially makes them less susceptible to deactivation by sulphur containing proteins and helping to overcome resistance mechanisms. The interaction of these metal complexes with fish sperm single-stranded DNA (ssDNA was studied electrochemically based on the oxidation signals of guanine and adenine. Differential pulse voltammetry was employed to monitor the DNA interaction in solution by using renewable pencil graphite electrode. The results indicate that ligands with different groups can strongly affect the interaction between [Pt(L] complexes and ssDNA due to sterical hindrances and complex [Pt(L1] has the best interaction with DNA among the five complexes.

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

Full Text Available OBJETIVO: Desvelar a percepção dos profissionais que atuam em Organizações de Procura de Órgãos sobre os fatores que facilitam e dificultam a entrevista familiar no processo de doação de órgãos e tecidos para transplante. MÉTODOS: Trata-se de pesquisa qualitativa, na vertente fenomenológica, modalidade "estrutura do fenômeno situado". Participaram do estudo 18 profissionais que atuavam em Organizações de Procura de Órgãos. RESULTADOS: Após a análise das entrevistas, foram revelados os fatores que facilitam e dificultam a entrevista familiar. CONCLUSÃO: As proposições que emergiram, revelaram que os fatores que facilitam e dificultam a entrevista familiar estão relacionados ao local da entrevista, à assistência prestada ao potencial doador e aos familiares, aos esclarecimentos fornecidos à família e a manifestação do potencial doador em vida sobre a decisão quanto à doação de órgãos.OBJETIVO: Develar la percepción de los profesionales que actúan en Organizaciones de Búsqueda de Órganos sobre los factores que facilitan y dificultan la entrevista familiar en el proceso de donación de órganos y tejidos para transplante. MÉTODOS: Se trata de una investigación cualitativa, en la vertiente fenomenológica, modalidad "estructura del fenómeno situado". Participaron en el estudio 18 profesionales que actuaban en Organizaciones de Búsqueda de Órganos. RESULTADOS: Después del análisis de las entrevistas, fueron revelados los factores que facilitan y dificultan la entrevista familiar. CONCLUSIÓN: Las proposiciones que emergieron, revelaron que los factores que facilitan y dificultan la entrevista familiar están relacionados al local de la entrevista, a la asistencia prestada al donador en potencia y a los familiares, a las aclaraciones dadas a la familia y la manifestación del potencial donador, en vida, sobre su decisión respecto a la donación de órganos.OBJECTIVE: To unveil the perceptions of

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…

Social prejudice hindering proper use of car safety seats.

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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.

First-principles study of (Ba ,Ca ) TiO3 and Ba (Ti ,Zr ) O3 solid solutions

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Amoroso, Danila; Cano, Andrés; Ghosez, Philippe

2018-05-01

(Ba ,Ca ) TiO3 and Ba (Ti ,Zr ) O3 solid solutions are the building blocks of lead-free piezoelectric materials that attract a renewed interest. We investigate the properties of these systems by means of first-principles calculations, with a focus on the lattice dynamics and the competition between different ferroelectric phases. We first analyze the four parent compounds in order to compare their properties and their different tendency towards ferroelectricity. The core of our study is systematic characterization of the binary systems (Ba ,Ca ) TiO3 and Ba (Ti ,Zr ) O3 within both the virtual crystal approximation and direct supercell calculations. In the case of Ca doping, we find a gradual transformation from B -site to A -site ferroelectricity due to steric effects that largely determines the behavior of the system. In the case of Zr doping, in contrast, the behavior is eventually dominated by cooperative Zr-Ti motions and the local electrostatics. In addition, our comparative study reveals that the specific microscopic physics of these solids sets severe limits to the applicability of the virtual crystal approximation for these systems.

Internalized Racism, Perceived Racism, and Ethnic Identity: Exploring Their Relationship in Latina/o Undergraduates

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Hipolito-Delgado, Carlos P.

2016-01-01

For Latina/o undergraduates, ethnic identity is an important construct linked to self-esteem and educational attainment. Internalized and perceived racism have been hypothesized to hinder ethnic identity development in Latina/o undergraduates. To assess if internalized and perceived racism were inversely related to ethnic identity, the author…

Mixed-linker UiO-66: structure-property relationships revealed by a combination of high-resolution powder X-ray diffraction and density functional theory calculations.

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Taddei, Marco; Tiana, Davide; Casati, Nicola; van Bokhoven, Jeroen A; Smit, Berend; Ranocchiari, Marco

2017-01-04

The use of mixed-linker metal-organic frameworks (MIXMOFs) is one of the most effective strategies to modulate the physical-chemical properties of MOFs without affecting the overall crystal structure. In many instances, MIXMOFs have been recognized as solid solutions, with random distribution of ligands, in agreement with the empirical rule known as Vegard's law. In this work, we have undertaken a study combining high-resolution powder X-ray diffraction (HR-PXRD) and density functional theory (DFT) calculations with the aim of understanding the reasons why UiO-66-based amino- and bromo-functionalized MIXMOFs (MIXUiO-66) undergo cell expansion obeying Vegard's law and how this behaviour is related to their physical-chemical properties. DFT calculations predict that the unit cell in amino-functionalized UiO-66 experiences only minor expansion as a result of steric effects, whereas major modification to the electronic features of the framework leads to weaker metal-linker interaction and consequently to the loss of stability at higher degrees of functionalization. For bromo-functionalized UiO-66, steric repulsion due to the size of bromine yields a large cell expansion, but the electronic features remain very similar to pristine UiO-66, preserving the stability of the framework upon functionalization. MIXUiO-66 obtained by either direct synthesis or by post-synthetic exchange shows Vegard-like behaviour, suggesting that both preparation methods yield solid solutions, but the thermal stability and the textural properties of the post-synthetic exchanged materials do not display a clear dependence on the chemical composition, as observed for the MOFs obtained by direct synthesis.

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.

Extremely high efficient nanoreactor with Au@ZnO catalyst for photocatalysis

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Su, Chung-Yi; Yang, Tung-Han; Gurylev, Vitaly; Huang, Sheng-Hsin; Wu, Jenn-Ming; Perng, Tsong-Pyng

2015-10-01

We fabricated a photocatalytic Au@ZnO@PC (polycarbonate) nanoreactor composed of monolayered Au nanoparticles chemisorbed on conformal ZnO nanochannel arrays within the PC membrane. A commercial PC membrane was used as the template for deposition of a ZnO shell into the pores by atomic layer deposition (ALD). Thioctic acid (TA) with sufficient steric stabilization was used as a molecular linker for functionalization of Au nanoparticles in a diameter of 10 nm. High coverage of Au nanoparticles anchored on the inner wall of ZnO nanochannels greatly improved the photocatalytic activity for degradation of Rhodamine B. The membrane nanoreactor achieved 63% degradation of Rhodamine B within only 26.88 ms of effective reaction time owing to its superior mass transfer efficiency based on Damköhler number analysis. Mass transfer limitation can be eliminated in the present study due to extremely large surface-to-volume ratio of the membrane nanoreactor.

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...

Spin-Orbit Interaction and Kondo Scattering at the PrAlO3/SrTiO3 Interface

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Mozaffari, Shirin; Guchhait, Samaresh; Markert, John

We have investigated the effect of oxygen content, in the PO2 range of 6 ×10-6 - 1 ×10-3 torr, on the spin-orbit (SO) interaction at PrAlO3/SrTiO3 interface. The most-conducting 2-D-like PrAlO3 interfaces were not as conducting as comparable LaAlO3 samples, indicating either a steric or mixed-valent effect. The least-conducting, most oxygenated PrAlO3 interface exhibits hole conductivity, a departure from the typical electron-doped behavior. For 10-5 and 10-4 torr samples, high-temperature metallic behavior is accompanied by an upturn in resistivity at low temperatures, consistent with Kondo scattering theory; analysis gives a Kondo temperature 17 K. The magnetoresistance (MR) for the low PO2-grown samples was modeled with a positive part due to weak anti-localization (WAL) from a strong SO interaction, and a negative part due to the Kondo effect. The variation of MR suggests a strong SO interaction for the 10-5 torr sample with HSO = 1.25 T in both field orientations. The WAL effect is smaller for higher PO2-grown samples, where the high-field MR is dominated by the Kondo effect.

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.

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)

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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),...

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

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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.

Control of charge transfer by conformational and electronic effects: Donor-donor and donor-acceptor phenyl pyrroles

International Nuclear Information System (INIS)

Neubauer, Antje; Bendig, Juergen; Rettig, Wolfgang

2009-01-01

Derivatives of N-pyrrolobenzene with a para-donor and a para-acceptor substituent on the benzene ring are compared. It is shown that by a suitable increase of the donor strength of the pyrrolo group, CT fluorescence can be achieved even for donor-donor-substituted benzenes. The ICT emission for sterically hindered compounds is more forbidden than that of unhindered phenyl pyrroles. This suggests conformational effects which induce a narrower twist angle distribution around a perpendicular minimum in the excited state.

Using the general-purpose reactivity indicator: challenging examples.

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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.

Effect of hydration on the amide I band in the binary solvents dioxane-D2O and dioxane-H2O

International Nuclear Information System (INIS)

Kobayashi, M.; Kobayashi, M.

1980-01-01

Hydration of amides in aqueous solutions has been studied by measuring the infrared spectra of amides (benzamide, p-methoxybenzamide, and ropionamide) in dioxane-D 2 O and dioxane-H 2 O mixtures. The absorption due to the C=O stretching (or amide I band) exhibited a very remarkable red shift accompanied by a characteristic change of the band shape as the water content in the medium increased. The spectral change is attributed to the change of the hydration state at the carbonyl oxygen. In the aqueous mixtures, amide molecules participate in an equilibrium among various states of hydration. The weighted mean frequency of the ν/sub C = O/ absorption, anti ν/sub C = O/, varied in proportion to the water contained in the medium. The difference between the anti ν/sub C = O/ value in pure water and that in pure dioxane,Δ anti ν, was used as a measure of the maximum degree of hydration. It was larger for propionamide than for the aromatic amides, suggesting that the steric effect of the substituents is of major importance in hydration. The isotope effect, Δ anti ν/sub D 2 O//Δ anti ν/sub H 2 O/, in the range from 1.4 to 1.6 for all cases examined, indicated that stronger hydration of amides occurred with D 2 O than with H 2 O

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

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.

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.

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.

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.

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.

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.

Surface structures and dielectric response of ultrafine BaTiO3 particles

International Nuclear Information System (INIS)

Jiang, B.; Peng, J.L.; Bursill, L.A.

1998-01-01

Characteristic differences are observed for the dielectric response and microstructures of BaTiO 3 nanoscale fine powders prepared using sol gel (SG) and steric acid gel (SAG) methods. The former exhibit a critical size below which there is no paraelectric/ferroelectric phase transition whereas BaTiO 3 prepared via the SAG route remained cubic for all conditions. Atomic resolution images of both varieties showed a high density of interesting surface steps and facets. Computer simulated images of surface structure models showed that the outer (100) surface was typically a BaO layer and that at corners and ledges the steps are typically finished with Ba+2 ions; i.e. the surfaces and steps are Ba-rich. Otherwise the surfaces were typically clean and free of amorphous layers. The relationship between the observed surfaces structures and theoretical models for size effects on the dielectric properties is discussed. (authors)

Asymmetric synthesis of quaternary aryl amino acid derivatives via a three-component aryne coupling reaction

Directory of Open Access Journals (Sweden)

Elizabeth P. Jones

2011-11-01

Full Text Available A method was developed for the synthesis of α-alkyl, α-aryl-bislactim ethers in good to excellent yields and high diastereoselectivities, consisting of a facile one-pot procedure in which the aryl group is introduced by means of a nucleophilic addition to benzyne and the alkyl group by alkylation of a resultant benzylic anion. Hydrolysis of the sterically less hindered adducts gave the corresponding quaternary amino acids with no racemization, whereas hydrolytic ring opening gave the corresponding valine dipeptides from bulkier bislactims.

Silver-Catalyzed Cyclopropanation of Alkenes Using N-Nosylhydrazones as Diazo Surrogates.

Science.gov (United States)

Liu, Zhaohong; Zhang, Xinyu; Zanoni, Giuseppe; Bi, Xihe

2017-12-15

An efficient silver-catalyzed [2 + 1] cyclopropanation of sterically hindered internal alkenes with diazo compounds in which room-temperature-decomposable N-nosylhydrazones are used as diazo surrogates is reported. The unexpected unique catalytic activity of silver was ascribed to its dual role as a Lewis acid activating alkene substrates and as a transition metal forming silver carbenoids. A wide range of internal alkenes, including challenging diarylethenes, were suitable for this protocol, thereby affording a variety of cyclopropanes with high efficiency in a stereoselective manner under mild conditions.

Pd-PEPPSI-IPent-SiO2 : A Supported Catalyst for Challenging Negishi Coupling Reactions in Flow.

Science.gov (United States)

Price, Gregory A; Hassan, Abbas; Chandrasoma, Nalin; Bogdan, Andrew R; Djuric, Stevan W; Organ, Michael G

2017-10-16

A silica-supported precatalyst, Pd-PEPPSI-IPent-SiO 2 , has been prepared and evaluated for its proficiency in the Negishi cross-coupling of hindered and electronically deactivated coupling partners. The precatalyst Pd-PEPPSI-IPent loaded onto packed bed columns shows high catalytic activity for the room-temperature coupling of deactivated/hindered biaryl partners. Also for the first time, the flowed Csp 3 -Csp 2 coupling of secondary alkylzinc reagents to (hetero)aromatics has been achieved with high selectivity with Pd-PEPPSI-IPent-SiO 2 . These couplings required residence times as short as 3 minutes to effect completion of these challenging transformations with excellent selectivity for the nonrearranged product. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

Effect of Commercial SiO2 and SiO2 from rice husk ash loading on biodegradation of Poly (lactic acid) and crosslinked Poly (lactic acid)

Science.gov (United States)

Prapruddivongs, C.; Apichartsitporn, M.; Wongpreedee, T.

2017-09-01

In this work, biodegradation behavior of poly (lactic acid) (PLA) and crosslinked PLA filled with two types of SiO2, precipitated SiO2 (commercial SiO2) and SiO2 from rice husk ash, were studied. Rice husks were first treated with 2 molar hydrochloric acid (HCl) to produce high purity SiO2, before burnt in a furnace at 800°C for 6 hours. All components were melted bending by an internal mixer then hot pressed using compression molder to form tested specimens. FTIR spectra of SiO2 and PLA samples were investigated. The results showed the lack of silanol group (Si-OH) of rice husk ash after steric acid surface modification, while the addition of particles can affect the crosslinking of the PLA. For biodegradation test by evaluating total amount of carbon dioxide (CO2) evolved during 60 days incubation at a controlled temperature of 58±2°C, the results showed that the biodegradation of crosslinked PLA occurred slower than the neat PLA. However, SiO2 incorporation enhanced the degree of biodegradation In particular, introducing commercial SiO2 in PLA and crosslinked PLA tended to clearly increase the degree of biodegradation as a consequence of the more accelerated hydrolysis degradation.

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....

Lesion Orientation of O4-Alkylthymidine Influences Replication by Human DNA Polymerase η.

Science.gov (United States)

O'Flaherty, D K; Patra, A; Su, Y; Guengerich, F P; Egli, M; Wilds, C J

2016-08-01

DNA lesions that elude repair may undergo translesion synthesis catalyzed by Y-family DNA polymerases. O 4 -Alkylthymidines, persistent adducts that can result from carcinogenic agents, may be encountered by DNA polymerases. The influence of lesion orientation around the C4- O 4 bond on processing by human DNA polymerase η (hPol η ) was studied for oligonucleotides containing O 4 -methylthymidine, O 4 -ethylthymidine, and analogs restricting the O 4 -methylene group in an anti -orientation. Primer extension assays revealed that the O 4 -alkyl orientation influences hPol η bypass. Crystal structures of hPol η •DNA•dNTP ternary complexes with O 4 -methyl- or O 4 -ethylthymidine in the template strand showed the nucleobase of the former lodged near the ceiling of the active site, with the syn - O 4 -methyl group engaged in extensive hydrophobic interactions. This unique arrangement for O 4 -methylthymidine with hPol η , inaccessible for the other analogs due to steric/conformational restriction, is consistent with differences observed for nucleotide incorporation and supports the concept that lesion conformation influences extension across DNA damage. Together, these results provide mechanistic insights on the mutagenicity of O 4 MedT and O 4 EtdT when acted upon by hPol η .

Direct inelastic scattering of oriented NO from Ag(111) and Pt(111)

International Nuclear Information System (INIS)

Tenner, M.G.; Kuipers, E.W.; Kleyn, A.W.; Stolte, S.

1991-01-01

A pulsed supersonic and cold oriented beam of NO molecules is incident upon the (111) face of clean Ag and Pt single crystal surfaces. The steric effect in the scattered density distributions is determined by a quadrupole mass spectrometer. It is found that the steric effect in the peak in the distribution of direct inelastically scattered molecules depends linearly on the reflection angle. In all circumstances O-end collisions lead to scattering angles more inclined towards the surface than N-end collisions. For the Pt(111) surface a much stronger steric effect is measured than for the Ag(111) surface. The steric effect seems to scale with the incident normal velocity. These strong steric effects can be explained by the larger trapping probability for the N-end orientation and a leverage effect due to the high trapping probability

Diastereomerically and enantiomerically pure 2,3-disubstituted pyrrolidines from 2,3-aziridin-1-ols using a sulfoxonium ylide: a one-carbon homologative relay ring expansion.

Science.gov (United States)

Schomaker, Jennifer M; Bhattacharjee, Somnath; Yan, Jun; Borhan, Babak

2007-02-21

An ylide-based aza-Payne rearrangement of 2,3-aziridin-1-ols leads to an efficient process for the preparation of pyrrolidines. The aza-Payne rearrangement under basic reaction conditions favors the formation of epoxy amines. Subsequent nucleophilic attack of the epoxide by the ylide yields a bis-anion, which upon a 5-exo-tet ring-closure yields the desired pyrrolidine, thus completing the relay of the three-membered to the five-membered nitrogen-containing ring system. This process takes place with complete transfer of stereochemical fidelity and can be applied to sterically hindered aziridinols.

Design, synthesis and cellular metabolism study of 4'-selenonucleosides.

Science.gov (United States)

Yu, Jinha; Sahu, Pramod K; Kim, Gyudong; Qu, Shuhao; Choi, Yoojin; Song, Jayoung; Lee, Sang Kook; Noh, Minsoo; Park, Sunghyouk; Jeong, Lak Shin

2015-01-01

4'-seleno-homonucleosides were synthesized as next-generation nucleosides, and their cellular phosphorylation was studied to confirm the hypothesis that bulky selenium atom can sterically hinder the approach of cellular nucleoside kinase to the 5'-OH for phosphorylation. 4'-seleno-homonucleosides (n = 2), with one-carbon homologation, were synthesized through a tandem seleno-Michael addition-SN2 ring cyclization. LC-MS analysis demonstrated that they were phosphorylated by cellular nucleoside kinases, resulting in anticancer activity. The bulky selenium atom played a key role in deciding the phosphorylation by cellular nucleoside kinases. [Formula: see text].

1,3,4-Tri-O-acetyl-2-N-(trifluoroacetyl-β-l-fucose

Directory of Open Access Journals (Sweden)

David C. McCutcheon

2014-02-01

Full Text Available The title compound, C14H18F3NO8, was produced through conjugation of 1,3,4-tri-O-acetyl-2-azidodeoxy-α,β-l-fucose with trifluoroacetyl chloride in the presence of bis(diphenylphosphinoethane in tetrahydrofuran at room temperature. The X-ray crystal structure reveals that the β-anomer of the product mixture crystallizes from ethyl acetate/hexanes. The compound exists in a typical chair conformation with the maximum possible number of substituents, four out of five, located in the sterically preferred equatorial positions. The major directional force facilitating packing of the molecules are N—H...O hydrogen bonds involving the amide moieties of neighboring molecules, which connect molecules stacked along the a-axis direction into infinite strands with a C11(4 graph-set motif. Formation of the strands is assisted by a number of weaker C—H...O interactions involving the methine and methyl H atoms. These strands are connected through further C—H...O and C—H...F interactions into a three dimensional network

Adsorption and decomposition of H{sub 2}O on cobalt surfaces: A DFT study

Energy Technology Data Exchange (ETDEWEB)

Ma, F.F.; Ma, S.H., E-mail: msh8586@163.com; Jiao, Z.Y.; Dai, X.Q.

2016-10-30

Highlights: • Molecular water weakly binds to Co surfaces and it is feasible to desorption from the clean surfaces. • The presence of atomic oxygen has a prominent promotion effect on the dissociation of water into hydroxyl, especially on O-covered Co(110) no extra energy is needed to dissociate H{sub 2}O. • Distinctively, the presence of hydroxyl hinders the dissociation of water molecule. • The analysis of microscopic decomposition behaviors demonstrates that molecular water adsorbs dissociatively with the aid of pre-adsorbed oxygen atom, forming OH radicals chemisorbed on the considered surfaces. - Abstract: Water adsorption and dissociation on clean and O-covered Co(100), Co(110) and Co(111) surfaces are studied using the density functional theory calculations. The results indicate that molecular water weakly binds to the surfaces and is feasible to desorption from the clean surfaces. Moreover, the pre-adsorption of O atom increases the binding of water to the surfaces, and prominently decreases the activation barriers of water dissociation into OH, especially on Co(110) surface. In contrast, the activation barrier for OH dissociation is slightly affected in the presence of O atom. Overall, this study reveals that O-assisted H{sub 2}O favorably adsorbs dissociatively, forming OH chemisorbed on the surfaces, which further hinders H{sub 2}O dissociation, and also illustrates the fact that molecular water dissociation is structure-sensitive on metal surfaces.

Magnetic Pd-Fe{sub 3}O{sub 4} heterodimer nanocrystals as recoverable catalysts for ligand-free hiyama cross-coupling reactions

Energy Technology Data Exchange (ETDEWEB)

Lee, Woong Sup; Byun, Sang Moon; Kwon, Jung Min; Kim, B. Moon [Dept. of Chemistry, College of Natural Sciences, Seoul National University, Seoul (Korea, Republic of)

2016-12-15

Ligand-free Hiyama cross-coupling reaction was achieved through the use of Pd-Fe{sub 3}O{sub 4} heterodimeric nanocrystals (1 mol% in Pd) as recyclable catalysts. The nanocrystal catalysts exhibited good activities accommodating a variety of substrates including aryl bromides and iodides with substituents of varying electronic and steric properties. Furthermore, the nanocrystal catalyst could be conveniently recovered with the aid of an external magnet and recycled five times without the loss of catalytic activity to a considerable degree.

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.

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.

Manganese-Oxygen Intermediates in O-O Bond Activation and Hydrogen-Atom Transfer Reactions.

Science.gov (United States)

Rice, Derek B; Massie, Allyssa A; Jackson, Timothy A

2017-11-21

Biological systems capitalize on the redox versatility of manganese to perform reactions involving dioxygen and its derivatives superoxide, hydrogen peroxide, and water. The reactions of manganese enzymes influence both human health and the global energy cycle. Important examples include the detoxification of reactive oxygen species by manganese superoxide dismutase, biosynthesis by manganese ribonucleotide reductase and manganese lipoxygenase, and water splitting by the oxygen-evolving complex of photosystem II. Although these enzymes perform very different reactions and employ structurally distinct active sites, manganese intermediates with peroxo, hydroxo, and oxo ligation are commonly proposed in catalytic mechanisms. These intermediates are also postulated in mechanisms of synthetic manganese oxidation catalysts, which are of interest due to the earth abundance of manganese. In this Account, we describe our recent efforts toward understanding O-O bond activation pathways of Mn III -peroxo adducts and hydrogen-atom transfer reactivity of Mn IV -oxo and Mn III -hydroxo complexes. In biological and synthetic catalysts, peroxomanganese intermediates are commonly proposed to decay by either Mn-O or O-O cleavage pathways, although it is often unclear how the local coordination environment influences the decay mechanism. To address this matter, we generated a variety of Mn III -peroxo adducts with varied ligand environments. Using parallel-mode EPR and Mn K-edge X-ray absorption techniques, the decay pathway of one Mn III -peroxo complex bearing a bulky macrocylic ligand was investigated. Unlike many Mn III -peroxo model complexes that decay to oxo-bridged-Mn III Mn IV dimers, decay of this Mn III -peroxo adduct yielded mononuclear Mn III -hydroxo and Mn IV -oxo products, potentially resulting from O-O bond activation of the Mn III -peroxo unit. These results highlight the role of ligand sterics in promoting the formation of mononuclear products and mark an important

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...

2'-O-methylation in mRNA disrupts tRNA decoding during translation elongation.

Science.gov (United States)

Choi, Junhong; Indrisiunaite, Gabriele; DeMirci, Hasan; Ieong, Ka-Weng; Wang, Jinfan; Petrov, Alexey; Prabhakar, Arjun; Rechavi, Gideon; Dominissini, Dan; He, Chuan; Ehrenberg, Måns; Puglisi, Joseph D

2018-03-01

Chemical modifications of mRNA may regulate many aspects of mRNA processing and protein synthesis. Recently, 2'-O-methylation of nucleotides was identified as a frequent modification in translated regions of human mRNA, showing enrichment in codons for certain amino acids. Here, using single-molecule, bulk kinetics and structural methods, we show that 2'-O-methylation within coding regions of mRNA disrupts key steps in codon reading during cognate tRNA selection. Our results suggest that 2'-O-methylation sterically perturbs interactions of ribosomal-monitoring bases (G530, A1492 and A1493) with cognate codon-anticodon helices, thereby inhibiting downstream GTP hydrolysis by elongation factor Tu (EF-Tu) and A-site tRNA accommodation, leading to excessive rejection of cognate aminoacylated tRNAs in initial selection and proofreading. Our current and prior findings highlight how chemical modifications of mRNA tune the dynamics of protein synthesis at different steps of translation elongation.

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.

The structural chemistry of metallocorroles: combined X-ray crystallography and quantum chemistry studies afford unique insights.

Science.gov (United States)

Thomas, Kolle E; Alemayehu, Abraham B; Conradie, Jeanet; Beavers, Christine M; Ghosh, Abhik

2012-08-21

Although they share some superficial structural similarities with porphyrins, corroles, trianionic ligands with contracted cores, give rise to fundamentally different transition metal complexes in comparison with the dianionic porphyrins. Many metallocorroles are formally high-valent, although a good fraction of them are also noninnocent, with significant corrole radical character. These electronic-structural characteristics result in a variety of fascinating spectroscopic behavior, including highly characteristic, paramagnetically shifted NMR spectra and textbook cases of charge-transfer spectra. Although our early research on corroles focused on spectroscopy, we soon learned that the geometric structures of metallocorroles provide a fascinating window into their electronic-structural characteristics. Thus, we used X-ray structure determinations and quantum chemical studies, chiefly using DFT, to obtain a comprehensive understanding of metallocorrole geometric and electronic structures. This Account describes our studies of the structural chemistry of metallocorroles. At first blush, the planar or mildly domed structure of metallocorroles might appear somewhat uninteresting particularly when compared to metalloporphyrins. Metalloporphyrins, especially sterically hindered ones, are routinely ruffled or saddled, but the missing meso carbon apparently makes the corrole skeleton much more resistant to nonplanar distortions. Ruffling, where the pyrrole rings are alternately twisted about the M-N bonds, is energetically impossible for metallocorroles. Saddling is also uncommon; thus, a number of sterically hindered, fully substituted metallocorroles exhibit almost perfectly planar macrocycle cores. Against this backdrop, copper corroles stand out as an important exception. As a result of an energetically favorable Cu(d(x2-y2))-corrole(π) orbital interaction, copper corroles, even sterically unhindered ones, are inherently saddled. Sterically hindered substituents

An Inactive Geminin Mutant That Binds Cdt1

Directory of Open Access Journals (Sweden)

Marissa Suchyta

2015-05-01

Full Text Available The initiation of DNA replication is tightly regulated in order to ensure that the genome duplicates only once per cell cycle. In vertebrate cells, the unstable regulatory protein Geminin prevents a second round of DNA replication by inhibiting the essential replication factor Cdt1. Cdt1 recruits mini-chromosome maintenance complex (MCM2-7, the replication helicase, into the pre-replication complex (pre-RC at origins of DNA replication. The mechanism by which Geminin inhibits MCM2-7 loading by Cdt1 is incompletely understood. The conventional model is that Geminin sterically hinders a direct physical interaction between Cdt1 and MCM2-7. Here, we describe an inactive missense mutant of Geminin, GemininAWA, which binds to Cdt1 with normal affinity yet is completely inactive as a replication inhibitor even when added in vast excess. In fact, GemininAWA can compete with GemininWT for binding to Cdt1 and prevent it from inhibiting DNA replication. GemininAWA does not inhibit the loading of MCM2-7 onto DNA in vivo, and in the presence of GemininAWA, nuclear DNA is massively over-replicated within a single S phase. We conclude that Geminin does not inhibit MCM loading by simple steric interference with a Cdt1-MCM2-7 interaction but instead works by a non-steric mechanism, possibly by inhibiting the histone acetyltransferase HBO1.

Synthesis of anatase TiO2 nanoparticles with beta-cyclodextrin as a supramolecular shell.

Science.gov (United States)

Li, Landong; Sun, Xiaohong; Yang, Yali; Guan, Naijia; Zhang, Fuxiang

2006-11-20

We report a novel, green hydrothermal-synthesis route to well-dispersed anatase TiO2 nanoparticles with particle sizes of 9-16 nm in the presence of beta-CD (beta-cyclodextrin). During the synthesis process, the CD-containing synthesis mixture assembled in both longitudinal and latitudinal directions. Driven by the interaction between molecules, the beta-CDs assembled in the longitudinal direction to form long-chain compounds, whereas in the latitudinal direction, they tended to form regular aggregates through coordination with the Ti species from the hydrolysis of tetrabutyl titanate. In view of the effect of the coordination and the steric hindrance of beta-CDs as a supramolecular shell, homogeneous nuclei and slow growth of TiO2 crystals during the synthesis process was observed, which was responsible for the formation of uniform TiO2 nanoparticles. The low beta-CD dosage and the high product yield (>90%) demonstrated well the potential of this synthesis route in the large-scale industrial production of anatase nanoparticles.

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.

ZnO nanorod–templated well-aligned ZrO2 nanotube arrays for fibroblast adhesion and proliferation

International Nuclear Information System (INIS)

Lu, Zhisong; Hu, Weihua; Ming Li, Chang; Zhu, Zhihong; Liu, Jinping

2014-01-01

Cellular responses to porous tubular structures have recently been investigated in highly ordered ZrO 2 nanotube arrays fabricated with anodization. However, the potential applications of the nanotube arrays are hindered by instrument requirements and substrate limitations, as well as by the complicated processes needed for synthesis. In this work, ZrO 2 nanotube arrays were synthesized by in situ hydrolysis of zirconium propoxide with a zinc oxide nanorod array–based template. Fibroblast cells were able to grow on the nanotube array surface with produced elongated filopodia. Studies of the capability of cell growth and the expression of adhesion- and proliferation-related genes reveal that ZrO 2 nanotube arrays may provide a better environment for cell adhesion and growth than a flat titanium surface. These findings not only provide fundamental insight into cell response to nanostructures but also provide an opportunity to use a unique approach to fabricate ZrO 2 nanotube array structures for potential implant applications. (papers)

Nanosilica supported CaO: A regenerable and mechanically hard CO2 sorbent at Ca-looping conditions

International Nuclear Information System (INIS)

Sanchez-Jimenez, P.E.; Perez-Maqueda, L.A.; Valverde, J.M.

2014-01-01

Highlights: • A synthetic CO 2 sorbent is prepared by impregnation of calcium nitrate on a nanosilica matrix. • Sintering of the nascent CaO in the calcination stage of carbonation/calcination cycles is hindered. • CaO conversion reaches a stable value well above the residual conversion of natural limestone. • Particle fragmentation as caused by ultrasonic irradiation in a liquid dispersion is hindered. - Abstract: This work presents a CO 2 sorbent that may be synthesized from low-cost and widely available materials following a simple method basically consisting of impregnation of a nanostructured silica support with a saturated solution of calcium nitrate. In a first impregnation stage, the use of a stoichiometric CaO/SiO 2 ratio serves to produce a calcium silicate matrix after calcination. This calcium silicate matrix acts as a thermally stable and mechanically hard support for CaO deposited on it by further impregnation. The CaO-impregnated sorbent exhibits a stable CaO conversion at Ca-looping conditions whose value depends on the CaO wt% deposited on the calcium silicate matrix, which can be increased by successive reimpregnations. A 10 wt% CaO impregnated sorbent reaches a stable conversion above 0.6 whereas the stable conversion of a 30 wt% CaO impregnated sorbent is around 0.3, which is much larger than the residual conversion of CaO derived from natural limestone (between 0.07 and 0.08). Moreover, particle size distribution measurements of samples predispersed in a liquid and subjected to high energy ultrasonic waves indicate that the CaO-impregnated sorbent has a relatively high mechanical strength as compared to limestone derived CaO

Influence of temperature and solvent concentration on the kinetics of the enzyme carbonic anhydrase in carbon capture technology

DEFF Research Database (Denmark)

Gladis, Arne; Deslauriers, Maria Gundersen; Fosbøl, Philip Loldrup

2017-01-01

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: the primary amine monoethanolamine (MEA), the sterically hindered primary amine 2-amino-2-methyl-1-propanol (AMP), the tertiary amine N......-methyl-diethanolamine (MDEA) and the carbonate salt solution K2CO3 were compared in concentrations from 5 to 50 wt% in a temperature range of 298–328 K with and without enzyme. Necessary mass transfer parameters such as liquid side mass transfer coefficient and solvent and enzyme reaction rates were determined...

Decomposition rates of radiopharmaceutical indium chelates in serum

International Nuclear Information System (INIS)

Yeh, S.M.; Meares, C.F.; Goodwin, D.A.

1979-01-01

The rates at which six small aminopolycarboxylate chelates of trivalent 111 In and three protein-bound chelates of 111 In deliver indium to the serum protein transferrin have been studied in sterile human serum at pH 7.3, 37 deg C. Sterically hindered chelates containing a substituent on an ethylene carbon of EDTA decompose with rates in the range 0.03 to 0.11% per day - one to two orders of magnitude slower than other chelates. Only small differences are observed between rates of decomposition for low-molecular-weight chelates and for protein-bound chelates having analogous structures. (author)

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.

Hardness properties and microscopic investigation of crack- crystal interaction in SiO(2)-MgO-Al(2)O(3)-K(2)O-B(2)O(3)-F glass ceramic system.

Science.gov (United States)

Roy, Shibayan; Basu, Bikramjit

2010-01-01

In view of the potential engineering applications requiring machinability and wear resistance, the present work focuses to evaluate hardness property and to understand the damage behavior of some selected glass-ceramics having different crystal morphologies with SiO(2)-MgO-Al(2)O(3)-K(2)O-B(2)O(3)-F composition, using static micro-indentation tests as well as dynamic scratch tests, respectively. Vickers hardness of up to 5.5 GPa has been measured in glass-ceramics containing plate like mica crystals. Scratch tests at a high load of 50 Nin artificial saliva were carried out in order to simulate the crack-microstructure interaction during real-time abrasion wear and machining operation. The experimental observations indicate that the novel "spherulitic-dendritic shaped "crystals, similar to the plate like crystals, have the potential to hinder the scratching induced crack propagation. In particular, such potential of the 'spherulitic-dendritic' crystals become more effective due to the larger interfacial area with the glass matrix as well as the dendritic structure of each mica plate, which helps in crack deflection and crack blunting, to a larger extent.While modest damage tolerant behavior is observed in case of 'spherulitic-dendritic' crystal containing material, severe brittle fracture of plate like crystals were noted, when both were scratched at 50 N load.

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.

Electronic structures of N- and C-doped NiO from first-principles calculations

International Nuclear Information System (INIS)

Long, Run; English, Niall J.; Mooney, Damian A.

2010-01-01

The large intrinsic band gap of NiO has hindered severely its potential application under visible-light irradiation. In this Letter, we have performed first-principles calculations on the electronic properties of N- and C-doped NiO to ascertain if its band gap may be narrowed theoretically. It was found that impurity bands driven by N 2p or C 2p states appear in the band gap of NiO and that some of these locate at the conduction band minimum, which leads to a significant band gap narrowing. Our results show that N-doped NiO may serve as a potential photocatalyst relative to C-doped NiO, due to the presence of some recombination centres in C-doped NiO.

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.

Myelography iodinated contrast media. I. Unraveling the atropisomerism properties in solution.

Science.gov (United States)

Fontanive, Luca; D'Amelio, Nicola; Cesàro, Attilio; Gamini, Amelia; Tavagnacco, Letizia; Paolantoni, Marco; Brady, John W; Maiocchi, Alessandro; Uggeri, Fulvio

2015-06-01

The present work reports a thorough conformational analysis of iodinated contrast media: iomeprol, iopamidol (the world's most utilized contrast agent), and iopromide. Its main aim is the understanding of the complex structural features of these atropisomeric molecules, characterized by the presence of many conformers with hindered rotations, and of the role of atropisomerism in the physicochemical properties of their aqueous solutions. The problem was tackled by using an extensive analysis of (13)C NMR data on the solutions of whole molecules and of simple precursors in addition to FT-IR investigation and molecular simulations. This analysis demonstrated that out of the many possible atropisomers, only a few are significantly populated, and their relative population is provided. The conformational analysis also indicated that the presence of a sterically hindered amidic bond, allowing a significant population of cis forms (E in iopromide and exo in iomeprol), may be the basis for an increased thermodynamic solubility of concentrated solutions of iomeprol.

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.

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.

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.

Photocatalysis and characterization of the gel-derived TiO{sub 2} and P-TiO{sub 2} transparent thin films

Energy Technology Data Exchange (ETDEWEB)

Yu, Hsuan-Fu, E-mail: hfyu@mail.tku.edu.tw [Department of Chemical and Materials Engineering, Ceramic Materials Laboratory, Tamkang University, Taipei 25137, Taiwan (China); Energy and Opto-Electronic Materials Research Center, Tamkang University, Taipei 25137, Taiwan (China); Wang, Chang-Wen [Department of Chemical and Materials Engineering, Ceramic Materials Laboratory, Tamkang University, Taipei 25137, Taiwan (China)

2011-07-29

The gel-derived TiO{sub 2} and P-TiO{sub 2} transparent films coated on fused-SiO{sub 2} substrates were prepared using a spin-coating technique. Effects of phosphorus dopants and calcination temperature on crystal structure, crystallite size, microstructure, light transmittance and photocatalytic activity of the films were investigated. By introducing P atoms to Ti-O framework, the growth of anatase crystallites was hindered and the crystal structure of anatase-TiO{sub 2} could withstand temperature up to 900 deg. C. The photocatalytic activities of the prepared films were characterized using the characteristic time constant ({tau}) for the photocatalytic reaction. The titania film with a smaller {tau} value possesses a higher photocatalytic ability. After exposing to 365-nm UV light for 12 h, the P-TiO{sub 2} films calcined between 600 deg. C and 900 deg. C can photocatalytically decomposed {>=} 84 mol% of the methylene blue in water with corresponding {tau} {<=} 7.1 h, which were better than the pure TiO{sub 2} films prepared at the same calcination temperature.

Using TiO2 as a Conductive Protective Layer for Photocathodic H2 Evolution

DEFF Research Database (Denmark)

Seger, Brian; Pedersen, Thomas; Laursen, Anders Bo

2013-01-01

Surface passivation is a general issue for Si-based photoelectrodes because it progressively hinders electron conduction at the semiconductor/electrolyte interface. In this work, we show that a sputtered 100 nm TiO2 layer on top of a thin Ti metal layer may be used to protect an n+p Si photocatho...

Transfer of preheat-treated SnO 2 via a sacrificial bridge-type ZnO layer for ethanol gas sensor

KAUST Repository

Lee, Da Hoon

2017-08-05

The progress in developing the microelectromechanical system (MEMS) heater-based SnO2 gas sensors was hindered by the subsequent heat treatment of the tin oxide (SnO2), nevertheless it is required to obtain excellent sensor characteristics. During the sintering process, the MEMS heater and the contact electrodes can be degraded at such a high temperature, which could reduce the sensor response and reliability. In this research, we presented a process of preheating the printed SnO2 sensing layer on top of a sacrificial bridge-type ZnO layer at such a high temperature, followed by transferring it onto the contact electrodes of sensor device by selective etching of the sacrificial ZnO layer. Therefore, the sensor device was not exposed to the high sintering temperature. The SnO2 gas sensor fabricated by the transfer process exhibited a rectangular sensing curve behavior with a rapid response of 52 s at 20 ppm ethanol concentration. In addition, reliable and repeatable sensing characteristics were obtained even at an ethanol gas concentration of 5 ppm.

Transfer of preheat-treated SnO 2 via a sacrificial bridge-type ZnO layer for ethanol gas sensor

KAUST Repository

Lee, Da Hoon; Kang, Sun Kil; Pak, Yusin; Lim, Namsoo; Lee, Ryeri; Kumaresan, Yogeenth; Lee, Sungeun; Lee, Chaedeok; Ham, Moon-Ho; Jung, Gun Young

2017-01-01

The progress in developing the microelectromechanical system (MEMS) heater-based SnO2 gas sensors was hindered by the subsequent heat treatment of the tin oxide (SnO2), nevertheless it is required to obtain excellent sensor characteristics. During the sintering process, the MEMS heater and the contact electrodes can be degraded at such a high temperature, which could reduce the sensor response and reliability. In this research, we presented a process of preheating the printed SnO2 sensing layer on top of a sacrificial bridge-type ZnO layer at such a high temperature, followed by transferring it onto the contact electrodes of sensor device by selective etching of the sacrificial ZnO layer. Therefore, the sensor device was not exposed to the high sintering temperature. The SnO2 gas sensor fabricated by the transfer process exhibited a rectangular sensing curve behavior with a rapid response of 52 s at 20 ppm ethanol concentration. In addition, reliable and repeatable sensing characteristics were obtained even at an ethanol gas concentration of 5 ppm.

Ultrafast Librational Relaxation of H2O in Liquid Water

DEFF Research Database (Denmark)

Petersen, Jakob; Møller, Klaus Braagaard; Rey, Rossend

2013-01-01

The ultrafast librational (hindered rotational) relaxation of a rotationally excited H2O molecule in pure liquid water is investigated by means of classical nonequilibrium molecular dynamics simulations and a power and work analysis. This analysis allows the mechanism of the energy transfer from...... the excited H2O to its water neighbors, which occurs on a sub-100 fs time scale, to be followed in molecular detail, i.e., to determine which water molecules receive the energy and in which degrees of freedom. It is found that the dominant energy flow is to the four hydrogen-bonded water partners in the first...

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.

A conformational study of proline derivatives

Directory of Open Access Journals (Sweden)

M.E. Kamwaya

2002-12-01

Full Text Available From the study of the structures and molecular conformations of a number of proline derivatives, some conclusions were drawn. The widening effect of angle Cα-C'-N' is caused by steric repulsion between a hydrogen atom at Cα of the preceding prolyl residue with any other at either Cα or Cδ of the pyrrolidine ring cis to it. This effect is influenced by the distance between the said hydrogen atoms: the nearer this distance is, the greater is the steric repulsion and the wider is the angle of steric repulsion. The ratio of the angle of steric repulsion to the distance between Cα and the following Cα (or Cδ cis to it is approximately 40 and 41 for peptides with trans and cis configurations, respectively. The torsion angle ranges for χ1, χ3, χ 4, θ and φ in these derivatives are widened more than usual. The highest vibration, which more often takes place at either the Cβ or Cγ of the pyrrolidine ring, does so not necessarily at the one that is puckered. A Δ&psi -relationship is established, for the determination of α-helixity or collageneity, also in small peptides and amino acids that contain proline. The Δ&psi-relationship is versatile and gives about +180o and –180o for the two categories, respectively. The distance between the carbonyl and hydroxyl (or otherwise terminal end atoms is minimal (2.2 Å and constant, for all peptides. The ratios of the angles at the carbonyl carbons (O'-C'-N' or (O'-C'-O' to this distance is also constant: 56 and 57 for the cis and trans confirgurations, respectively; i.e. a proline O'-C'-N'- (or O'-C'-O'-test, hereinafter called the CT-test, has been established for the determination of cis and trans configurations. It is also established in these proline derivatives, that whereas puckering takes place at Cβ for the CS form, it does so at Cγ for the C2 form.

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.

Structure–Activity Relationship To Screen Ni–Bisphosphine Complexes for the Oxidative Coupling of CO2 and Ethylene

KAUST Repository

Al-Ghamdi, Miasser

2017-03-07

Density functional theory calculations have been used to investigate competition between inner- and outer-sphere reaction pathways in the oxidative coupling of CO2 and ethylene for a set of 12 Ni–bisphosphine complexes, in order to build a QSAR approach correlating catalyst structure to calculated energy barriers for CO2 activation. The ligands were selected to explore different substituents on the P atoms (cyclohexyl, phenyl, and tert-butyl) and different lengths of the tether connecting the P atoms, −(CH2)n– with n = 1–3. As expected, the conclusion is that the inner-sphere reaction pathway is favored with unhindered ligands, while the outer-sphere reaction pathway is favored with hindered ligands. To find a possible correlation with molecular descriptors, we started using the buried volume as a steric descriptor. A reasonable correlation could be found for the energy barrier along the inner-sphere pathway, while scarce correlation was found for the energy barrier along the outer-sphere pathway, indicating that the steric bulkiness of the ligand disfavors approach of CO2 to the metal center. Much stronger correlation between the ligand structure and the energy barrier along the inner-sphere pathway was achieved when the steric descriptor was augmented by an electronic descriptor, consisting of the partial charge on the Ni atom. The much better correlation suggests that bisphosphine ligands have a non-negligible electronic impact on the catalyst performance.

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

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

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.

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.

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

Synthesis, characterization and antifungal efficacy of C-coordinated O-carboxymethyl chitosan Cu(II) complexes.

Science.gov (United States)

Liu, Weixiang; Qin, Yukun; Liu, Song; Xing, Ronge; Yu, Huahua; Chen, Xiaolin; Li, Kecheng; Li, Pengcheng

2017-03-15

A novel type of O-carboxymethyl chitosan Schiff bases (O-CSPX) was synthesized via a condensation reaction. After the coordination reaction of cupric ions, Cu(II) complexes (O-CSPX-Cu) were achieved. The theoretical structure of O-CSPX-Cu calculated by Gaussian 09 reveals that the copper ions underwent dsp 2 hybridization, coordinated by the carbon atom in the p-π conjugate group and the oxygen atoms in the acetate ion. Then, the structures were confirmed by FT-IR, 1 H NMR, CP-MAS 13 C NMR, elemental analysis, DSC and XRD. The antifungal properties of O-CSPX-Cu against Phytophthora capsici (P. capsici), Gibberella zeae (G. zeae) and Glomerella cingulata (G. cingulata) were evaluated at concentrations ranging from 0.05mg/mL to 0.20mg/mL. The experiments indicated that the derivatives have significantly enhanced antifungal activity after copper ion complexation compared with the original chitosan. Moreover, it was shown that 0.20mg/mL of O-CSP3-Cu and O-CSP4-Cu can 100% inhibit the growth of P. capsici. The experimental results reveal that the antifungal efficiency is related to the space steric hindrance on the benzene ring, which may provide a novel direction for the development of copper fungicides. Copyright © 2016 Elsevier Ltd. All rights reserved.

Optimization of charge transfer and transport processes at the CdSe quantum dots/TiO2 nanorod interface by TiO2 interlayer passivation

International Nuclear Information System (INIS)

Jaramillo-Quintero, O A; Rincon, M E; Triana, M A

2017-01-01

Surface trap states hinder charge transfer and transport properties in TiO 2 nanorods (NRs), limiting its application on optoelectronic devices. Here, we study the interfacial processes between rutile TiO 2 NR and CdSe quantum dots (QDs) using TiO 2 interlayer passivation treatments. Anatase or rutile TiO 2 thin layers were deposited on an NR surface by two wet-chemical deposition treatments. Reduced interfacial charge recombination between NRs and CdSe QDs was observed by electrochemical impedance spectroscopy with the introduction of TiO 2 thin film interlayers compared to bare TiO 2 NRs. These results can be ascribed to in-gap trap state passivation of the TiO 2 NR surface, which led to an increase in open circuit voltage. Moreover, the rutile thin layer was more efficient than anatase to promote a higher photo-excited electron transfer from CdSe QDs to TiO 2 NRs due to a large driving force for charge injection, as confirmed by surface photovoltage spectroscopy. (paper)

New Ru(II) complexes for dual photoreactivity: ligand exchange and (1)O2 generation.

Science.gov (United States)

Knoll, Jessica D; Albani, Bryan A; Turro, Claudia

2015-08-18

Uncovering the factors that govern the electronic structure of Ru(II)-polypyridyl complexes is critical in designing new compounds for desired photochemical reactions, and strategies to tune excited states for ligand dissociation and (1)O2 production are discussed herein. The generally accepted mechanism for photoinduced ligand dissociation proposes that population of the dissociative triplet ligand field ((3)LF) state proceeds through thermal population from the vibrationally cooled triplet metal-to-ligand charge transfer ((3)MLCT) state; however, temperature-dependent emission spectroscopy provides varied activation energies using the emission and ligand exchange quantum yields for [Ru(bpy)2(L)2](2+) (bpy = 2,2'-bipyridine; L = CH3CN or py). This suggests that population of the (3)LF state proceeds from the vibrationally excited (3)MLCT state. Because the quantum yield of ligand dissociation for nitriles is much more efficient than that for py, steric bulk was introduced into the ligand set to distort the pseudo-octahedral geometry and lower the energy of the (3)LF state. The py dissociation quantum yield with 500 nm irradiation in a series of [Ru(tpy)(NN)(py)](2+) complexes (tpy = 2,2':6',2″-terpyridine; NN = bpy, 6,6'-dimethyl-2,2'-bipyridine (Me2bpy), 2,2'-biquinoline (biq)) increases by 2-3 orders of magnitude with the sterically bulky Me2bpy and biq ligands relative to bpy. Ultrafast transient absorption spectroscopy reveals population of the (3)LF state within 3-7 ps when NN is bulky, and density functional theory calculations support stabilized (3)LF states. Dual activity via ligand dissociation and (1)O2 production can be achieved by careful selection of the ligand set to tune the excited-state dynamics. Incorporation of an extended π system in Ru(II) complexes such as [Ru(bpy)(dppn)(CH3CN)2](2+) (dppn = benzo[i]dipyrido[3,2-a:2',3'-c]phenazine) and [Ru(tpy)(Me2dppn)(py)](2+) (Me2dppn = 3,6-dimethylbenzo[i]dipyrido[3,2-a:2',3'-c]phenazine) introduces

New Ru(II) Complexes for Dual Photoreactivity: Ligand Exchange and 1O2 Generation

Science.gov (United States)

Knoll, Jessica D.; Albani, Bryan A.; Turro, Claudia

2016-01-01

CONSPECTUS Uncovering the factors that govern the electronic structure of Ru(II)–polypyridyl complexes is critical in designing new compounds for desired photochemical reactions, and strategies to tune excited states for ligand dissociation and 1O2 production are discussed herein. The generally accepted mechanism for photoinduced ligand dissociation proposes that population of the dissociative triplet ligand field (3LF) state proceeds through thermal population from the vibrationally cooled triplet metal-to-ligand charge transfer (3MLCT) state; however, temperature-dependent emission spectroscopy provides varied activation energies using the emission and ligand exchange quantum yields for [Ru(bpy)2(L)2]2+ (bpy = 2,2′-bipyridine; L = CH3CN or py). This suggests that population of the 3LF state proceeds from the vibrationally excited 3MLCT state. Because the quantum yield of ligand dissociation for nitriles is much more efficient than that for py, steric bulk was introduced into the ligand set to distort the pseudo-octahedral geometry and lower the energy of the 3LF state. The py dissociation quantum yield with 500 nm irradiation in a series of [Ru(tpy)(NN)(py)]2+ complexes (tpy = 2,2′:6′,2″-terpyridine; NN = bpy, 6,6′-dimethyl-2,2′-bipyridine (Me2bpy), 2,2′-biquinoline (biq)) increases by 2–3 orders of magnitude with the sterically bulky Me2bpy and biq ligands relative to bpy. Ultrafast transient absorption spectroscopy reveals population of the 3LF state within 3–7 ps when NN is bulky, and density functional theory calculations support stabilized 3LF states. Dual activity via ligand dissociation and 1O2 production can be achieved by careful selection of the ligand set to tune the excited-state dynamics. Incorporation of an extended π system in Ru(II) complexes such as [Ru(bpy)(dppn)(CH3CN)2]2+ (dppn = benzo[i]dipyrido[3,2-a:2′,3′-c]phenazine) and [Ru(tpy)(Me2dppn)(py)]2+ (Me2dppn = 3,6-dimethylbenzo[i]dipyrido[3,2-a:2′,3�

Preparation of stable magnetic nanofluids containing Fe3O4@PPy nanoparticles by a novel one-pot route

Directory of Open Access Journals (Sweden)

Zhao Baobao

2011-01-01

Full Text Available Abstract Stable magnetic nanofluids containing Fe3O4@Polypyrrole (PPy nanoparticles (NPs were prepared by using a facile and novel method, in which one-pot route was used. FeCl3·6H2O was applied as the iron source, and the oxidizing agent to produce PPy. Trisodium citrate (Na3cit was used as the reducing reagent to form Fe3O4 NPs. The as-prepared nanofluid can keep long-term stability. The Fe3O4@PPy NPs can still keep dispersing well after the nanofluid has been standing for 1 month and no sedimentation is found. The polymerization reaction of the pyrrole monomers took place with Fe3+ ions as the initiator, in which these Fe3+ ions remained in the solution adsorbed on the surface of the Fe3O4 NPs. Thus, the core-shell NPs of Fe3O4@PPy were obtained. The particle size of the as-prepared Fe3O4@PPy can be easily controlled from 7 to 30 nm by the polymerization reaction of the pyrrole monomers. The steric stabilization and weight of the NPs affect the stability of the nanofluids. The as-prepared Fe3O4@PPy NPs exhibit superparamagnetic behavior.

Single Step In Situ Synthesis and Optical Properties of Polyaniline/ZnO Nanocomposites

Directory of Open Access Journals (Sweden)

Deepali Sharma

2014-01-01

Full Text Available Polyaniline/ZnO nanocomposites were prepared by in situ oxidative polymerization of aniline monomer in the presence of different weight percentages of ZnO nanostructures. The steric stabilizer added to prevent the agglomeration of nanostructures in the polymer matrix was found to affect the final properties of the nanocomposite. ZnO nanostructures of various morphologies and sizes were prepared in the absence and presence of sodium lauryl sulphate (SLS surfactant under different reaction conditions like in the presence of microwave radiation (microwave oven, under pressure (autoclave, under vacuum (vacuum oven, and at room temperature (ambient condition. The conductivity of these synthesized nanocomposites was evaluated using two-probe method and the effect of concentration of ZnO nanostructures on conductivity was observed. X-ray diffraction (XRD, scanning electron microscopy (SEM, transmission electron microscopy (TEM, Fourier transform infrared spectroscopy (FTIR, and UV-visible (UV-VIS spectroscopy techniques were used to characterize nanocomposites. The optical energy band gap of the nanocomposites was calculated from absorption spectra and ranged between 1.5 and 3.21 eV. The reported values depicted the blue shift in nanocomposites as compared to the band gap energies of synthesized ZnO nanostructures. The present work focuses on the one-step synthesis and potential use of PANI/ZnO nanocomposite in molecular electronics as well as in optical devices.

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.

ATLAS I/O Performance Optimization in As-Deployed Environments

CERN Document Server

Maier, Thomas; The ATLAS collaboration; Bhimji, Wahid; Elmsheuser, Johannes; van Gemmeren, Peter; Malon, David; Krumnack, Nils

2015-01-01

I/O is a fundamental determinant in the overall performance of physics analysis and other data-intensive scientific computing. It is, further, crucial to effective resource delivery by the facilities and infrastructure that support data-intensive science. To understand I/O performance, clean measurements in controlled environments are essential, but effective optimization requires as well an understanding of the complicated realities of as-deployed environments. These include a spectrum of local and wide-area data delivery and resilience models, heterogeneous storage systems, matches and mismatches between data organization and access patterns, multi-user considerations that may help or hinder individual job performance, and more. The ATLAS experiment has organized an interdisciplinary working group of I/O, persistence, analysis framework, distributed infrastructure, site deployment, and external experts to understand and improve I/O performance in preparation for Run 2 of the Large Hadron Collider. The adopt...

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.

Mechanism study on the influence of in situ SO{sub x} removal on N{sub 2}O emission in CFB boiler

Energy Technology Data Exchange (ETDEWEB)

Wu, Lingnan, E-mail: wulingnan@126.com [School of Energy, Power and Mechanical Engineering, North China Electric Power University, 102206 Beijing (China); National Engineering Laboratory for Biomass Power Generation Equipment, North China Electric Power University, 102206 Beijing (China); Qin, Wu, E-mail: qinwugx@126.com [National Engineering Laboratory for Biomass Power Generation Equipment, North China Electric Power University, 102206 Beijing (China); Hu, Xiaoying, E-mail: huxy@ncepu.edu.cn [National Engineering Laboratory for Biomass Power Generation Equipment, North China Electric Power University, 102206 Beijing (China); Dong, Changqing, E-mail: cqdong1@163.com [National Engineering Laboratory for Biomass Power Generation Equipment, North China Electric Power University, 102206 Beijing (China); Yang, Yongping, E-mail: yypncepu@163.com [School of Energy, Power and Mechanical Engineering, North China Electric Power University, 102206 Beijing (China)

2015-04-01

Highlights: • The presence of SO{sub 2} would hinder N{sub 2}O decomposition on CaO (1 0 0) surface. • N{sub 2}O decomposition pathway on deSO{sub x} intermediate was proposed. • Temperature dependence of the reaction pathway was considered. • Surface recovery process was the rate-determining step for N{sub 2}O catalytic decomposition. - Abstract: The influence of in situ deSO{sub x} process on N{sub 2}O emission in CFB boiler was studied using density functional theory calculations. The competitive adsorption of SO{sub 2} and N{sub 2}O on pure CaO (1 0 0) surface was first studied and the reaction priority was determined. Results showed that SO{sub 2} was more likely to adsorb on CaO (1 0 0) surface O anion site, which hindered the catalytic decomposition of N{sub 2}O on CaO (1 0 0) surface and sulfurized the CaO (1 0 0) surface under reducing atmosphere. Then a partially sulfurized CaO (1 0 0) surface was established to study the catalytic activity of deSO{sub x} reaction intermediate on N{sub 2}O decomposition. The O atom transfer process and the surface recovery process were two key steps for N{sub 2}O decomposition and the rate-determining step was the latter one. The sulfurization of the surface could deactivate its catalytic activity on N{sub 2}O decomposition compared with pure CaO (1 0 0) surface but it was still better than that of pure CaS (1 0 0) surface. The free Gibbs energy was calculated to incorporate the temperature dependence of respective reactions. When temperature was higher than 373 K, the surface recovery was more likely to proceed via the LH route.

Gummic acid stabilized γ-Fe2O3 aqueous suspensions for biomedical applications

International Nuclear Information System (INIS)

Papaefthymiou, G. C.; Rabias, I.; Fardis, M.; Devlin, E.; Boukos, N.; Tsitrouli, D.; Papavassiliou, G.

2009-01-01

Biomedical applications of magnetic nanoparticles depend critically on their preparation as aqueous colloidal suspensions, or ferrofluids, with long term stability under physiological conditions. Dispersion of the magnetic nanoparticles is generally achieved by the use of protein cages, polysaccharide, polypeptide and charged macromolecular coatings, which minimize interparticle magnetic interactions, particle agglomeration and precipitation. The synthesis and characterization of gummic-acid stabilized maghemite ferrofluids is reported. X-ray diffraction, transmission electron microscope and dynamic light scattering measurements give a γ-Fe 2 O 3 magnetic core diameter of 8 nm and a nanocomposite particle hydrodynamic diameter of 50 nm. Moessbauer and magnetization measurements indicate the presence of isolated, sterically stabilized superparamagnetic nanoparticles resistant to aging, and thus, promising agents for the production of novel magneto-pharmaceuticals.

Hollow NiO nanofibers modified by citric acid and the performances as supercapacitor electrode

International Nuclear Information System (INIS)

Ren, Bo; Fan, Meiqing; Liu, Qi; Wang, Jun; Song, Dalei; Bai, Xuefeng

2013-01-01

Graphical abstract: The possible formation process of NiO nanofibers without citric acid (a), and modified by citric acid (b). When the nanofibers is modified by citric acid, the nickel citrate is produced by complexing action of citric acid and nickel nitrate. Because of the larger space steric hindrance, the structure is limited by the molecular geometry. Under high temperature, the hollow nanofibers composed of NiO slices formed after the removal of PVP. Highlights: ► The method of obtaining hollow nanofibers is raised for the first time. ► The prepared NiO nanofibers are hollow tube and comprised of many NiO sheets. ► The hollow structure facilitated the electrolyte penetration. ► The hollow NiO nanofibers have good electrochemical properties. -- Abstract: NiO nanofibers modified by citric acid (NiO/CA) for supercapacitor material have been fabricated by electrospinning process. The characterizations of the nanofibers are investigated by Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Electrochemical properties are characterized by cyclic voltammetry, galvanostatic charge/discharge measurements, and electrochemical impedance spectroscopy. Results show that the NiO/CA nanofibers are hollow tube and comprised of many NiO sheets. Furthermore, the NiO/CA nanofibers have good electrochemical reversibility and display superior capacitive performance with large capacitance (336 F g −1 ), which is 2.5 times of NiO electrodes. Moreover, the NiO/CA nanofibers show excellent cyclic performance after 1000 cycles

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.

Synthesis and characterization of novel triptycene dianhydrides and polyimides of intrinsic microporosity based on 3,3ʹ-dimethylnaphthidine

KAUST Repository

Ghanem, Bader

2016-08-29

Two intrinsically microporous polyimides were obtained by high-temperature, one-pot poly-condensation reaction of novel triptycene-based dianhydrides containing dimethyl- or diisopropyl-bridgehead groups with a commercially available highly sterically hindered 3,3 \\'-dimethylnaphthidine (DMN) diamine monomer. The dimethyl bridgehead groups in the triptycene building block provided the DMN-based polyimide (TDA1-DMN) with larger surface area (760 m(2) g(-1)) than the diisopropyl-based polyimide (TDA1-DMN) (680 m(2) g(-1)), greater fraction of ultramicroporosity, as observed from N-2 and CO2 NLDFT adsorption analysis, and higher gas permeability and selectivity. Wide-angle X-ray diffraction (WAXD) measurements demonstrated that TDA1-DMN and TDAi3-DMN exhibited a bimodal pore size distribution, where TDA1-DMN showed smaller d-spacing values and broader intensity peaks. Both TDADMN-based polyimides showed very high gas permeabilities with moderate selectivities. For example, fresh TDA1-DMN exhibited an O-2 permeability of 783 Barrer coupled with an O-2/N-2 selectivity of 4.3 and H-2 permeability of 3050 Barrer with H-2/N-2 selectivity of 16.7, values that surpassed the 2008 Robeson permeability/selectivity upper bounds. Physical aging of the TDA-DMN polyimide films over a period of 250 days showed relatively small changes in permeability (similar to 20%) and selectivity (similar to 5%). (C) 2016 Elsevier Ltd. All rights reserved.

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.

Synergetic effect between adsorption and photodegradation on nanostructured TiO{sub 2}/activated carbon fiber felt porous composites for toluene removal

Energy Technology Data Exchange (ETDEWEB)

Li, Min; Lu, Bin; Ke, Qin-Fei; Guo, Ya-Jun; Guo, Ya-Ping, E-mail: ypguo@shnu.edu.cn

2017-07-05

Highlights: • Nanostructured TiO{sub 2}/activated carbon fiber felt porous composites are prepared. • Nanostructures TiO{sub 2} particles on fibers are constructed by nanocrystals. • They have synergetic adsorption-photocatalytic activities for toluene removal. • The adsorption efficiency reaches 98% at toluene concentrations <1150 ppm. • Carbon fibers can hinder the recombination of electron-hole pairs on TiO{sub 2}. - Abstract: The low quantum efficiency and limited adsorption efficiency of TiO{sub 2} makes it only fit for the removal of VOCs with low concentrations. Herein, we for the first time fabricated nanostructured TiO{sub 2}/activated carbon fiber felt (TiO{sub 2}/ACFF) porous composites by the in situ deposition of TiO{sub 2} microspheres on the carbon fibers in ACFF. Interestingly, the TiO{sub 2} microspheres exhibit hierarchical nanostructures constructed by nanocrystals as building blocks. The TiO{sub 2}/ACFF porous composites possess excellent adsorption and photodegradation properties for toluene because of the synergetic effects between the nanostructured TiO{sub 2} and ACFF. The adsorption efficiencies of the TiO{sub 2}/ACFF porous composites reach approximately 98% at the toluene concentration (<1150 ppm) and approximately 77% even at the high concentration of 6900 ppm. Moreover, the ACFF in the TiO{sub 2}/ACFF porous composites significantly enhances photocatalytic property for toluene by hindering the recombination of electron-hole pairs, reducing the TiO{sub 2} band gap energy (E{sub g}) to 2.95 eV and accelerating toluene adsorption. At the toluene concentrations of 230 ppm and 460 ppm, the photocatalytic oxidation efficiency of toluene into CO{sub 2} arrives at 100% and 81.5%, respectively. Therefore, the TiO{sub 2}/ACFF porous composites with synergetic adsorption and photocatalytic activities have great potentials for toluene removal.

Synthesis of mesoporous TS-1 using a hybrid SiO2–TiO2 xerogel for catalytic oxidative desulfurization

International Nuclear Information System (INIS)

Yang, Seung-Tae; Jeong, Kwang-Eun; Jeong, Soon-Yong; Ahn, Wha-Seung

2012-01-01

Graphical abstract: Display Omitted Highlights: ► Meso-TS-1 catalyst was synthesized using a SiO 2 –TiO 2 xerogel with an organosilane precursor. ► Hierarchical pore structure was confirmed by characterization of the materials. ► Catalytic activity was tested using oxidative desulfurization of the model sulfur compounds. ► Meso-TS-1 demonstrated significantly improved catalytic activity than TS-1. -- Abstract: Mesoporous TS-1 (M-TS-1) was synthesized using a hybrid SiO 2 –TiO 2 xerogel combined with an organosilane precursor. Prepared samples were characterized by XRD, UV–vis spectroscopy, SEM, and N 2 adsorption–desorption measurement. M-TS-1, prepared in 2 days, showed high crystallinity and the best textural properties among the samples. The N 2 adsorption–desorption isotherms of M-TS-1 exhibited a hysteresis loop at pressure higher than P/P 0 = 0.4, clearly indicating the existence of mesopores. M-TS-1 has significantly larger mesopore volume (0.48 cm 3 /g) than that of conventional TS-1 (0.07 cm 3 /g), and showed a narrow peak centered at ca. 6.3 nm. In the oxidative desulfurization reaction, M-TS-1 was more active than conventional TS-1 at the same Ti-loading; M-TS-1 produced a dibenzothiophene (DBT) conversion of 96%, whereas conventional TS-1 produced a final DBT conversion of 5.6% after a reaction time of 180 min. Oxidative desulfurization over TS-1 was influenced both by electron density and steric hindrance in the sulfur compounds tested.

Exchange-coupled Fe3O4/CoFe2O4 nanoparticles for advanced magnetic hyperthermia

Science.gov (United States)

Glassell, M.; Robles, J.; Das, R.; Phan, M. H.; Srikanth, H.

Iron oxide nanoparticles especially Fe3O4, γ-Fe2O3 have been extensively studied for magnetic hyperthermia because of their tunable magnetic properties and stable suspension in superparamagnetic regime. However, their relatively low heating capacity hindered practical application. Recently, a large improvement in heating efficiency has been reported in exchange-coupled nanoparticles with exchange coupling between soft and hard magnetic phases. Here, we systematically studied the effect of core and shell size on the heating efficiency of the Fe3O4/CoFe2O4 core/shell nanoparticles. The nanoparticles were synthesized using thermal decomposition of organometallic precursors. Transmission electron microscopy (TEM) showed formation of spherical shaped Fe3O4 and Fe3O-/CoFe2O4 nanoparticles. Magnetic measurements showed high magnetization (≅70 emu/g) and superparamagnetic behavior for the nanoparticles at room temperature. Magnetic hyperthermia results showed a large increase in specific absorption rate (SAR) for 8nm Fe3O4/CoFe2O4 compared to Fe3O4 nanoparticles of the same size. The heating efficiency of the Fe3O4/CoFe2O4 with 1 nm CoFe2O4 (shell) increased from 207 to 220 W/g (for 800 Oe) with increase in core size from 6 to 8 nm. The heating efficiency of the Fe3O4/CoFe2O4 with 2 nm CoFe2O4 (shell) and core size of 8 nm increased from 220 to 460 W/g (for 800 Oe). These exchange-coupled Fe3O4/CoFe2O4 core/shell nanoparticles can be a good candidate for advanced hyperthermia application.

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.)

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...

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

Solid-state synthesis of Li_4Ti_5O_1_2 whiskers from TiO_2-B

International Nuclear Information System (INIS)

Yao, Wenjun; Zhuang, Wei; Ji, Xiaoyan; Chen, Jingjing; Lu, Xiaohua; Wang, Changsong

2016-01-01

Highlights: • The Li_4Ti_5O_1_2 whiskers were synthesized from TiO_2-B whiskers via a solid state reaction. • The TiO_2-B crystal structure for lithium diffusion is easier than anatase. • The separated diffusion and reaction process is crucial for the solid-state syntheses of Li_4Ti_5O_1_2 whiskers. - Abstract: In this work, Li_4Ti_5O_1_2 (LTO) was synthesized from the precursors of TiO_2-B and anatase whiskers, respectively. The synthesized LTO whiskers from TiO_2-B whiskers via a solid state reaction at 650 °C have a high degree of crystallinity with an average diameter of 300 nm. However, when anatase whiskers were used as the precursor, only particle morphology LTO was produced at 750 °C. The further analysis of the precursors, the intermediate products and the final products reveal that the crystal structure of the anatase hinders the diffusion of lithium, leading to a typical reaction–diffusion process. Under this condition, only particle morphology LTO can be produced. However, the crystal structure of the TiO_2-B is easy for lithium diffusion and the process is performed in two separated steps (i.e., diffusion and reaction), which makes it possible to decrease the solid-state reaction temperature down to 650 °C and then maintain the morphologies of whiskers.

Electrografting of alkyl films at low driving force by diverting the reactivity of aryl radicals derived from diazonium salts.

Science.gov (United States)

Hetemi, Dardan; Kanoufi, Frédéric; Combellas, Catherine; Pinson, Jean; Podvorica, Fetah I

2014-11-25

Alkyl and partial perfluoroalkyl groups are strongly attached to carbon surfaces through (i) the abstraction of the iodine atom from an iodoalkane by the sterically hindered 2,6-dimethylphenyl radical and (ii) the reaction of the ensuing alkyl radical with the carbon surface. Since the 2,6-dimethylphenyl radical is obtained at -0.25 V/Ag/AgCl by reducing the corresponding diazonium salt, the electrografting reaction is facilitated by ∼1.7 V by comparison with the direct electrografting of the iodo compounds. Layers of various thicknesses, including monolayers, are obtained by controlling the time duration of the electrolysis. The grafted films are characterized by electrochemistry, IR, XPS, ellipsometry, and water contact angles.

Xanthine and 8-oxoguanine in G-quadruplexes: formation of a G·G·X·O tetrad.

Science.gov (United States)

Cheong, Vee Vee; Heddi, Brahim; Lech, Christopher Jacques; Phan, Anh Tuân

2015-12-02

G-quadruplexes are four-stranded structures built from stacked G-tetrads (G·G·G·G), which are planar cyclical assemblies of four guanine bases interacting through Hoogsteen hydrogen bonds. A G-quadruplex containing a single guanine analog substitution, such as 8-oxoguanine (O) or xanthine (X), would suffer from a loss of a Hoogsteen hydrogen bond within a G-tetrad and/or potential steric hindrance. We show that a proper arrangement of O and X bases can reestablish the hydrogen-bond pattern within a G·G·X·O tetrad. Rational incorporation of G·G·X·O tetrads in a (3+1) G-quadruplex demonstrated a similar folding topology and thermal stability to that of the unmodified G-quadruplex. pH titration conducted on X·O-modified G-quadruplexes indicated a protonation-deprotonation equilibrium of X with a pKa ∼6.7. The solution structure of a G-quadruplex containing a G·G·X·O tetrad was determined, displaying the same folding topology in both the protonated and deprotonated states. A G-quadruplex containing a deprotonated X·O pair was shown to exhibit a more electronegative groove compared to that of the unmodified one. These differences are likely to manifest in the electronic properties of G-quadruplexes and may have important implications for drug targeting and DNA-protein interactions. © The Author(s) 2015. Published by Oxford University Press on behalf of Nucleic Acids Research.

Rapid and large-scale synthesis of Co3O4 octahedron particles with very high catalytic activity, good supercapacitance and unique magnetic property

CSIR Research Space (South Africa)

Chowdhury, M

2015-12-01

Full Text Available Scarcity of rapid and large scale synthesis of functional materials, hinders the progress from laboratory scale to commercial applications. In this study, we report a rapid and large scale synthesis of Co(Sub3)O(sub4) octahedron micron size (1.3 µm...

Highly Durable Na2V6O16·1.63H2O Nanowire Cathode for Aqueous Zinc-Ion Battery.

Science.gov (United States)

Hu, Ping; Zhu, Ting; Wang, Xuanpeng; Wei, Xiujuan; Yan, Mengyu; Li, Jiantao; Luo, Wen; Yang, Wei; Zhang, Wencui; Zhou, Liang; Zhou, Zhiqiang; Mai, Liqiang

2018-03-14

Rechargeable aqueous zinc-ion batteries are highly desirable for grid-scale applications due to their low cost and high safety; however, the poor cycling stability hinders their widespread application. Herein, a highly durable zinc-ion battery system with a Na 2 V 6 O 16 ·1.63H 2 O nanowire cathode and an aqueous Zn(CF 3 SO 3 ) 2 electrolyte has been developed. The Na 2 V 6 O 16 ·1.63H 2 O nanowires deliver a high specific capacity of 352 mAh g -1 at 50 mA g -1 and exhibit a capacity retention of 90% over 6000 cycles at 5000 mA g -1 , which represents the best cycling performance compared with all previous reports. In contrast, the NaV 3 O 8 nanowires maintain only 17% of the initial capacity after 4000 cycles at 5000 mA g -1 . A single-nanowire-based zinc-ion battery is assembled, which reveals the intrinsic Zn 2+ storage mechanism at nanoscale. The remarkable electrochemical performance especially the long-term cycling stability makes Na 2 V 6 O 16 ·1.63H 2 O a promising cathode for a low-cost and safe aqueous zinc-ion battery.

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

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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.

Secondary promoters in alumina-supported nickel-molybdenum hydroprocessing catalysts

Energy Technology Data Exchange (ETDEWEB)

Lewis, J.M.

1992-01-01

Two secondary promoters, phosphorus and fluoride, have been investigated for their influences on the physicochemical properties of alumina-supported nickel-molybdenum hydroprocessing catalysts. Model compound reactions and infrared spectroscopy were used to probe the functionalities of the different catalysts, and the catalysts were tested in the hydroprocessing of a low-nitrogen and a high-nitrogen (quinoline-spiked) gas oil feed to assess the utility of the model compound reaction studies. Fluoride-promoted catalysts with high cumene hydrocracking activity and with comparable thiophene hydrodesulphurization (HDS) activity to Ni-Mo/Al[sub 2]O[sub 3] can be prepared by coimpregnation of the F, Ni and Mo additives. Fluoride promotes the hydrogenation (HYD) and HDS activity of Ni-Mo/Al[sub 2]O[sub 3] in the hydroprocessing (HYD) and HDS activity of Ni-Mo/Al[sub 2]O[sub 3] in the hydroprocessing of a low-nitrogen feed. Fluoride promotes the quinoline hydrodenitrogenation (HDN) activity of Ni-Mo/Al[sub 2]O[sub 3] catalysts. Impregnation of phosphorus prior to the metal additives results in catalysts which are more active in HDS. Phosphorus increases indirectly the Broensted acidity of the catalyst by increasing the activity of the MoS[sub 2]-associated acid sites. Phosphorus promotes the HDSW and HYD activities of Ni-Mo/Al[sub 2]O[sub 3] in the hydroprocessing of the low-N feed. A promotional effect of phosphorus is seen in quinoline HDN. P- and F-promoted Ni-MO/Al[sub 2]O[sub 3] catalysts are very active in quinoline HDN and maintain good activity in HDS and HYD of the high-N feed. Thiophene HDS was a good reaction for probing the activity of catalysts in the HDS of sterically-unhindered molecules, but an inaccurate probe for the HDS of hindered compounds.

Theoretical Time Dependent Thermal Neutron Spectra and Reaction Rates in H2O and D2O

International Nuclear Information System (INIS)

Purohit, S.N.

1966-04-01

The early theoretical and experimental time dependent neutron thermalization studies were limited to the study of the transient spectrum in the diffusion period. The recent experimental measurements of the time dependent thermal neutron spectra and reaction rates, for a number of moderators, have generated considerable interest in the study of the time dependent Boltzmann equation. In this paper we present detailed results for the time dependent spectra and the reaction rates for resonance detectors using several scattering models of H 2 O and D 2 O. This study has been undertaken in order to interpret the integral time dependent neutron thermalization experiments in liquid moderators which have been performed at the AB Atomenergi. The proton gas and the deuteron gas models are inadequate to explain the measured reaction rates in H 2 O and D 2 O. The bound models of Nelkin for H 2 O and of Butler for D 2 O give much better agreement with the experimental results than the gas models. Nevertheless, some disagreement between theoretical and experimental results still persists. This study also indicates that the bound model of Butler and the effective mass 3. 6 gas model of Brown and St. John give almost identical reaction rates. It is also surprising to note that the calculated reaction rate for Cd for the Butler model appears to be in better agreement with the experimental results of D 2 O than of the Nelkin model with H 2 O experiments. The present reaction rate studies are sensitive enough so as to distinguish between the gas model and the bound model of a moderator. However, to investigate the details of a scattering law (such as the effect of the hindered rotations in H 2 O and D 2 O and the weights of different dynamical modes) with the help of these studies would require further theoretical as well as experimental investigations. Theoretical results can be further improved by improving the source for thermal neutrons, the group structure and the scattering

17O NMR Studies of the Solvation State of cissolidustrans Isomers of Amides and Model Protected Peptides

Science.gov (United States)

Gerothanassis; Vakka; Troganis

1996-06-01

17O shielding constants have been utilized to investigate solvation differences of the cissolidustrans isomers of N-methylformamide (NMF), N-ethylformamide (NEF), and tert-butylformamide (TBF) in a variety of solvents with particular emphasis on aqueous solution. Comparisons are also made with protected peptides of the formulas CH3CO-YOH, CH3CO-Y-NHR (Y = Pro, Sar), and CH3CO-Y-Z-NHR (Y = Pro; Z = D-Ala) selectively enriched in 17O at the acetyl oxygen atom. Hydration at the amide oxygen induces large and specific modifications of the 17O shielding constants, which are practically the same for the cis and trans isomers of NMF, NEF, and the protected peptides. For tert-butylformamide, the strong deshielding of the trans isomer compared to that of the cis isomer may be attributed to an out-of-plane (torsion-angle) deformation of the amide bond andsolidusor a significant reduction of solvation of the trans isomer due to steric inhibition of the bulky tert-butyl group. Good linear correlation between delta(17O) of amides and delta(17O) of acetone was found for different solvents which have varying dielectric constants and solvation abilities. Sum-over-states calculations, within the solvaton model, underestimate effects of the dielectric constant of the medium on 17O shielding, while finite-perturbation-theory calculations give good agreement with the experiment.

Graphene Modified TiO2 Composite Photocatalysts: Mechanism, Progress and Perspective

Science.gov (United States)

Tang, Bo; Chen, Haiqun; Peng, Haoping; Wang, Zhengwei; Huang, Weiqiu

2018-01-01

Graphene modified TiO2 composite photocatalysts have drawn increasing attention because of their high performance. Some significant advancements have been achieved with the continuous research, such as the corresponding photocatalytic mechanism that has been revealed. Specific influencing factors have been discovered and potential optimizing methods are proposed. The latest developments in graphene assisted TiO2 composite photocatalysts are abstracted and discussed. Based on the primary reasons behind the observed phenomena of these composite photocatalysts, probable development directions and further optimizing strategies are presented. Moreover, several novel detective technologies—beyond the decomposition test—which can be used to judge the photocatalytic performances of the resulting photocatalysts are listed and analyzed. Although some objectives have been achieved, new challenges still exist and hinder the widespread application of graphene-TiO2 composite photocatalysts, which deserves further study. PMID:29439545

The role of Sr2+ on the structure and reactivity of SrO-CaO-ZnO-SiO2 ionomer glasses.

Science.gov (United States)

Boyd, Daniel; Towler, Mark R; Watts, Sally; Hill, Robert G; Wren, Anthony W; Clarkin, Owen M

2008-02-01

The suitability of Glass Polyalkenoate Cements (GPCs) for use in orthopaedics is retarded by the presence in the glass phase of aluminium, a neurotoxin. Unfortunately, the aluminium ion plays an integral role in the setting process of GPCs and its absence is likely to hinder cement formation. However, the authors have previously shown that aluminium free GPCs may be formulated based on calcium zinc silicate glasses and these novel materials exhibit significant potential as hard tissue biomaterials. To further improve their potential, and given that Strontium (Sr) based drugs have had success in the treatment of osteoporosis, the authors have substituted Calcium (Ca) with Sr in the glass phase of a series of aluminium free GPCs. However to date little data exists on the effect SrO has on the structure and reactivity of SrO-CaO-ZnO-SiO(2) glasses. The objective of this work was to characterise the effect of the Ca/Sr substitution on the structure of such glasses, and evaluate the subsequent reactivity of these glasses with an aqueous solution of Polyacrylic acid (PAA). To this end (29)Si MAS-NMR, differential scanning calorimetry (DSC), X-ray diffraction, and network connectivity calculations, were used to characterize the structure of four strontium calcium zinc silicate glasses. Following glass characterization, GPCs were produced from each glass using a 40 wt% solution of PAA (powder:liquid = 2:1.5). The working times and setting times of the GPCs were recorded as per International standard ISO9917. The results acquired as part of this research indicate that the substitution of Ca for Sr in the glasses examined did not appear to significantly affect the structure of the glasses investigated. However it was noted that increasing the amount of Ca substituted for Sr did result in a concomitant increase in setting times, a feature that may be attributable to the higher basicity of SrO over CaO.

Characterization of CaSn(OH6 and CaSnO3 Nanostructures Synthesized by a New Precursor

Directory of Open Access Journals (Sweden)

S. Moshtaghi

2015-04-01

Full Text Available In this paper, calcium stannate nanoparticles were synthesized by a fast and simple co-precipitation procedure. For CaSnO3 preparation ammonia was used as precipitation agent. The effect of various surfactants such as cationic, anionic and neutral on the morphology of the products was investigated. By changing in Ca(Sal2 as a new precursor different morphologies were obtained. Ligand as a capping agent with steric hindrance leads to preparation of product with lower particle size. These semiconductor nanostructures have photo-catalyst activities and can degrade organic dyes as water pollution. The synthesized materials were characterized by X-ray diffraction (XRD technique, scanning electron microscopy (SEM Fourier transform infrared (FT-IR and UV-visible spectroscopy.

17O NMR Studies of the Solvation State of cis/trans Isomers of Amides and Model Protected Peptides

Science.gov (United States)

Gerothanassis, Ioannis P.; Vakka, Constantina; Troganis, Anastasios

1996-06-01

17O shielding constants have been utilized to investigate solvation differences of the cis/trans isomers ofN-methylformamide (NMF),N-ethylformamide (NEF), andtert-butylformamide (TBF) in a variety of solvents with particular emphasis on aqueous solution. Comparisons are also made with protected peptides of the formulas CH3CO-YOH, CH3CO-Y-NHR (Y = Pro, Sar), and CH3CO-Y-Z-NHR (Y = Pro; Z =D-Ala) selectively enriched in17O at the acetyl oxygen atom. Hydration at the amide oxygen induces large and specific modifications of the17O shielding constants, which are practically the same for the cis and trans isomers of NMF, NEF, and the protected peptides. Fortert-butylformamide, the strong deshielding of the trans isomer compared to that of the cis isomer may be attributed to an out-of-plane (torsion-angle) deformation of the amide bond and/or a significant reduction of solvation of the trans isomer due to steric inhibition of the bulkytert-butyl group. Good linear correlation between δ(17O) of amides and δ(17O) of acetone was found for different solvents which have varying dielectric constants and solvation abilities. Sum-over-states calculations, within the solvaton model, underestimate effects of the dielectric constant of the medium on17O shielding, while finite-perturbation-theory calculations give good agreement with the experiment.

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

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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.

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.

Exploring conditions for the enhancement of acene semiconductors through the use of the Diels-alder reaction

Science.gov (United States)

Qualizza, Brittni A.

This dissertation demonstrates the application of SAMs to the surface of acene crystals, specifically of tetracene and rubrene, using the Diels-Alder reaction. The second chapter details preliminary reaction results and two analytical methods which were employed to confirm adsorption of the dienophile on the surface of single crystals, tetracene and rubrene. These were mass spectrometry and X-ray photoelectron spectroscopy (XPS). Mass spectrometry experiments distinguish the chemical identity of adduct on the crystals and also it discerned chemi- and physisorbed molecules from one another. XPS was used to prove face selectivity of the reaction by the detection of dichloromaleic anhydride. From a mechanistic standpoint, this system demonstrated unusual steric effects: the reaction of one face of the tetracene crystal was virtually inert, while another face was facile. The dienophiles' steric bulk was also expected to play critical role for these confined systems, however analysis of surface data was hindered by the relative lack of corresponding solution kinetic data. While the rate of anthracene's reaction has been studied extensively with a range of dienophiles and tetracene/pentacene has been studied theoretically (with limited experimental reports), an expansive report was generated to aid in future interpretations of acene systems. These kinetic results constitute chapter three.

Clearance and Biodistribution of Liposomally Encapsulated Nitroxides: A Model for Targeted Delivery of Electron Paramagnetic Resonance Imaging Probes to Tumors

Science.gov (United States)

Burks, Scott R.; Legenzov, Eric A.; Rosen, Gerald M.

2011-01-01

Electron paramagnetic resonance (EPR) imaging using nitroxides as molecular probes is potentially a powerful tool for the detection and physiological characterization of micrometastatic lesions. Encapsulating nitroxides in anti-HER2 immunoliposomes at high concentrations to take advantage of the “self-quenching” phenomenon of nitroxides allows generation of robust EPR signals in HER2-overexpressing breast tumor cells with minimal background from indifferent tissues or circulating liposomes. We investigated the in vivo pharmacological properties of nitroxides encapsulated in sterically stabilized liposomes designed for long circulation times. We show that circulation times of nitroxides can be extended from hours to days; this increases the proportion of liposomes in circulation to enhance tumor targeting. Furthermore, nitroxides encapsulated in sterically stabilized anti-HER2 immunoliposomes can be delivered to HER2-overexpressing tumors at micromolar concentrations, which should be imageable by EPR. Lastly, after in vivo administration, liposomally encapsulated nitroxide signal also appears in the liver, spleen, and kidneys. Although these organs are spatially distinct and would not hinder tumor imaging in our model, understanding nitroxide signal retention in these organs is essential for further improvements in EPR imaging contrast between tumors and other tissues. These results lay the foundation to use liposomally delivered nitroxides and EPR imaging to visualize tumor cells in vivo. PMID:21737567

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)

Effect of sulfate ions on the crystallization and photocatalytic activity of TiO2/diatomite composite photocatalyst

Science.gov (United States)

Zhang, Jinjun; Wang, Xiaoyan; Wang, Jimei; Wang, Jing; Ji, Zhijiang

2016-01-01

TiO2 nanoparticles were immobilized on diatomite by hydrolysis-deposition method using titanium tetrachloride as precursor. The effect of sulfate ions on the crystallization and photocatalytic activity of TiO2/diatomite composite photocatalyst was characterized by TG-DSC, XRD, BET surface area, SEM, FT-IR spectroscopy, XPS and UV-vis diffuse reflectance spectra. The results indicate that addition of a small amount of sulfate ions promotes the formation of anatase phase and inhibits the transformation from anatase to rutile. On the other hand, sulfate ions immobilized on the surface of TiO2/diatomite have strong affinity for electrons, capturing the photo-generated electrons, which hinders the recombination of electrons and holes.

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.

Enhanced photoelectrocatalytic performance of α-Fe2O3 thin films by surface plasmon resonance of Au nanoparticles coupled with surface passivation by atom layer deposition of Al2O3.

Science.gov (United States)

Liu, Yuting; Xu, Zhen; Yin, Min; Fan, Haowen; Cheng, Weijie; Lu, Linfeng; Song, Ye; Ma, Jing; Zhu, Xufei

2015-12-01

The short lifetime of photogenerated charge carriers of hematite (α-Fe2O3) thin films strongly hindered the PEC performances. Herein, α-Fe2O3 thin films with surface nanowire were synthesized by electrodeposition and post annealing method for photoelectrocatalytic (PEC) water splitting. The thickness of the α-Fe2O3 films can be precisely controlled by adjusting the duration of the electrodeposition. The Au nanoparticles (NPs) and Al2O3 shell by atom layer deposition were further introduced to modify the photoelectrodes. Different constructions were made with different deposition orders of Au and Al2O3 on Fe2O3 films. The Fe2O3-Au-Al2O3 construction shows the best PEC performance with 1.78 times enhancement by localized surface plasmon resonance (LSPR) of NPs in conjunction with surface passivation of Al2O3 shells. Numerical simulation was carried out to investigate the promotion mechanisms. The high PEC performance for Fe2O3-Au-Al2O3 construction electrode could be attributed to the Al2O3 intensified LSPR, effective surface passivation by Al2O3 coating, and the efficient charge transfer due to the Fe2O3-Au Schottky junctions.

Solid-state synthesis of Li{sub 4}Ti{sub 5}O{sub 12} whiskers from TiO{sub 2}-B

Energy Technology Data Exchange (ETDEWEB)

Yao, Wenjun [State Key Laboratory of Materials-Oriented Chemical Engineering, College of Chemical Engineering, Nanjing Tech University, No. 5 Xin Mofan Road, Nanjing 210009 (China); Zhuang, Wei [State Key Laboratory of Materials-Oriented Chemical Engineering, College of Chemical Engineering, Nanjing Tech University, No. 5 Xin Mofan Road, Nanjing 210009 (China); College of Biotechnology and Pharmaceutical Engineering, National Engineering Technique Research Center for Biotechnology, Nanjing Tech University, No. 30, Puzhu South Road, Nanjing 211816 (China); Ji, Xiaoyan [Division of Energy Science/Energy Engineering, Luleå University of Technology, Luleå 97187 Sweden (Sweden); Chen, Jingjing; Lu, Xiaohua [State Key Laboratory of Materials-Oriented Chemical Engineering, College of Chemical Engineering, Nanjing Tech University, No. 5 Xin Mofan Road, Nanjing 210009 (China); Wang, Changsong, E-mail: wcs@njtech.edu.cn [State Key Laboratory of Materials-Oriented Chemical Engineering, College of Chemical Engineering, Nanjing Tech University, No. 5 Xin Mofan Road, Nanjing 210009 (China)

2016-03-15

Highlights: • The Li{sub 4}Ti{sub 5}O{sub 12} whiskers were synthesized from TiO{sub 2}-B whiskers via a solid state reaction. • The TiO{sub 2}-B crystal structure for lithium diffusion is easier than anatase. • The separated diffusion and reaction process is crucial for the solid-state syntheses of Li{sub 4}Ti{sub 5}O{sub 12} whiskers. - Abstract: In this work, Li{sub 4}Ti{sub 5}O{sub 12} (LTO) was synthesized from the precursors of TiO{sub 2}-B and anatase whiskers, respectively. The synthesized LTO whiskers from TiO{sub 2}-B whiskers via a solid state reaction at 650 °C have a high degree of crystallinity with an average diameter of 300 nm. However, when anatase whiskers were used as the precursor, only particle morphology LTO was produced at 750 °C. The further analysis of the precursors, the intermediate products and the final products reveal that the crystal structure of the anatase hinders the diffusion of lithium, leading to a typical reaction–diffusion process. Under this condition, only particle morphology LTO can be produced. However, the crystal structure of the TiO{sub 2}-B is easy for lithium diffusion and the process is performed in two separated steps (i.e., diffusion and reaction), which makes it possible to decrease the solid-state reaction temperature down to 650 °C and then maintain the morphologies of whiskers.

The metal-insulator transition of RNiO3 perovskites. What can we learn from neutron diffraction?

International Nuclear Information System (INIS)

Medarde, M.L.

1996-01-01

RNiO 3 perovskites (R = rare earth) provide a remarkable opportunity to study the relationship between structural and physical properties since by moving along the 4f rare earth series, the evolution of several transport and magnetic properties can be nicely correlated to the steric effects associated with the lanthanide contraction. The most appealing example is probably the metal-insulator transition discovered for the compounds with R≠La, whose critical temperature T M-I increases with decreasing size of the rare earth ion. In this lecture, a summary of the most relevant neutron diffraction results on this system is presented. Moreover, the nickelates are used as an example to illustrate the performance of the diffractometers HRPT and DMCG to be installed at the SINQ. (author) 12 figs., 2 tabs., 17 refs

Synthesis of mesoporous TS-1 using a hybrid SiO{sub 2}–TiO{sub 2} xerogel for catalytic oxidative desulfurization

Energy Technology Data Exchange (ETDEWEB)

Yang, Seung-Tae [Department of Chemical Engineering, Inha University, Incheon 402-751 (Korea, Republic of); Jeong, Kwang-Eun; Jeong, Soon-Yong [Research Center for Green Catalysis, Division of Green Chemistry and Engineering Research, Korea Research Institute of Chemical Technology, P.O. Box 107, 141 Gajeong-ro, Yuseong, Daejeon 305-600 (Korea, Republic of); Ahn, Wha-Seung, E-mail: whasahn@inha.ac.kr [Department of Chemical Engineering, Inha University, Incheon 402-751 (Korea, Republic of)

2012-12-15

Graphical abstract: Display Omitted Highlights: ► Meso-TS-1 catalyst was synthesized using a SiO{sub 2}–TiO{sub 2} xerogel with an organosilane precursor. ► Hierarchical pore structure was confirmed by characterization of the materials. ► Catalytic activity was tested using oxidative desulfurization of the model sulfur compounds. ► Meso-TS-1 demonstrated significantly improved catalytic activity than TS-1. -- Abstract: Mesoporous TS-1 (M-TS-1) was synthesized using a hybrid SiO{sub 2}–TiO{sub 2} xerogel combined with an organosilane precursor. Prepared samples were characterized by XRD, UV–vis spectroscopy, SEM, and N{sub 2} adsorption–desorption measurement. M-TS-1, prepared in 2 days, showed high crystallinity and the best textural properties among the samples. The N{sub 2} adsorption–desorption isotherms of M-TS-1 exhibited a hysteresis loop at pressure higher than P/P{sub 0} = 0.4, clearly indicating the existence of mesopores. M-TS-1 has significantly larger mesopore volume (0.48 cm{sup 3}/g) than that of conventional TS-1 (0.07 cm{sup 3}/g), and showed a narrow peak centered at ca. 6.3 nm. In the oxidative desulfurization reaction, M-TS-1 was more active than conventional TS-1 at the same Ti-loading; M-TS-1 produced a dibenzothiophene (DBT) conversion of 96%, whereas conventional TS-1 produced a final DBT conversion of 5.6% after a reaction time of 180 min. Oxidative desulfurization over TS-1 was influenced both by electron density and steric hindrance in the sulfur compounds tested.

Gas swelling behaviour at different stages in Li4Ti5O12/LiNi1/3Co1/3Mn1/3O2 pouch cells

Science.gov (United States)

Liu, Wei; Liu, Haohan; Wang, Qian; Zhang, Jian; Xia, Baojia; Min, Guoquan

2017-11-01

Gas swelling behaviour is a major drawback of batteries that are based on Li4Ti5O12 anode materials and hinders their application. In this article, the morphology and electronic structure changes of Li4Ti5O12 electrodes at ageing and cycling stages are investigated using scanning electron microscopy, X-ray absorption near-edge structure and X-ray photoelectron spectroscopy. A simple method that uses an air bag to collect the generated gases was conducted and the gases were then characterised by gas chromatography/mass spectrometry. The results indicate that the charge transformation of Ti ions would aggravate the gas swelling behaviour. The solid electrolyte interphase (SEI) films form on the surface of the Li4Ti5O12 particles and become thicker with increasing charge state. The gas components change significantly during the ageing and cycling, indicating the complexity of the gas swelling mechanism.

A velhice, entre o normal e o patológico Old age, normality versus pathology

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Daniel Groisman

2002-04-01

Full Text Available Com a ascensão do envelhecimento da população brasileira ao posto de 'problema social', assistimos a um crescimento cada vez maior do número de especialistas dedicados a este 'grupo etário': os geriatras e gerontólogos, que ocupam papel de destaque na formulação das novas formas de gestão da velhice. No entanto, a gerontologia parece ter problemas internos na sua formulação como campo de saber, que parecem comprometer sua consolidação como profissão e seu reconhecimento como disciplina científica. No presente artigo, procuramos chamar atenção para as dificuldades que a gerontologia encontra para delimitar seu campo e definir seu objeto. Sustentamos que tais dificuldades parecem derivar de uma questão central, que é a impossibilidade de serem delimitadas as fronteiras entre o normal e o patológico, na velhice. Por fim, analisamos a questão sob um ponto de vista histórico, à luz do processo de constituição do saber médico sobre o envelhecimento.Since life expectancy of Brazilian population increased and aging was considered a "social problem", there has been a boom of specialists in old age. Gerontologists and geriatricians are now playing a relevant role in setting new trends to the management of issues related to old age. However, gerontology as a field of knowledge seems to have internal questions that apparently hinder its professional consolidation and its scientific recognition. In this article, the author focus the difficulties gerontology has in order to delimitate its field of action and to define the object of its studies. The author argues that such difficulties derive from a central point: the impossibility to delimitate the frontiers between what is normal and what is pathological in old age. He also analyzes the constitution of medical knowledge on aging in a historical perspective.

Coordination structure of adsorbed Zn(II) at Water-TiO2 interfaces

Energy Technology Data Exchange (ETDEWEB)

He, G.; Pan, G.; Zhang, M.; Waychunas, G.A.

2011-01-15

The local structure of aqueous metal ions on solid surfaces is central to understanding many chemical and biological processes in soil and aquatic environments. Here, the local coordination structure of hydrated Zn(II) at water-TiO{sub 2} interfaces was identified by extended X-ray absorption fine structure (EXAFS) and X-ray absorption near-edge structure (XANES) spectroscopy combined with density functional theory (DFT) calculations. A nonintegral coordination number of average {approx}4.5 O atoms around a central Zn atom was obtained by EXAFS analysis. DFT calculations indicated that this coordination structure was consistent with the mixture of 4-coordinated bidentate binuclear (BB) and 5-coordinated bidentate mononuclear (BM) metastable equilibrium adsorption (MEA) states. The BB complex has 4-coordinated Zn, while the monodentate mononuclear (MM) complex has 6-coordinated Zn, and a 5-coordinated adsorbed Zn was found in the BM adsorption mode. DFT calculated energies showed that the lower-coordinated BB and BM modes were thermodynamically more favorable than the higher-coordinated MM MEA state. The experimentally observed XANES fingerprinting provided additional direct spectral evidence of 4- and 5-coordinated Zn-O modes. The overall spectral and computational evidence indicated that Zn(II) can occur in 4-, 5-, and 6-oxygen coordinated sites in different MEA states due to steric hindrance effects, and the coexistence of different MEA states formed the multiple coordination environments.

Reproducibility and Variability of I/O Performance on BG/Q: Lessons Learned from a Data Aggregation Algorithm

Energy Technology Data Exchange (ETDEWEB)

Tessier, Francois [Argonne National Lab. (ANL), Argonne, IL (United States); Vishwanath, Venkatram [Argonne National Lab. (ANL), Argonne, IL (United States)

2017-11-28

Reading and writing data efficiently from different tiers of storage is necessary for most scientific simulations to achieve good performance at scale. Many software solutions have been developed to decrease the I/O bottleneck. One wellknown strategy, in the context of collective I/O operations, is the two-phase I/O scheme. This strategy consists of selecting a subset of processes to aggregate contiguous pieces of data before performing reads/writes. In our previous work, we implemented the two-phase I/O scheme with a MPI-based topology-aware algorithm. Our algorithm showed very good performance at scale compared to the standard I/O libraries such as POSIX I/O and MPI I/O. However, the algorithm had several limitations hindering a satisfying reproducibility of our experiments. In this paper, we extend our work by 1) identifying the obstacles we face to reproduce our experiments and 2) discovering solutions that reduce the unpredictability of our results.

Polymers with complexing properties. Simple poly(amino acids)

Science.gov (United States)

Roque, J. M.

1978-01-01

The free amino (0.3 equiv/residue) and carboxyl (0.5 equiv/residue) groups of thermal polylysine increased dramatically on treatment with distilled water. The total hydrolysis of such a polymer was abnormal in that only about 50% of the expected amino acids were recovered. Poly (lysine-co-alanine-co-glycine) under usual conditions hydrolyzed completely in 8 hours; whereas, when it was pretreated with diazomethane, a normal period of 24 hours was required to give (nearly) the same amounts of each free amino acid as compared with those obtained from the untreated polymer. The amino groups of the basic thermal poly(amino acids) were sterically hindered. The existence of nitrogen atoms linking two or three chains and reactive groups (anhydride, imine) were proposed.

Preparation by Poly(Acrylic Acid) Sol-Gel Method and Thermoelectric Properties of γ-Na x CoO2 Bulk Materials

Science.gov (United States)

Li, Xiaoyu; Zhang, Li; Tang, Xinfeng

2017-11-01

γ-Na x CoO2 single-phase powders have been synthesized by a poly(acrylic acid) (PAA) sol-gel (SG) method, and γ-Na x CoO2 bulk ceramic fabricated using spark plasma sintering. The effects of the PAA concentration on the sample phase composition and morphology were investigated. The thermoelectric properties of the γ-Na x CoO2 bulk ceramic were also studied. The results show that the PAA concentration did not significantly affect the crystalline phase of the product. However, agglomeration of γ-Na x CoO2 crystals was suppressed by the steric effect of PAA. The Na x CoO2 bulk ceramic obtained using the PAA SG method had higher crystallographic anisotropy, better chemical homogeneity, and higher density than the sample obtained by solid-state reaction (SSR), leading to improved thermoelectric performance. The PAA SG sample had power factor (in-plane PF = σS 2) of 0.61 mW m-1 K-2 and dimensionless figure of merit ( ZT) along the in-plane direction of 0.19 at 900 K, higher than for the SSR sample (in-plane PF = 0.51 mW m-1 K-2, in-plane ZT = 0.17). These results demonstrate that a simple and feasible PAA SG method can be used for synthesis of Na x CoO2 ceramics with improved thermoelectric properties.

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)

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.

The metal-insulator transition of RNiO{sub 3} perovskites. What can we learn from neutron diffraction?

Energy Technology Data Exchange (ETDEWEB)

Medarde, M L [Paul Scherrer Inst. (PSI), Villigen (Switzerland)

1996-11-01

RNiO{sub 3} perovskites (R = rare earth) provide a remarkable opportunity to study the relationship between structural and physical properties since by moving along the 4f rare earth series, the evolution of several transport and magnetic properties can be nicely correlated to the steric effects associated with the lanthanide contraction. The most appealing example is probably the metal-insulator transition discovered for the compounds with R{ne}La, whose critical temperature T{sub M-I} increases with decreasing size of the rare earth ion. In this lecture, a summary of the most relevant neutron diffraction results on this system is presented. Moreover, the nickelates are used as an example to illustrate the performance of the diffractometers HRPT and DMCG to be installed at the SINQ. (author) 12 figs., 2 tabs., 17 refs.

Reactivity of phosphorene with a 3d element trioxide (CrO3) considering van der Waals molecular interactions: a DFT-D2 study.

Science.gov (United States)

Rubio-Pereda, Pamela; Cocoletzi, Gregorio H

2017-02-01

First-principle calculations are performed to investigate the interaction between clean black phosphorene and the CrO 3 molecule which is known to be a powerful oxidizer and a suspected carcinogen. Van der Waals forces are included in all calculations through empirical corrections. Energetics studies are first done to determine the structural stability. Then charge density, Löwdin population analysis and electronic states are evaluated. Results show that the CrO 3 molecule, with an acceptor electron character, is chemisorbed on the phosphorene surface inducing minimal geometrical distortions, however, after adsorption, a partial charge gradient is produced between the P atoms located at the phosphorene upper and lower planes. Furthermore, variations on the CrO 3 concentration causes different interaction strengths. At high concentrations of adsorbed CrO 3 molecules, the interaction with the surface becomes stronger due to an increased steric effect between neighboring molecules. Nevertheless, this effect along with the geometrical distortions produced on the phosphorene structure, due to the large number of molecules adsorbed, leads to a decrement on the adsorption energy. It is expected that the reported results may render phosphorene as a promising material for application as a gas sensor.

Factors influencing catalytic behavior of titanium complexes bearing bisphenolate ligands toward ring-opening polymerization of L-lactide and ε-caprolactone

Directory of Open Access Journals (Sweden)

M-T. Jiang

2018-02-01

Full Text Available A series of titanium complexes bearing substituted diphenolate ligands (RCH(phenolate2, where R = H, CH3, o-OTs-phenyl, o-F-phenyl, o-OMe-phenyl, 2,4-OMe-phenyl was synthesized and studied as catalysts for the ring opening polymerization of L-lactide and ε-caprolactone. Ligands were designed to probe the role of chelate effect and steric effect in the catalytic performance. From the structure of triphenolate (with one extra coordination site than diphenolate ligand Ti complex, TriOTiOiPr2, we found no additional chelation to influence the catalytic activity of Ti complexes. It was found that bulky aryl groups in the diphenolate ligands decreased the rate of polymerization most. We conclude that steric effect is the most controlling factor in these polymerization reactions by using Ti complexes bearing diphenolate ligands as catalysts since it is responsible for the exclusion of needed space for incoming monomer by the bulky substituents on the catalyst.

Large-Scale Synthesis of Transition-Metal-Doped TiO2 Nanowires with Controllable Overpotential

Energy Technology Data Exchange (ETDEWEB)

Liu, Bin; Chen, HaoMing; Liu, Chong; Andrews, Sean; Han, Chris; Yang, Peidong

2013-03-13

Practical implementation of one-dimensional semiconductors into devices capable of exploiting their novel properties is often hindered by low product yields, poor material quality, high production cost, or overall lack of synthetic control. Here, we show that a molten-salt flux scheme can be used to synthesize large quantities of high-quality, single-crystalline TiO2 nanowires with controllable dimensions. Furthermore, in situ dopant incorporation of various transition metals allows for the tuning of optical, electrical, and catalytic properties. With this combination of control, robustness, and scalability, the molten-salt flux scheme can provide high-quality TiO2 nanowires to satisfy a broad range of application needs from photovoltaics to photocatalysis.

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.

Synthesis of boron-containing heterocyclic compounds

International Nuclear Information System (INIS)

Azev, Yuri; Slepukhina, Irina; Gabel, Detlef

2004-01-01

The synthesis of boron-containing 1,3,5-triazines and 1,2,4-triazines is described. Derivatives of 1,3,5-triazine containing the o-carborane cluster have been obtained by reacting the corresponding propargyl derivatives with B 10 H 14 . Derivatives of 1,2,4-triazine containing the B 12 H 12 2- cluster have been obtained by nucleophilic substitution of ethylsulfone derivatives with B 12 H 11 SH 2- . They have been isolated in their ring-protonated form. Reaction of RNH 2 -B 8 H 11 NH-R with stericly demanding heterocycles failed, either for steric or for solubility reasons

Application of Ti/RuO{sub 2}-Ta{sub 2}O{sub 5} electrodes in the electrooxidation of ethanol and derivants: Reactivity versus electrocatalytic efficiency

Energy Technology Data Exchange (ETDEWEB)

Ribeiro, J.; De Andrade, A.R. [Departamento de Quimica, Faculdade de Filosofia Ciencias e Letras de Ribeirao Preto, Universidade de Sao Paulo, 14040-9010 Ribeirao Preto, SP (Brazil); Purgato, F.L.S. [Departamento de Quimica, Faculdade de Filosofia Ciencias e Letras de Ribeirao Preto, Universidade de Sao Paulo, 14040-9010 Ribeirao Preto, SP (Brazil); Equipe Electrocatalyse, UMR 6503 CNRS, Universite de Poitiers, 40 Avenue du Recteur Pineau 86022 Poitiers Cedex (France); Kokoh, K.B.; Leger, J.-M. [Equipe Electrocatalyse, UMR 6503 CNRS, Universite de Poitiers, 40 Avenue du Recteur Pineau 86022 Poitiers Cedex (France)

2008-11-15

The influence of the preparation method on the performance of RuO{sub 2}-Ta{sub 2}O{sub 5} electrodes was evaluated toward the ethanol oxidation reaction (EOR). Freshly prepared RuO{sub 2}-Ta{sub 2}O{sub 5} thin films containing between 30 and 80 at.% Ru were prepared by two different methods: the modified Pechini-Adams method (DPP) and standard thermal decomposition (STD). Electrochemical investigation of the electrode containing RuO{sub 2}-Ta{sub 2}O{sub 5} thin films was conducted as a function of electrode composition in a 0.5-mol dm{sup -3} H{sub 2}SO{sub 4} solution, in the presence and absence of ethanol and its derivants (acetaldehyde and acetic acid). At a low ethanol concentration (5 mmol dm{sup -3}), ethanol oxidation leads to high yields of acetic acid and CO{sub 2}. On the other hand, an increase in ethanol concentration (15-1000 mmol dm{sup -3}) favors acetaldehyde formation, so acetic acid and CO{sub 2} production is hindered, in this case. Electrodes prepared by DPP provide higher current efficiency than STD electrodes for all the investigated ethanol concentrations. This may be explained by the increase in electrode area obtained with the DPP preparation method compared with STD. (author)

Cu_2O Hybridized Titanium Carbide with Open Conductive Frameworks for Lithium-ion Batteries

International Nuclear Information System (INIS)

Zhang, Huang; Dong, Hui; Zhang, Xuan; Xu, Yunlong; Fransaer, Jan

2016-01-01

Though MXenes, a new family of 2D transition metal carbides, are generating considerable interests as electrode materials for batteries and supercapacitors, further application is hindered by their low capacities and poor rate capabilities. Here we propose a simple route for the synthesis of Cu_2O particle hybridized titanium carbide Ti_2CT_x (T = O, OH) composites via a solvothermal method. Electrodes containing Cu_2O/MXene were fabricated without carbon black, and tested as anodes for lithium ion batteries. A discharge capacity of 143 mAh g"−"1 was obtained at a discharge current density of 1000 mA g"−"1 and the capacity retention was near 100% after 200 cycles. The hybrid electrodes with open conductive frameworks exhibited significantly improved electrochemical performance, suggesting a new method for preparing MXene-based composites for energy storage application.

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.

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

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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.

Controlled nitric oxide production via O(1D) + N2O reactions for use in oxidation flow reactor studies

Science.gov (United States)

Lambe, Andrew; Massoli, Paola; Zhang, Xuan; Canagaratna, Manjula; Nowak, John; Daube, Conner; Yan, Chao; Nie, Wei; Onasch, Timothy; Jayne, John; Kolb, Charles; Davidovits, Paul; Worsnop, Douglas; Brune, William

2017-06-01

Oxidation flow reactors that use low-pressure mercury lamps to produce hydroxyl (OH) radicals are an emerging technique for studying the oxidative aging of organic aerosols. Here, ozone (O3) is photolyzed at 254 nm to produce O(1D) radicals, which react with water vapor to produce OH. However, the need to use parts-per-million levels of O3 hinders the ability of oxidation flow reactors to simulate NOx-dependent secondary organic aerosol (SOA) formation pathways. Simple addition of nitric oxide (NO) results in fast conversion of NOx (NO + NO2) to nitric acid (HNO3), making it impossible to sustain NOx at levels that are sufficient to compete with hydroperoxy (HO2) radicals as a sink for organic peroxy (RO2) radicals. We developed a new method that is well suited to the characterization of NOx-dependent SOA formation pathways in oxidation flow reactors. NO and NO2 are produced via the reaction O(1D) + N2O → 2NO, followed by the reaction NO + O3 → NO2 + O2. Laboratory measurements coupled with photochemical model simulations suggest that O(1D) + N2O reactions can be used to systematically vary the relative branching ratio of RO2 + NO reactions relative to RO2 + HO2 and/or RO2 + RO2 reactions over a range of conditions relevant to atmospheric SOA formation. We demonstrate proof of concept using high-resolution time-of-flight chemical ionization mass spectrometer (HR-ToF-CIMS) measurements with nitrate (NO3-) reagent ion to detect gas-phase oxidation products of isoprene and α-pinene previously observed in NOx-influenced environments and in laboratory chamber experiments.

Theoretical Time Dependent Thermal Neutron Spectra and Reaction Rates in H{sub 2}O and D{sub 2}O

Energy Technology Data Exchange (ETDEWEB)

Purohit, S N

1966-04-15

The early theoretical and experimental time dependent neutron thermalization studies were limited to the study of the transient spectrum in the diffusion period. The recent experimental measurements of the time dependent thermal neutron spectra and reaction rates, for a number of moderators, have generated considerable interest in the study of the time dependent Boltzmann equation. In this paper we present detailed results for the time dependent spectra and the reaction rates for resonance detectors using several scattering models of H{sub 2}O and D{sub 2}O. This study has been undertaken in order to interpret the integral time dependent neutron thermalization experiments in liquid moderators which have been performed at the AB Atomenergi. The proton gas and the deuteron gas models are inadequate to explain the measured reaction rates in H{sub 2}O and D{sub 2}O. The bound models of Nelkin for H{sub 2}O and of Butler for D{sub 2}O give much better agreement with the experimental results than the gas models. Nevertheless, some disagreement between theoretical and experimental results still persists. This study also indicates that the bound model of Butler and the effective mass 3. 6 gas model of Brown and St. John give almost identical reaction rates. It is also surprising to note that the calculated reaction rate for Cd for the Butler model appears to be in better agreement with the experimental results of D{sub 2}O than of the Nelkin model with H{sub 2}O experiments. The present reaction rate studies are sensitive enough so as to distinguish between the gas model and the bound model of a moderator. However, to investigate the details of a scattering law (such as the effect of the hindered rotations in H{sub 2}O and D{sub 2}O and the weights of different dynamical modes) with the help of these studies would require further theoretical as well as experimental investigations. Theoretical results can be further improved by improving the source for thermal neutrons, the

Prediction of absolute infrared intensities for the fundamental vibrations of H2O2

Science.gov (United States)

Rogers, J. D.; Hillman, J. J.

1981-01-01

Absolute infrared intensities are predicted for the vibrational bands of gas-phase H2O2 by the use of a hydrogen atomic polar tensor transferred from the hydroxyl hydrogen atom of CH3OH. These predicted intensities are compared with intensities predicted by the use of a hydrogen atomic polar tensor transferred from H2O. The predicted relative intensities agree well with published spectra of gas-phase H2O2, and the predicted absolute intensities are expected to be accurate to within at least a factor of two. Among the vibrational degrees of freedom, the antisymmetric O-H bending mode nu(6) is found to be the strongest with a calculated intensity of 60.5 km/mole. The torsional band, a consequence of hindered rotation, is found to be the most intense fundamental with a predicted intensity of 120 km/mole. These results are compared with the recent absolute intensity determinations for the nu(6) band.

Protective Effects of Dihydromyricetin against •OH-Induced Mesenchymal Stem Cells Damage and Mechanistic Chemistry

Directory of Open Access Journals (Sweden)

Xican Li

2016-05-01

Full Text Available As a natural flavonoid in Ampelopsis grossedentata, dihydromyricetin (DHM, 2R,3R-3,5,7,3′,4′,5′-hexahydroxy-2,3-dihydroflavonol was observed to increase the viability of •OH-treated mesenchymal stem cells using a MTT [3-(4,5-dimethylthiazol-2-yl-2,5-diphenyl] assay and flow cytometry analysis. This protective effect indicates DHM may be a beneficial agent for cell transplantation therapy. Mechanistic chemistry studies indicated that compared with myricetin, DHM was less effective at ABTS+• (2,2′-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid radical scavenging and reducing Cu2+, and had higher •O2− and DPPH• (1,1-diphenyl-2-picrylhydrazyl radical scavenging activities. Additionally, DHM could also chelate Fe2+ to give an absorption maximum at 589 nm. Hence, such protective effect of DHM may arise from its antioxidant activities which are thought to occur via direct radical-scavenging and Fe2+-chelation. Direct radical-scavenging involves an electron transfer (ET pathway. The hydrogenation of the 2,3-double bond is hypothesized to reduce the ET process by blocking the formation of a larger π-π conjugative system. The glycosidation of the 3–OH in myricitrin is assumed to sterically hinder atom transfer in the •O2− and DPPH• radical-scavenging processes. In DHM, the Fe2+-chelating effect can actually be attributed to the 5,3′,4′,5′–OH and 4–C=O groups, and the 3–OH group itself can neither scavenge radicals nor chelate metal.

A practical pathway for the preparation of Fe_2O_3 decorated TiO_2 photocatalyst with enhanced visible-light photoactivity

International Nuclear Information System (INIS)

Cheng, Li; Qiu, Shoufei; Chen, Juanrong; Shao, Jian; Cao, Shunsheng

2017-01-01

Shifting the ultra-violet of titania to visible light driven photocatalysis can be realized by coupling with metallic or non-metallic elements. However, time-consuming multi-step process and significant loss of UV photocatalytic activity of such TiO_2-based photocatalysts severely hinder their practical applications. In this work, we explore the idea of creating a practical method for the preparation of Fe_2O_3 decorated TiO_2 (TiO_2/Fe_2O_3) photocatalyst with controlled visible-light photoactivity. This method only involves the calcination of the mixture (commercial P25 powders and magnetic Fe_3O_4 nanoparticles) prepared by a mechanical process. The morphology and properties of TiO_2/Fe_2O_3 composites were characterized by Transmission electron microscope, X-ray diffraction, UV–vis spectroscopy, and X-ray photoelectron spectroscopy. Results confirm the fusion of TiO_2 and Fe_2O_3, which promotes photo-generated electrons/holes migration and separation. Because of the strong synergistic effect, the as-synthesized TiO_2/Fe_2O_3 composites manifest an enhanced visible-light photocatalytic activity. Especially, the TiO_2/Fe_2O_3 photocatalyst is very easy to be constructed via an one-step protocol that efficiently overcomes the time-consuming multi-step processes used in existed strategies for the preparation of Fe_2O_3/TiO_2 photocatalysts, providing a new insight into the practical application of TiO_2/Fe_2O_3 visible light photocatalyst. - Highlights: • We introduced a practical preparation of Fe_2O_3 decorated TiO_2 photocatalyst. • TiO_2/Fe_2O_3 was developed using commercial precursors in a high efficient manner. • Visible-light activity of TiO_2/Fe_2O_3 could be tuned by changing amount of Fe_3O_4 precursor. • TiO_2/Fe_2O_3 exhibited a higher visible-light photocatalytic activity than P25.

Relation between frequency and H bond length in heavy water: Towards the understanding of the unusual properties of H bond dynamics in nanoporous media

International Nuclear Information System (INIS)

Pommeret, Stanislas; Leicknam, Jean-Claude; Bratos, Savo; Musat, Raluca; Renault, Jean Philippe

2009-01-01

The published work on H bond dynamics mainly refers to diluted solutions HDO/D 2 O rather than to normal water. The reasons for this choice are both theoretical and experimental. Mechanical isolation of the OH vibrator eliminating the resonant energy transfer makes it a better probe of the local H bond network, while the dilution in heavy water reduces the infrared absorption, which permits the use of thicker experimental cells. The isotopic substitution does not alter crucially the nature of the problem. The length r of an OH . . . O group is statistically distributed over a large interval comprised between 2.7 and 3.2 A with a mean value r 0 = 2.86 A. Liquid water may thus be viewed as a mixture of hydrogen bonds of different length. Two important characteristics of hydrogen bonding must be mentioned. (i) The OH stretching vibrations are strongly affected by this interaction. The shorter the length r of the hydrogen bond, the strongest the H bond link and the lower is its frequency ω: the covalent OH bond energy is lent to the OH. . .O bond and reinforces the latter. A number of useful relationships between ω and r were published to express this correlation. The one adopted in our previous work is the relationship due to Mikenda. (ii) Not only the OH vibrations, but also the HDO rotations are influenced noticeably by hydrogen bonding. This is due to steric forces that hinder the HDO rotations. As they are stronger in short than in long hydrogen bonds, rotations are slower in the first case than in the second. This effect was only recently discovered, but its existence is hardly to be contested. In the present contribution, we want to revisit the relationship between the frequency of the OH vibrator and the distance OH. . .O.

Embedding ultrafine ZnSnO3 nanoparticles into reduced graphene oxide composites as high-performance electrodes for lithium ion batteries

Science.gov (United States)

Ma, Yuhang; Jiang, Ranran; Li, Dan; Dong, Yutao; Liu, Yushan; Zhang, Jianmin

2018-05-01

Ultrafine ZnSnO3 nanoparticles, with an average diameter of 45 nm, homogeneously grown on reduced graphene oxide (rGO) have been successfully fabricated via methods of low temperature coprecipitation, colloid electrostatic self-assembly, and hydrothermal treatment. The uniformly distributed ZnSnO3 nanocrystals could inhibit the restacking of rGO sheets. In turn, the existence of rGO could hinder the growth and aggregation of ZnSnO3 nanoparticles in the synthesis process, increase the conductivity of the composite, and buffer the volume expansion of the ZnSnO3 nanocrystals upon lithium ion insertion and extraction. The obtained ZnSnO3/rGO exhibited superior cycling stability with a discharge/charge capacity of 718/696 mA h g-1 after 100 cycles at a current density of 0.1 A g-1.

Effect of Ce Doping on RGO-TiO2 Nanocomposite for High Photoelectrocatalytic Behavior

Directory of Open Access Journals (Sweden)

Md. Rakibul Hasan

2014-01-01

Full Text Available Ce doped RGO-TiO2 composite films on ITO substrates were prepared by sol-gel process using tetrabutyl titanate and reduced graphene oxide (RGO as the starting materials. The sample was designed for the photoelectrocatalytic applications. The obtained samples were characterized by X-ray diffraction, UV-vis absorption spectroscopy, scanning electron microscopy, and Fourier transformed infrared spectroscopy. The results showed that doping of Ce on RGO-TiO2 composite film inhibited the TiO2 anatase-rutile phase transformation. In this case, Ce atoms could serve as dispersion oxide and suppress the recombination of photoinduced electron-hole pairs. Besides, the change in absorbance from UV to visible region was observed in Ce doped RGO-TiO2 nanocomposite films. The Ce doped RGO-TiO2 composite film showed higher photoelectrochemical performance than that of RGO-TiO2 composite and pure TiO2 under solar simulator irradiation. The main reason might be attributed to the optimum content of Ce that could act as electrons acceptor to hinder the recombination loss and facilitate the better transportation for photoinduced charge carriers.

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.

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

Potential rare-earth modified CeO{sub 2} catalysts for soot oxidation. Part III. Effect of dopant loading and calcination temperature on catalytic activity with O{sub 2} and NO + O{sub 2}

Energy Technology Data Exchange (ETDEWEB)

Krishna, K.; Bueno-Lopez, A.; Makkee, M.; Moulijn, J.A. [Catalysis Engineering, DelftChemTech, Delft University of Technology, Julianalaan 136, NL 2628 BL Delft (Netherlands)

2007-09-26

CeO{sub 2} and CeReO{sub xy} catalysts are prepared by the calcination at different temperatures (y = 500-1000 C) and having a different composition (Re = La{sup 3+} or Pr{sup 3+/4+}{sub ,} 0-90 wt.%). The catalysts are characterised by XRD, H{sub 2}-TPR, Raman, and BET surface area. The soot oxidation is studied with O{sub 2} and NO + O{sub 2} in the tight and loose contact conditions, respectively. CeO{sub 2} sinters between 800-900 C due to a grain growth, leading to an increased crystallite size and a decreased BET surface area. La{sup 3+} or Pr{sup 3+/4+} hinders the grain growth of CeO{sub 2} and, thereby, improving the surface catalytic properties. Using O{sub 2} as an oxidant, an improved soot oxidation is observed over CeLaO{sub xy} and CePrO{sub xy} in the whole dopant weight loading and calcination temperature range studied, compared with CeO{sub 2}. Using NO + O{sub 2}, the soot conversion decreased over CeLaO{sub xy} catalysts calcined below 800 C compared with the soot oxidation over CeO{sub 2y}. CePrO{sub xy}, on the other hand, showed a superior soot oxidation activity in the whole composition and calcination temperature range using NO + O{sub 2}. The improvement in the soot oxidation activity over the various catalysts with O{sub 2} can be explained based on an improvement in the external surface area. The superior soot oxidation activity of CePrO{sub xy} with NO + O{sub 2} is explained by the changes in the redox properties of the catalyst as well as surface area. CePrO{sub xy}, having 50 wt.% of dopant, is found to be the best catalyst due to synergism between cerium and praseodymium compared to pure components. NO into NO{sub 2} oxidation activity, that determines soot oxidation activity, is improved over all CePrO{sub x} catalysts. (author)

One-pot, three-component synthesis of highly substituted pyridines ...

Indian Academy of Sciences (India)

Administrator

trile in the presence of nanocrystalline magnesium oxide provides the highly substituted pyridine derivatives in moderate to ..... NAP–MgO (0⋅1 g), ethanol (5 mL) at reflux temperature b ... difference in the electronic and steric properties of.

Stability and aggregation of nanoscale titanium dioxide particle (nTiO2): Effect of cation valence, humic acid, and clay colloids.

Science.gov (United States)

Tang, Zhong; Cheng, Tao

2018-02-01

Fate and transport of engineered nanoscale titanium dioxide (nTiO 2 ) have received much attention during the past decade. The aggregation and stability of nTiO 2 in water with complicated components, however, have not been fully examined. The objective of this paper is to determine the individual and synergistic effect of cation valence, humic acid, and clay colloids on nTiO 2 stability and aggregation, and elucidate the related mechanisms. We conducted systematic laboratory experiments to determine nTiO 2 stability and aggregation in NaCl and MgCl 2 solutions, both in the absence and presence of humic acid and illite colloids. Results showed that Mg 2+ , in comparison to Na + , could make the zeta potential of nTiO 2 more positive, and shift the point of zero charge of nTiO 2 (pH pzc,TiO2 ) towards higher pH. We also found that nTiO 2 are destabilized by illite colloids at pH < pH pzc,TiO2 through formation of illite-nTiO 2 hetero-aggregates, but are not interfered by illite colloids at higher pH. HA was found to make nTiO 2 stable via electrostatic and steric effects, both in the absence and presence of illite colloids. Calculated interaction energy based on DLVO theory revealed that instability of the nTiO 2 suspensions is mainly caused by primary minima, and that secondary minima normally do not destabilize the suspension, even though they are found to promote aggregation. Copyright © 2017 Elsevier Ltd. All rights reserved.

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.

Carbon Dioxide-Mediated C(sp3)-H Arylation of Amine Substrates.

Science.gov (United States)

Kapoor, Mohit; Liu, Daniel; Young, Michael C

2018-05-25

Elaborating amines via C-H functionalization has been an important area of research over the past decade but has generally relied on an added directing group or sterically hindered amine approach. Since free-amine-directed C(sp 3 )-H activation is still primarily limited to cyclization reactions and to improve the sustainability and reaction scope of amine-based C-H activation, we present a strategy using CO 2 in the form of dry ice that facilitates intermolecular C-H arylation. This methodology has been used to enable an operationally simple procedure whereby 1° and 2° aliphatic amines can be arylated selectively at their γ-C-H positions. In addition to potentially serving as a directing group, CO 2 has also been demonstrated to curtail the oxidation of sensitive amine substrates.

The features of nucleophilic substitution of the nitro group in 4-alkyl-6-nitro-1,2,4-triazolo[5,1-c][1,2,4]triazines

Directory of Open Access Journals (Sweden)

E. N. Ulomsky

2017-05-01

Full Text Available The nucleophilic substitution of the nitro group of 4-alkyl-6-nitro-4,7-dihydro-1,2,4-triazolo[5,1-c][1,2,4]triazine-7-ones on the example of interactionwith morpholine was studied. It is established that under the action of excess cycloalkylimine at room temperature the unusual easy disclosure of triazine cycle with the formation of sterically hindered hydrazones occurs which are the key intermediates for further transformations. The carrying of reaction at elevated temperatures leads to the formation of products of substitution of the nitro group with the amine and also with morpholyl hydrazones which are the products of hydrolysis of amides of hydrazones and subsequent decarboxylation. Thus, the nucleophilic substitution of the nitro group in the described triazolotriazines flows through the ANRORC mechanism.

Determination of the evaporation coefficient of D2O

Directory of Open Access Journals (Sweden)

R. C. Cohen

2008-11-01

Full Text Available The evaporation rate of D2O has been determined by Raman thermometry of a droplet train (12–15 μm diameter injected into vacuum (~10-5 torr. The cooling rate measured as a function of time in vacuum was fit to a model that accounts for temperature gradients between the surface and the core of the droplets, yielding an evaporation coefficient (γe of 0.57±0.06. This is nearly identical to that found for H2O (0.62±0.09 using the same experimental method and model, and indicates the existence of a kinetic barrier to evaporation. The application of a recently developed transition-state theory (TST model suggests that the kinetic barrier is due to librational and hindered translational motions at the liquid surface, and that the lack of an isotope effect is due to competing energetic and entropic factors. The implications of these results for cloud and aerosol particles in the atmosphere are discussed.

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.

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.

A study of PbTiO sub 3 crystallization in pure and composite nanopowders prepared by the sol-gel technique

CERN Document Server

Cernansky, M; Kral, K; Krupkova, R

2002-01-01

In this investigation the crystallization of PbTiO sub 3 upon annealing of pure nanopowders and PbTiO sub 3 -SiO sub 2 (1:1 v/v) nanocomposite powders prepared by the sol-gel technique was studied. Using x-ray diffraction phase analysis, the start of PbTiO sub 3 crystallization in pure PbTiO sub 3 powders was detected at 400 sup o C. Distinct crystallization of PbTiO sub 3 in PbTiO sub 3 -SiO sub 2 nanocomposites starts at 700 sup o C, whereas SiO sub 2 remains amorphous. There are indications that an interface interaction between the PbTiO sub 3 and the SiO sub 2 phase plays an important role in hindering the crystallization of PbTiO sub 3. The particle size (size of coherently scattering regions) was estimated from the broadening of the x-ray diffraction line profiles. The average size of PbTiO sub 3 nanocrystallites increases with temperature and time of annealing, the influence of temperature being more significant than that of the annealing time. Differential scanning calorimetry confirmed the results of...

Influence of crystallinity on CO gas sensing for TiO{sub 2} films

Energy Technology Data Exchange (ETDEWEB)

Seeley, Zachary Mark [School of Mechanical and Materials Engineering, Washington State University, Pullman, WA 99164-2920 (United States); Bandyopadhyay, Amit [School of Mechanical and Materials Engineering, Washington State University, Pullman, WA 99164-2920 (United States)], E-mail: amitband@wsu.edu; Bose, Susmita [School of Mechanical and Materials Engineering, Washington State University, Pullman, WA 99164-2920 (United States)

2009-08-15

In the present research, carbon monoxide (CO) gas sensing response was studied for TiO{sub 2} thick films calcined and sintered between 700 and 900 deg. C. Crystalline phase, crystallite size, surface area, particle size, and amorphous content were measured for the calcined powder. Crystallinity of the powder was found to affect sensing response significantly towards CO. Anatase phase of TiO{sub 2} thick film was stable up to 900 deg. C however, as calcination temperature increased from 700 to 900 deg. C, surface area and amorphous phase content decreased. Films calcined and sintered at 700 deg. C showed a lower response towards CO than those calcined at 800 deg. C. Upon increasing the calcination temperature further, particle growth and reduced surface area hindered the sensing response. A calcination temperature of 800 deg. C was necessary to achieve sufficient order in the crystal structure leading to more efficient adsorption and desorption of oxygen ions on the surface of TiO{sub 2}.

Carbon nanotube-wrapped Fe2O3 anode with improved performance for lithium-ion batteries

Directory of Open Access Journals (Sweden)

Guoliang Gao

2017-03-01

Full Text Available Metall oxides have been proven to be potential candidates for the anode material of lithium-ion batteries (LIBs because they offer high theoretical capacities, and are environmentally friendly and widely available. However, the low electronic conductivity and severe irreversible lithium storage have hindered a practical application. Herein, we employed ethanolamine as precursor to prepare Fe2O3/COOH-MWCNT composites through a simple hydrothermal synthesis. When these composites were used as electrode material in lithium-ion batteries, a reversible capacity of 711.2 mAh·g−1 at a current density of 500 mA·g−1 after 400 cycles was obtained. The result indicated that Fe2O3/COOH-MWCNT composite is a potential anode material for lithium-ion batteries.

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).

Physicochemical properties and drug release behavior of biguanidino and O-carboxymethyl chitosan microcapsules.

Science.gov (United States)

Huo, Weiqiang; Zhang, Weixin; Wang, Wei; Zhou, Xiaohua

2014-09-01

Two types of microcapsules (MCs) were prepared by the emulsion cross-linking method, where biguanidino chitosan (BGCS)and O-carboxymethyl chitosan (O-CMCS) served as the wall materials, and the antibacterial agent 2,4-diamino-6-(2-pyridyl)-1,3,5-triazine (PyTNH) served as a model water-soluble drug. The physicochemical performance of the MCs and their drug release behavior were investigated by Fourier transform infrared spectroscopy, thermogravimetric analysis/derivative thermogravimetric analysis, scanning electron microscopy, and swelling and in vitro drug release studies of the two MCs with unmodified chitosan-MCs (CS-MCs) used as the control. The results indicated that the degree of cross-linking, encapsulation efficiency, and thermal stability of the shell wall of the BGCS-microcapsules (BGCS-MCs) were much higher than those of the control and the O-CMCS-microcapsules (CMCS-MCs), owing to the reduction of steric hindrance and development of the conjugation effect in the cross-linking process. Studies on the swelling and in vitro drug-release behavior revealed a sustained release effect of the BGCS-MCs. Moreover, the CMCS-MCs were found to exhibit a pH-dependent drug release behavior, which can be attributed to the successive formation of H-bonds and repulsive forces with the change in the pH of the medium. Based on these results, the swelling-release models and the drug release kinetics of BGCS-MCs and CMCS-MCs are proposed. Copyright © 2014 Elsevier B.V. All rights reserved.

Composition and structural study of solution-processed Zn(S,O,OH) thin films grown using H{sub 2}O{sub 2} based deposition route

Energy Technology Data Exchange (ETDEWEB)

Buffière, M., E-mail: marie.buffiere@imec.be [Institut des Matériaux Jean Rouxel (IMN)-UMR 6502, Université de Nantes, CNRS, 2 rue de la Houssinière, BP 32229, 44322 Nantes Cedex 3 (France); 44Solar, 14 rue Kepler, 44240 La Chapelle-sur-Erdre (France); Gautron, E. [Institut des Matériaux Jean Rouxel (IMN)-UMR 6502, Université de Nantes, CNRS, 2 rue de la Houssinière, BP 32229, 44322 Nantes Cedex 3 (France); Hildebrandt, T. [Institut de Recherche et Développement sur l' Energie Photovoltaïque (IRDEP)-UMR 7174 EDF-CNRS-ENSCP, 6 quai Watier-78401 Chatou Cedex (France); Harel, S.; Guillot-Deudon, C.; Arzel, L. [Institut des Matériaux Jean Rouxel (IMN)-UMR 6502, Université de Nantes, CNRS, 2 rue de la Houssinière, BP 32229, 44322 Nantes Cedex 3 (France); Naghavi, N. [Institut de Recherche et Développement sur l' Energie Photovoltaïque (IRDEP)-UMR 7174 EDF-CNRS-ENSCP, 6 quai Watier-78401 Chatou Cedex (France); Barreau, N. [Institut des Matériaux Jean Rouxel (IMN)-UMR 6502, Université de Nantes, CNRS, 2 rue de la Houssinière, BP 32229, 44322 Nantes Cedex 3 (France); Kessler, J. [Institut des Matériaux Jean Rouxel (IMN)-UMR 6502, Université de Nantes, CNRS, 2 rue de la Houssinière, BP 32229, 44322 Nantes Cedex 3 (France); 44Solar, 14 rue Kepler, 44240 La Chapelle-sur-Erdre (France)

2013-05-01

Recent results have revealed that the low deposition time issue of chemical bath deposited (CBD) Zn(S,O,OH) buffer layer used in Cu(In,Ga)Se{sub 2} (CIGSe) solar cells could be resolved using H{sub 2}O{sub 2} as an additive in the chemical bath solution. Although the use of this additive does not hinder the electrical properties of the resulting Zn(S,O,OH)-buffered CIGSe solar cells, the impact of H{sub 2}O{sub 2} on the Zn(S,O,OH) properties remains unclear. The present contribution aims at determining the chemical composition and the microstructure of Zn(S,O,OH) film deposited by CBD using the alternative deposition bath containing the standard zinc sulfate, thiourea, ammonia but also H{sub 2}O{sub 2} additive. Both X-ray photoemission spectroscopy and energy dispersive X-ray spectroscopy analyses reveal higher sulfur content in alternatively deposited Zn(S,O,OH), since the first step growth of the layer. According to transmission electron microscopy analyses, another consequence of the higher deposition rate achieved when adding H{sub 2}O{sub 2} in the bath is the modification of the absorber/buffer interface. This could be explained by the enhancement of the cluster growth mechanism of the layer. - Highlights: ► The Zn(S,O,OH) layer composition can vary with the chemical bath process used. ► The alternative process leads to a faster incorporation of sulfur in the layer. ► No ZnS epitaxial layer has been found at absorber/alternative buffer interface. ► The use of H{sub 2}O{sub 2} enhances the cluster-by-cluster growth mechanism.

Role of H2O2 in the photo-transformation of phenol in artificial and natural seawater

International Nuclear Information System (INIS)

Calza, Paola; Campra, Laura; Pelizzetti, Ezio; Minero, Claudio

2012-01-01

In previous works, it was observed that phenol photo-induced transformation in natural seawater (NSW) mediated by natural photosensitizers occurs and leads to the formation of numerous hydroxylated, condensed, halogenated and nitroderivatives. Irradiation of NSW added with phenol and iron species had provided the enhanced formation of several halophenols, suggesting a central role played by iron species on the phenol halogenation in marine water. In this paper, we focus on hydrogen peroxide, another key photosensitizer, and its interaction with iron species. The ability of Fe(II)/Fe(III) and H 2 O 2 species to act as photo-sensitizers towards the transformation of organic compounds in seawater was investigated under simulated solar radiation. Light activation is necessary to induce the transformation of phenol, as no degradation occurs in the dark when either H 2 O 2 or iron/H 2 O 2 are initially added to artificial seawater (ASW). Fe(II) is easily transformed into Fe(III), assessing that a Fenton reaction (dark, Fe(II)/H 2 O 2 ) does not take place in marine environment, in favour of a photo-activated reaction involving Fe(III) and H 2 O 2 . When NSW is spiked with H 2 O 2 and Fe(III), halophenols' and nitrophenols' concentration decreases and completely disappears at high hydrogen peroxide concentration. Since Fe(II) and Fe(III) in spiked seawater induce an enhanced formation of haloderivatives, an excess of hydrogen peroxide act as scavenger towards the photo-produced chloro/bromo radicals, so hindering halogenation process in seawater. Hence, even if hydrogen peroxide efficiently induces the ·OH radical formation, and could then promote the phenol phototransformation, nevertheless it is negligibly involved in the production of the intermediates formed during phenol photolysis in seawater, whose formation is necessarily linked to other photosensitizer species. - Highlights: ► Hydrogen peroxide-mediated solar-driven transformations of pollutant in seawater are

Ab initio study of the effect of Si on the phase stability and electronic structure of γ- and α-Al2O3

International Nuclear Information System (INIS)

Nahif, F; Music, D; Mráz, S; To Baben, M; Schneider, J M

2013-01-01

Using density functional theory, the effect of Si on the stability and electronic structure of γ- and α-Al 2 O 3 has been investigated. The concentration range from 0 to 5 at.% is probed and the additive is positioned at different substitutional sites in the γ-phase. The calculations for (Al,Si) 2 O 3 predict a trend towards spontaneous decomposition into α-/γ-Al 2 O 3 and SiO 2 . Therefore, the formation of the metastable γ-(Al,Si) 2 O 3 phase can only be expected during non-equilibrium processing where the decomposition is kinetically hindered. The Si-induced changes in stability of this metastable solid solution may be understood based on the electronic structure. As the Si concentration is increased, stiff silicon–oxygen bonds are formed giving rise to the observed stabilization of the γ-phase. (paper)

Implications of the formation of small polarons in Li2O2 for Li-air batteries

Science.gov (United States)

Kang, Joongoo; Jung, Yoon Seok; Wei, Su-Huai; Dillon, Anne C.

2012-01-01

Lithium-air batteries (LABs) are an intriguing next-generation technology due to their high theoretical energy density of ˜11 kWh/kg. However, LABs are hindered by both poor rate capability and significant polarization in cell voltage, primarily due to the formation of Li2O2 in the air cathode. Here, by employing hybrid density functional theory, we show that the formation of small polarons in Li2O2 limits electron transport. Consequently, the low electron mobility μ = 10-10-10-9 cm2/V s contributes to both the poor rate capability and the polarization that limit the LAB power and energy densities. The self-trapping of electrons in the small polarons arises from the molecular nature of the conduction band states of Li2O2 and the strong spin polarization of the O 2p state. Our understanding of the polaronic electron transport in Li2O2 suggests that designing alternative carrier conduction paths for the cathode reaction could significantly improve the performance of LABs at high current densities.

Alimentação mundial: uma reflexão sobre a história

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Edeli Simioni de Abreu

2001-12-01

Full Text Available A alimentação é fator primordial na rotina diária da humanidade, não apenas por ser necessidade básica, mas principalmente porque a sua obtenção tornou-se um problema de saúde pública, uma vez que o excesso ou falta podem causar doenças. O objetivo desse trabalho é fazer um estudo retrospectivo que venha oferecer subsídios para uma reflexão sobre o panorama da alimentação mundial. Através da evolução histórica da alimentação mundial verifica-se que gastronomia, recursos, hábitos e padrões alimentares, são aspectos importantes que nos auxiliam a refletir sobre a complexidade e a magnificência que permeiam as relações entre os diversos países. Quando se fala em alimentação não há como não pensar na conseqüência da falta da mesma: a fome. Problema de extrema gravidade que atinge milhões de pessoas em todo o mundo. As desigualdades econômicas e sociais têm impossibilitado que as populações, principalmente de países em desenvolvimento tenham acesso à alimentação. É importante perceber a emergência de decisões políticas que priorizem o desenvolvimento econômico através de uma melhor distribuição de renda e de uma política agrícola, auxiliadas por novas tecnologias.Food is a fundamental factor in the human daily routine, not only because it is a basic need, but also because access to it has become a Public Health problem given that both lack and excess may lead to disease. This study aimed at making a retrospective study to offer subsidies for a reflection about world alimentary patterns. The historic evolution of world nutrition reveals that gastronomy, resources, habits and food patterns are important aspects for a reflection on the complexity and richness among countries. When one talks about food it is impossible to forget hunger, a serious problem for it hits millions around the world. Economic and social inequality have hindered acess to food for populations, mainly in developing countries

Theoretical study of hydration in Y2Mo3O12: Effects on structure and negative thermal expansion

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Ming-Yi Wu

2015-02-01

Full Text Available We report ab-initio calculations of water absorption in Y2Mo3O12. The absorption geometry of H2O in Y2Mo3O12 and the binding property between H2O and Y2Mo3O12 have been first identified. Our calculated results show that water is chemisorbed in Y2Mo3O12 with O of the water binding to the Y3+ cation, which is further strengthened by hydrogen bonding between each of the hydrogen atoms of H2O and the bridge O in Y2Mo3O12, shared by polyhedrons YO6 and MoO4. The absorption of water leads to a reduced angle of Y-O-Mo and shortened Y-Mo distance, and consequently volume contraction of the material, almost linearly with the increasing number of water molecules per unit cell, up to eight in total. In addition, our phonon calculation show that the transverse vibration of Y-O-Mo is restricted due to water absorption, which in turn hinders the NTE, as it is mainly originated from this vibrational mode. Our results clarify further the fundamental mechanisms of the large volume shrinkage and the lost NTE of the framework oxide due to water absorption.

Rational design of hierarchical ZnO@Carbon nanoflower for high performance lithium ion battery anodes

Science.gov (United States)

liu, Huichao; Shi, Ludi; Li, Dongzhi; Yu, Jiali; Zhang, Han-Ming; Ullah, Shahid; Yang, Bo; Li, Cuihua; Zhu, Caizhen; Xu, Jian

2018-05-01

The rational structure design and strong interfacial bonding are crucially desired for high performance zinc oxide (ZnO)/carbon composite electrodes. In this context, micro-nano secondary structure design and strong dopamine coating strategies are adopted for the fabrication of flower-like ZnO/carbon (ZnO@C nanoflowers) composite electrodes. The results show the ZnO@C nanoflowers (2-6 μm) are assembled by hierarchical ZnO nanosheets (∼27 nm) and continuous carbon framework. The micro-nano secondary architecture can facilitate the penetration of electrolyte, shorten lithium ions diffusion length, and hinder the aggregation of the nanosheets. Moreover, the strong chemical interaction between ZnO and coating carbon layer via C-Zn bond improves structure stability as well as the electronic conductivity. As a synergistic result, when evaluated as lithium ion batteries (LIBs) anode, the ZnO@C nanoflower electrodes show high reversible capacity of ca. 1200 mA h g-1 at 0.1 A g-1 after 80 cycles. As well as good long-cycling stability (638 and 420 mA h g-1 at 1 and 5 A g-1 after 500 cycles, respectively) and excellent rate capability. Therefore, this rational design of ZnO@C nanoflowers electrode is a promising anode for high-performance LIBs.

Carbon dioxide removal in gas treating processes

Energy Technology Data Exchange (ETDEWEB)

Lidal, H

1992-06-01

The main contribution of this work is the development of a simple and reliable modelling technique on carbon dioxide removal describing the vapor-liquid equilibria of CO{sub 2} in aqueous alkanolamine solutions. By making use of measured pH data, the author has circumvented the problem of estimating interaction parameters, activity coefficients, and equilibrium constants in the prediction of vapor-liquid equilibria. The applicability of the model is best demonstrated on the tertiary amine system using MDEA. For this system, the VLE is accurately represented for temperatures in the range 25 to 140{sup o}C, for CO{sub 2} loadings from 0.001 to 1 mol/mol, and for amine molarities usually encountered in acid gas treating processes. The absorption of CO{sub 2} into solutions containing the sterically hindered amine AMP, is also well described by the model. The equilibrium of CO{sub 2} in mixed solvents containing a glycol (TEG,DEG) and an alkonolamine (MEA,DEA) has been measured at temperatures encountered in the absorption units. An equilibrium model has been developed for the CO{sub 2}/TEG/MEA system for estimation of CO{sub 2} partial pressures, covering loadings and temperatures for both absorption and desorption conditions. An important spin-off of the work described is that two new experimental set-ups have been designed and built. 154 refs., 38 figs., 22 tabs.

DNA-directed alkylating ligands as potential antitumor agents: sequence specificity of alkylation by intercalating aniline mustards.

Science.gov (United States)

Prakash, A S; Denny, W A; Gourdie, T A; Valu, K K; Woodgate, P D; Wakelin, L P

1990-10-23

The sequence preferences for alkylation of a series of novel parasubstituted aniline mustards linked to the DNA-intercalating chromophore 9-aminoacridine by an alkyl chain of variable length were studied by using procedures analogous to Maxam-Gilbert reactions. The compounds alkylate DNA at both guanine and adenine sites. For mustards linked to the acridine by a short alkyl chain through a para O- or S-link group, 5'-GT sequences are the most preferred sites at which N7-guanine alkylation occurs. For analogues with longer chain lengths, the preference of 5'-GT sequences diminishes in favor of N7-adenine alkylation at the complementary 5'-AC sequence. Magnesium ions are shown to selectively inhibit alkylation at the N7 of adenine (in the major groove) by these compounds but not the alkylation at the N3 of adenine (in the minor groove) by the antitumor antibiotic CC-1065. Effects of chromophore variation were also studied by using aniline mustards linked to quinazoline and sterically hindered tert-butyl-9-aminoacridine chromophores. The results demonstrate that in this series of DNA-directed mustards the noncovalent interactions of the carrier chromophores with DNA significantly modify the sequence selectivity of alkylation by the mustard. Relationships between the DNA alkylation patterns of these compounds and their biological activities are discussed.

Carbon dioxide removal in gas treating processes

International Nuclear Information System (INIS)

Lidal, H.

1992-06-01

The main contribution of this work is the development of a simple and reliable modelling technique on carbon dioxide removal describing the vapor-liquid equilibria of CO 2 in aqueous alkanolamine solutions. By making use of measured pH data, the author has circumvented the problem of estimating interaction parameters, activity coefficients, and equilibrium constants in the prediction of vapor-liquid equilibria. The applicability of the model is best demonstrated on the tertiary amine system using MDEA. For this system, the VLE is accurately represented for temperatures in the range 25 to 140 o C, for CO 2 loadings from 0.001 to 1 mol/mol, and for amine molarities usually encountered in acid gas treating processes. The absorption of CO 2 into solutions containing the sterically hindered amine AMP, is also well described by the model. The equilibrium of CO 2 in mixed solvents containing a glycol (TEG,DEG) and an alkonolamine (MEA,DEA) has been measured at temperatures encountered in the absorption units. An equilibrium model has been developed for the CO 2 /TEG/MEA system for estimation of CO 2 partial pressures, covering loadings and temperatures for both absorption and desorption conditions. An important spin-off of the work described is that two new experimental set-ups have been designed and built. 154 refs., 38 figs., 22 tabs

α″ Martensite and Amorphous Phase Transformation Mechanism in TiNbTaZr Alloy Incorporated with TiO2 Particles During Friction Stir Processing

Science.gov (United States)

Ran, Ruoshi; Liu, Yiwei; Wang, Liqiang; Lu, Eryi; Xie, Lechun; Lu, Weijie; Wang, Kuaishe; Zhang, Lai-Chang

2018-06-01

This work studied the formation of the α″ martensite and amorphous phases of TiNbTaZr alloy incorporated with TiO2 particles during friction stir processing. Formation of the amorphous phase in the top surface mainly results from the dissolution of oxygen, rearrangement of the lattice structure, and dislocations. High-stress stemming caused by dislocations and high-stress concentrations at crystal-amorphous interfaces promote the formation of α″ martensite. Meanwhile, an α″ martensitic transformation is hindered by oxygen diffusion from TiO2 to the matrix, thereby increasing resistance to shear.

Controlled nitric oxide production via O(1D  + N2O reactions for use in oxidation flow reactor studies

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A. Lambe

2017-06-01

Full Text Available Oxidation flow reactors that use low-pressure mercury lamps to produce hydroxyl (OH radicals are an emerging technique for studying the oxidative aging of organic aerosols. Here, ozone (O3 is photolyzed at 254 nm to produce O(1D radicals, which react with water vapor to produce OH. However, the need to use parts-per-million levels of O3 hinders the ability of oxidation flow reactors to simulate NOx-dependent secondary organic aerosol (SOA formation pathways. Simple addition of nitric oxide (NO results in fast conversion of NOx (NO + NO2 to nitric acid (HNO3, making it impossible to sustain NOx at levels that are sufficient to compete with hydroperoxy (HO2 radicals as a sink for organic peroxy (RO2 radicals. We developed a new method that is well suited to the characterization of NOx-dependent SOA formation pathways in oxidation flow reactors. NO and NO2 are produced via the reaction O(1D + N2O  →  2NO, followed by the reaction NO + O3  →  NO2 + O2. Laboratory measurements coupled with photochemical model simulations suggest that O(1D + N2O reactions can be used to systematically vary the relative branching ratio of RO2 + NO reactions relative to RO2 + HO2 and/or RO2 + RO2 reactions over a range of conditions relevant to atmospheric SOA formation. We demonstrate proof of concept using high-resolution time-of-flight chemical ionization mass spectrometer (HR-ToF-CIMS measurements with nitrate (NO3− reagent ion to detect gas-phase oxidation products of isoprene and α-pinene previously observed in NOx-influenced environments and in laboratory chamber experiments.

CO2 leakage-induced vegetation decline is primarily driven by decreased soil O2.

Science.gov (United States)

Zhang, Xueyan; Ma, Xin; Zhao, Zhi; Wu, Yang; Li, Yue

2016-04-15

To assess the potential risks of carbon capture and storage (CCS), studies have focused on vegetation decline caused by leaking CO2. Excess soil CO2 caused by leakage can affect soil O2 concentrations and soil pH, but how these two factors affect plant development remains poorly understood. This hinders the selection of appropriate species to mitigate potential negative consequences of CCS. Through pot experiments, we simulated CO2 leakage to examine its effects on soil pH and soil O2 concentrations. We subsequently assessed how maize growth responded to these changes in soil pH and O2. Decreased soil O2 concentrations significantly reduced maize biomass, and explained 69% of the biomass variation under CO2 leakage conditions. In contrast, although leaked CO2 changed soil pH significantly (from 7.32 to 6.75), it remained within the optimum soil pH range for maize growth. This suggests that soil O2 concentration, not soil pH, influences plant growth in these conditions. Therefore, in case of potential CO2 leakage risks, hypoxia-tolerant species should be chosen to improve plant survival, growth, and yield. Copyright © 2016 Elsevier Ltd. All rights reserved.

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.

Experimentação animal: ética e legislação brasileira Animal experimentation: ethics and the Brazilian legislation

Directory of Open Access Journals (Sweden)

Angélica Heringer de Rezende

2008-04-01

Full Text Available Este artigo trata da experimentação animal sob os pontos de vista da ética e da política, fazendo uma abordagem histórica do tema no cenário legislativo brasileiro. Os animais de laboratório desempenharam um papel decisivo para o desenvolvimento da ciência e continuam tendo um papel essencial na pesquisa biomédica, no entanto, sua utilização sempre despertou manifestação de diferentes naturezas. Apesar de as primeiras incursões na pesquisa experimental terem sido iniciadas há, pelo menos, quatro séculos, é incipiente o estabelecimento de normas que regulamentem a utilização de animais na América Latina. No Brasil, embora não haja uma lei específica em relação a essa utilização, algumas iniciativas já foram tomadas. As discussões sobre este tema continuam ocorrendo, contudo, a demora para definir uma lei que regulamente o uso de animais em pesquisa tem dificultado a padronização de procedimentos necessários à sistematização dos conhecimentos desenvolvidos no País.This article covers animal experimentation under the viewpoint of ethics and politics, and does a historical review of the theme in the Brazilian legislative scenario. Laboratory animals play a decisive role in the development of science and continue to have an essential role in biomedical research. However, their use always provoked manifestations of different natures. Even though the first incursions in experimental research began at least four centuries ago, the establishment of norms that regulate the use of animals in Latin America is incipient. In Brazil, although a specific law regarding this use does not exist, some initiatives have already been taken. The discussions on this theme continue to happen, however the delay to define a law that regulates the use of animals in research has hindered the standardization of procedures that are necessary to the systematization of the knowledge produced in the country.

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.

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.

Fatores críticos de sucesso da franquia - uma análise sob a óptica de ex-franqueados no município de São Paulo Critical aspects of franchise success as viewed by previous franchisees in São Paulo

Directory of Open Access Journals (Sweden)

Geraldo Luciano Toledo

2005-03-01

Full Text Available O presente artigo busca trazer uma contribuição ao estudo do sistema de franquias no Brasil a partir da investigação do relacionamento Franqueador/Franqueado, sob a óptica de ex-franqueados. A revisão bibliográfica que fundamenta o estudo apresenta uma discussão analítica sobre os principais aspectos que interferem no sucesso de uma unidade franqueada. Na condução da pesquisa empírica, de caráter predominantemente exploratório, foram entrevistados ex-franqueados de diferentes ramos de atividade. O trabalho conclui com a apresentação dos fatores que mais comumente conduzem à insatisfação dos franqueados e ao conseqüente desligamento de suas redes.To better understand the franchiser / franchisee relationship an investigation was made of franchising in Brazil from the point of view of ex-franchisees. A review of literature provided support for an analytical discussion on important aspects that hinder success in franchising. An empirical exploratory survey of ex-franchisees from various sectors of activity in the city of São Paulo was carried out to identify the factors that most frequently caused dissatisfaction and defection.

Electrochemical impedance spectroscopy analysis with a symmetric cell for LiCoO2 cathode degradation correlated with Co dissolution

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Hiroki Nara

2016-04-01

Full Text Available Static degradation of LiCoO2 cathodes is a problem that hinders accurate analysis using our developed separable symmetric cell. Therefore, in this study we investigate the static degradation of LiCoO2 cathodes in separable symmetric cells by electrochemical impedance spectroscopy (EIS and inductively coupled plasma analyses. EIS measurements of LiCoO2 cathodes are conducted in various electrolytes, with different anions and with or without HF and/or H2O. This allows us to determine the static degradation of LiCoO2 cathodes relative to their increase of charge transfer resistance. The increase of the charge transfer resistance of the LiCoO2 cathodes is attributed to cobalt dissolution from the active material of LiCoO2. Cobalt dissolution from LiCoO2 is revealed to occur even at low potential in the presence of HF, which is generated from LiPF6 and H2O. The results indicate that avoidance of HF generation is important for the analysis of lithium-ion battery electrodes by using the separable cell. These findings reveal the condition to achieve accurate analysis by EIS using the separable cell.

Influência das características ácido-básicas da superfície dos óxidos na estabilidade de suspensões cerâmicas de Al2O3 ou SnO2 com dispersantes comerciais Influence of acid-basic characteristic of Al2O3 or SnO2 surfaces on the stability of ceramic suspensions with commercial dispersants

Directory of Open Access Journals (Sweden)

D. Gouvêa

2001-03-01

Full Text Available Uma suspensão cerâmica estável pode ser obtida através da combinação de um pó cerâmico, um solvente e um dispersante. Polímeros adsorvidos às partículas de óxidos podem estabilizar uma suspensão através da formação de um potencial de repulsão entre as partículas que pode ser de origem eletrostática, estérica ou da combinação das duas. A adsorção depende das características da superfície dos óxidos cerâmicos utilizados. O SnO2 apresenta um ponto isoelétrico igual a 4 e a alumina igual a 8. A característica ácida da superfície do SnO2 faz com que ocorra uma competição entre a adsorção dos polímeros derivados de ácidos poliacrílicos e das hidroxilas. O aumento do potencial zeta ocorre devido à mudança do pH e não devido à adsorção dos polímeros. No caso da alumina, a superfície básica permite a adsorção dos polímeros e o aumento do potencial zeta sem que haja competição com os grupos OH-. Este estudo foi realizado através da medida simultânea de potencial zeta e pH das suspensões através da técnica ESA (Electrokinetic Sonic Amplitude.A stable ceramic dispersion can be obtained by mixing a ceramic powder, a solvent and a dispersant. Polymers adsorbed to ceramic particles may stabilize the dispersions by creating a repulsion charge among then.The stabilization has an electrostatic or steric origin, or even the sum of both processes. The adsorption depends on the characteristics of the powder surface. Isoelectric points (IEP of the SnO2 and alumina are 4 and 8, respectively. The basic/acid characteristic of the surface originates a competition between the adsorption of polymers derivated from polyacrilic acids and hidroxiles due to acidic characteristics of the SnO2 surface. In the other hand, alumina's basic surface allows polymers to adsorb and to increase the zeta potential without any competition between the dispersants and OH- ions. This study has been carried out by simultaneously

Conical angles of ligands - compounds of elements of the 6(16) and 7(17) groups. Levelling effect

International Nuclear Information System (INIS)

Imyanitov, N.S.

1991-01-01

In the framework of development of a unified system of electron and steric effects of ligand conical angles of 176 compounds R 2 X and RHal, where X=O, S, Se, Te; Hal=F, Cl, Br, I; R=H, Hal (only in the case of R 2 X), Alk or Ar, were calculated. A levelling effect of large X and Hal was pointed out: in the beginning of steric series the conical angles are determined by dimensions of X and Hal and not by R ones. Similar levelled values of conical angles for previously considered ligands on the basis of N, P, As, Sb, Bi, C, Si, Ge, Sn were also calculated

Design and synthesis of ruthenium(II) OCO pincer type NHC ...

Indian Academy of Sciences (India)

The tridentate nature of the tBu(OCO)2− ligand as well as some level of steric protection ... our previous results of ruthenium(II) o-hydroxyaryl sub- stituted bidentate NHC ...... (a) Ribelin T, Katz C E, English D G, Smith S,. Manukyan A K, Day ...

Combining ZnO/microwave treatment for changing wettability of WEEE styrene plastics (ABS and HIPS) and their selective separation by froth flotation

Science.gov (United States)

Thanh Truc, Nguyen Thi; Lee, Byeong-Kyu

2017-10-01

This study reports a simple froth flotation method to separate plastic wastes of acrylonitrile-butadiene-styrene (ABS) and high impact polystyrene (HIPS) after initial hydrophilization by coating the plastics with ZnO and microwave treatment. ABS and HIPS are typical styrene-based WEEE plastics having similar density and hydrophobicity, which hinders their separation for recycling. After coating with ZnO, 2-min microwave treatment rearranged the ABS surface and thus changed its molecular mobility and increased its hydrophilicity. The combined ZnO coating/microwave treatment facilitated the selective separation of ABS and HIPS with 100% and 95.2% recovery and 95.4% and 100% purity in froth flotation, respectively. The combination of ZnO coating-microwave treatment and froth flotation can be utilized as a selective ABS/HIPS separation technique for improved recycling of WEEE plastics.

CORRELATION ANALYSIS OF IR, 1 H- AND 13 C-NMR SPECTRAL DATA OF N-ALKYL AND N-CYCLOALKYL CYANOACETAMIDES

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Aleksandar D. Marinković

2011-09-01

Full Text Available Linear free energy relationships (LFER were applied to the IR, 1H- and 13C--NMR spectral data in N-alkyl and N-cycloalkyl cyanoacetamides. N-alkyl and N-cycloalkyl cyanocetamides were synthesized from corresponding amine and ethyl cyanoacetate. A number of substituents were employed for alkyl substitution, and fairly good correlations were obtained, using simple Hammett equation. In N-alkyl and N-cycloalkyl cyanoacetamides substituent cause SCS of N-H hydrogen primarily by steric interaction, polar subtituent effect influences SCS shift of C=O carbon, while steric effect of N-alkyl substituent causes IR stretching frequencies of N-H, C=O and CN group. The conformations of investigated compounds have been studied by the use of semiempirical PM6 method, and together with LFER analysis, give a better insight into the influence of such a structure on the transmission of electronic substituent effects. Negative ρ values for several correlations (reverse substituent effect were found.

Role of ligand basicity and stereochemistry in the extraction of plutonium(IV) isoxazolonates

International Nuclear Information System (INIS)

Mohapatra, P.K.; Manchanda, V.K.

2003-01-01

The extraction behaviour of plutonium (IV) was investigated from nitric acid and perchloric acid using 3-phenyl-4-benzoyl-5-isoxazolone (HPBI) as well as a mixture of HPBI and tri-n-octyl phosphine oxide (TOPO) in xylene. Studies on the binary extraction system Pu(IV)-HPBI indicated extraction of species of the type Pu(PBI) 4 . In the presence of TOPO, while species of the type Pu(PBI) 3 (ClO 4 ).(TOPO) and Pu(PBI) 4 .TOPO were co-extracted from perchloric acid medium, a mixture of Pu(PBI) 2 (NO 3 ) 2 .2TOPO, Pu(PBI) 3 (NO 3 ).(TOPO) and Pu(PBI) 4 .TOPO were co-extracted from nitric acid medium. In addition to the electronic factors, steric factors were found to play a significant role during the formation of binary/ternary/quaternary complexes. The steric hindrance due to the unusual conformation of the isoxazolone led to lowering of the equilibrium constants for both the binary and ternary extraction systems. Possible steric factor influences are explained with the help of molecular modelling. (orig.)

Ceramic membrane fouling during ultrafiltration of oil/water emulsions: roles played by stabilization surfactants of oil droplets.

Science.gov (United States)

Lu, Dongwei; Zhang, Tao; Ma, Jun

2015-04-07

Oil/water (O/W) emulsion stabilized by surfactants is the part of oily wastewater that is most difficult to handle. Ceramic membrane ultrafiltration presently is an ideal process to treat O/W emulsions. However, little is known about the fouling mechanism of the ceramic membrane during O/W emulsion treatment. This paper investigated how stabilization surfactants of O/W emulsions influence the irreversible fouling of ceramic membranes during ultrafiltration. An unexpected phenomenon observed was that irreversible fouling was much less when the charge of the stabilization surfactant of O/W emulsions is opposite to the membrane. The less ceramic membrane fouling in this case was proposed to be due to a synergetic steric effect and demulsification effect which prevented the penetration of oil droplets into membrane pores and led to less pore blockage. This proposed mechanism was supported by cross section images of fouled and virgin ceramic membranes taken with scanning electron microscopy, regression results of classical fouling models, and analysis of organic components rejected by the membrane. Furthermore, this mechanism was also verified by the existence of a steric effect and demulsification effect. Our finding suggests that ceramic membrane oppositely charged to the stabilization surfactant should be applied in ultrafiltration of O/W emulsions to alleviate irreversible membrane fouling. It could be a useful rule for ceramic membrane ultrafiltration of oily wastewater.

Ceramic membrane fouling during ultrafiltration of oil/water emulsions: Roles played by stabilization surfactants of oil droplets

KAUST Repository

Lu, Dongwei

2015-04-07

Oil/water (O/W) emulsion stabilized by surfactants is the part of oily wastewater that is most difficult to handle. Ceramic membrane ultrafiltration presently is an ideal process to treat O/W emulsions. However, little is known about the fouling mechanism of the ceramic membrane during O/W emulsion treatment. This paper investigated how stabilization surfactants of O/W emulsions influence the irreversible fouling of ceramic membranes during ultrafiltration. An unexpected phenomenon observed was that irreversible fouling was much less when the charge of the stabilization surfactant of O/W emulsions is opposite to the membrane. The less ceramic membrane fouling in this case was proposed to be due to a synergetic steric effect and demulsification effect which prevented the penetration of oil droplets into membrane pores and led to less pore blockage. This proposed mechanism was supported by cross section images of fouled and virgin ceramic membranes taken with scanning electron microscopy, regression results of classical fouling models, and analysis of organic components rejected by the membrane. Furthermore, this mechanism was also verified by the existence of a steric effect and demulsification effect. Our finding suggests that ceramic membrane oppositely charged to the stabilization surfactant should be applied in ultrafiltration of O/W emulsions to alleviate irreversible membrane fouling. It could be a useful rule for ceramic membrane ultrafiltration of oily wastewater. © 2015 American Chemical Society.

História, etnia e nação: o índio e a formação nacional sob a ótica de Caio Prado Júnior History, Ethny and nation: indians and the national construction according to caio prado Júnior's perspective

Directory of Open Access Journals (Sweden)

Vânia Maria Losada Moreira

2008-06-01

Full Text Available Neste artigo pretendemos analisar o argumento segundo o qual a mestiçagem foi o meio fundamental de integração do índio à sociedade dominante em expansão. Elegemos como foco principal de nosso estudo o livro Formação do Brasil Contemporâneo, deCaio Prado Jr., por se tratar da principal obra histórica do autor e aquela que o alçou como um dos maiores expoentes da historiografia nacional. Enfocaremos o papel desempenhado pela idéia de mestiçagem no mito de fundação da nação brasileira, a mestiçagem como principal meio de integração social do índio e, finalmente, algumas armadilhas que a idéia de miscigenação produz, impedindo uma apreensão crítica da presença indígena no processo de desenvolvimento histórico do Brasil e do povo brasileiro.In this article we discuss the argument that the race mixing was the fundamental factor for integrating the indian population in the Brazilian dominant society. We focus our attention on the myth created about the race mixing and the foundation of the Brazilian nation and on the race mixing as the main process of social integration of the indian population in the Brazilian society. Finally, we discuss some misleading conclusions that the race mixing has produced about this subject, which hinders a complete understanding about the indian contribution to the development of Brazil and of the Brazilian People. We consider the book from Caio Prado Jr., Formation of Contemporary Brazil as our main bibliographical source because its importance in the Brazilian historiography.

Investigation and Modelling of Diesel Hydrotreating Reactions

DEFF Research Database (Denmark)

Boesen, Rasmus Risum

on a commercial CoMo catalyst, and a simple kinetic model is presented. Hydrogenation of fused aromatic rings are known to be fast, and it is possible, that the reaction rates are limited by either internal or external mass transfer. An experiment conducted at industrial temperatures and pressure, using...... naphthalene as a model compound, have shown, that intra-particle diffusion resistance are likely to limit the reaction rate. In order to produce ULSD it is necessary to remove sulfur from some of the most refrac- tive sulfur compounds, such as sterically hindered dibenzothiophenes. Basic nitrogen com- pounds...... are known to inhibit certain hydrotreating reactions. Experimental results are pre- sented, showing the effect of 3 different nitrogen compounds, acridine, 1,4-dimethylcarabazole and 3-methylindole, on the hydrodesulfurization of a real feed and of a model compound, 4,6-dimethyldibenzothiophene. It is shown...

Capped Mesoporous Silica Nanoparticles for the Selective and Sensitive Detection of Cyanide.

Science.gov (United States)

Sayed, Sameh El; Licchelli, Maurizio; Martínez-Máñez, Ramón; Sancenón, Félix

2017-10-18

The development of easy and affordable methods for the detection of cyanide is of great significance due to the high toxicity of this anion and the potential risks associated with its pollution. Herein, optical detection of cyanide in water has been achieved by using a hybrid organic-inorganic nanomaterial. Mesoporous silica nanoparticles were loaded with [Ru(bipy) 3 ] 2+ , functionalized with macrocyclic nickel(II) complex subunits, and capped with a sterically hindering anion (hexametaphosphate). Cyanide selectively induces demetallation of nickel(II) complexes and the removal of capping anions from the silica surface, allowing the release of the dye and the consequent increase in fluorescence intensity. The response of the capped nanoparticles in aqueous solution is highly selective and sensitive towards cyanide with a limit of detection of 2 μm. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

A pulse radiolysis study of the reaction of hydroxyl radicals with trans-dihydroxo(1,4,8,11-tetraazacyclotetradecane)chromium(3)

International Nuclear Information System (INIS)

Moensted, O.; Nord, G.; Pagsberg, P.

1987-01-01

Hydroxyl radicals react rapidly with the title chromium(III) complex. In weakly alkaline solution, around pH≅ the product rearranges by a first-order process followed by a second-order process. This sequence is interpreted as the formation of a chromium(IV) complex which then forms a μ-peroxochromium(III) dimer. The dimer decomposes by a two-electron oxidation of the macrocyclic ligan with the concomitant formation of a double bond. In more strongly basic solution and also in dilute acid, the decay kinetics are more complicated. Supplementary measurements using trans-difluoro(1,4,8,11-tetraazacyclotetradecane)Chromium(III), which does not contain coordinated hydroxide, and cis-dihydroxo(rac-5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane)-chromium(III), for which dimerization is sterically hindered, support the above interpretation of the consecutive reactions for the title complex. (author)

Surface-enhanced Raman Spectroscopy of Ethephone Adsorbed on Silver Surface

International Nuclear Information System (INIS)

Lee, Chul Jae; Kim, Hee Jin; Karim, Mohammad Rezaul; Lee, Mu Sang

2006-01-01

We investigated the Surface-enhanced Raman Spectroscopy (SERS) spectrum of ethephone (2- chloroethylphosphonic acid). We observed significant signals in the ordinary Raman spectrum for solid-state ethephone as well as when it was adsorbed on a colloidal silver surface, strong vibrational signals were obtained at a very low concentration. The SERS spectra were obtained by silver colloids that were prepared by the γ - irradiation method. The influence of pH and the influence of anion (Cl - , Br - , I - ) on the adsorption orientation were investigated. Two different adsorption mechanisms were deduced, depending on the experimental conditions. The chlorine atom or the chlorine and two oxygen atoms were adsorbed on the colloidal silver surface. Among halide ions, Br - and I - were more strongly adsorbed on the colloidal silver surfaces. As a result, the adsorption of ethephone was less effective due to their steric hinderance

Directed evolution of a thermostable l-aminoacylase biocatalyst

DEFF Research Database (Denmark)

Parker, Brenda M.; Taylor, Ian N.; Woodley, John

2011-01-01

Enzymes from extreme environments possess highly desirable traits of activity and stability for application under process conditions. One such example is l-aminoacylase (E.C. 3.5.1.14) from Thermococcus litoralis (TliACY), which catalyzes the enantioselective amide hydrolysis of N-protected l......-amino acids, useful for resolving racemic mixtures in the preparation of chiral intermediates. Variants of this enzyme with improved activity and altered substrate preference are highly desirable. We have created a structural homology model of the enzyme and applied various two different directed evolution....... The substrate preference of wild type decreases with increasingly branched and sterically hindered substrates. However, the mutant S100T/M106K disrupted this simple trend by selectively improving the substrate preference for N-benzoyl valine, with a >30-fold shift in the ratio of kcat values for N...

As(III) oxidation by MnO2 during groundwater treatment.

Science.gov (United States)

Gude, J C J; Rietveld, L C; van Halem, D

2017-03-15

The top layer of natural rapid sand filtration was found to effectively oxidise arsenite (As(III)) in groundwater treatment. However, the oxidation pathway has not yet been identified. The aim of this study was to investigate whether naturally formed manganese oxide (MnO 2 ), present on filter grains, could abiotically be responsible for As(III) oxidation in the top of a rapid sand filter. For this purpose As(III) oxidation with two MnO 2 containing powders was investigated in aerobic water containing manganese(II) (Mn(II)), iron(II) (Fe(II)) and/or iron(III) (Fe(III)). The first MnO 2 powder was a very pure - commercially available - natural MnO 2 powder. The second originated from a filter sand coating, produced over 22 years in a rapid filter during aeration and filtration. Jar test experiments showed that both powders oxidised As(III). However, when applying the MnO 2 in aerated, raw groundwater, As(III) removal was not enhanced compared to aeration alone. It was found that the presence of Fe(II)) and Mn(II) inhibited As(III) oxidation, as Fe(II) and Mn(II) adsorption and oxidation were preferred over As(III) on the MnO 2 surface (at pH 7). Therefore it is concluded that just because MnO 2 is present in a filter bed, it does not necessarily mean that MnO 2 will be available to oxidise As(III). However, unlike Fe(II), the addition of Fe(III) did not hinder As(III) oxidation on the MnO 2 surface; resulting in subsequent effective As(V) removal by the flocculating hydrous ferric oxides. Copyright © 2016 Elsevier Ltd. All rights reserved.

Position of coordination of the lithium ion determines the regioselectivity of demethylations of 3,4-dimethoxymorphinans with L-selectride.

Science.gov (United States)

Wu, Huifang; Thatcher, Linn N; Bernard, Denzil; Parrish, Damon A; Deschamps, Jeffrey R; Rice, Kenner C; MacKerell, Alexander D; Coop, Andrew

2005-06-23

[reaction: see text] L-Selectride is an efficient agent for the 3-O-demethylation of opioids and is known to cleave the least hindered methoxyl group in a molecule. The treatment of a 3,4-dimethoxymorphinan containing a 6-ketal with L-Selectride gave selective 4-O-demethylation, rather than cleavage of the less hindered 3-methoxyl. In contrast, a 3,4-dimethoxymorphinan lacking a 6-ketal gave selective 3-O-demethylation, suggesting that the regiochemistry of L-Selectride-mediated O-demethylation can be manipulated through altering the position of coordination of the lithium ion.

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

Minimalismos, abolucionismos e eficienticismo: a crise do sistema penal entre a deslegitimação e a expansão

Directory of Open Access Journals (Sweden)

Vera Regina Pereira de Andrade

2006-06-01

Full Text Available O texto trata de contextualizar oMinimalismo e o Abolicionismo penal nohorizonte de crise de legitimidade oudeslegitimação do sistema penal, apontando parasua complexidade e pluralidade (o que impede sefale de minimalismo e abolicionismo no singulare para sua relação com o Eficientismo penal e aexpansão do sistema penal. Partindo do argumentoda existência de diferentes minimalismos eabolicionismos, tanto no plano teorético quantono plano prático-reformista, e das diferentesformas de pendularismo e cruzamento entreminimalismo-abolicionismo-eficientismo,fundamenta-se a tese de que a antítese doabolicionismo não é o minimalismo, mas oeficientismo penal, e o rumo da política criminal contemporânea que ele protagoniza (associado, paradoxalmente, ao minimalismo reformista. Conseqüentemente, o dilema do nosso tempo nãoé, como corriqueiramente se debate, a escolhabipolar entre minimalismo e abolicionismo, masa concorrência, absolutamente desleal, entre atotalizadora colonização do eficientismo e aaversão ao abolicionismo, mediados pelo pretensoequilíbrio prudente de minimalismos de híbridaidentidade.The text deals with contextualizar theMinimalism and the criminal Abolitionism in thehorizon of legitimacy crisis or non-legitimation ofthe criminal system , pointing with respect to itscomplexity and plurality (what it hinders if saysof minimalism and abolitionism in the singularand with respect to its relation with the criminalefficientism and the expansion of the criminalsystem. Breaking of the argument of the existenceof different minimalisms and abolitionisms, asmuch in the theoretical plan how much in the planpractical-reformist, e of the different forms ofpendularism and crossing between minimalismabolitionism-efficientism, it is based thesis of thatthe antithesis of the abolitionism is not theminimalism, but the criminal efficientism, the route of the criminal politics contemporary who it carries out (associated, paradoxicalally

1H NMR spectra part 31: 1H chemical shifts of amides in DMSO solvent.

Science.gov (United States)

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

2014-07-01

The (1)H chemical shifts of 48 amides in DMSO solvent are assigned and presented. The solvent shifts Δδ (DMSO-CDCl3 ) are large (1-2 ppm) for the NH protons but smaller and negative (-0.1 to -0.2 ppm) for close range protons. A selection of the observed solvent shifts is compared with calculated shifts from the present model and from GIAO calculations. Those for the NH protons agree with both calculations, but other solvent shifts such as Δδ(CHO) are not well reproduced by the GIAO calculations. The (1)H chemical shifts of the amides in DMSO were analysed using a functional approach for near ( ≤ 3 bonds removed) protons and the electric field, magnetic anisotropy and steric effect of the amide group for more distant protons. The chemical shifts of the NH protons of acetanilide and benzamide vary linearly with the π density on the αN and βC atoms, respectively. The C=O anisotropy and steric effect are in general little changed from the values in CDCl3. The effects of substituents F, Cl, Me on the NH proton shifts are reproduced. The electric field coefficient for the protons in DMSO is 90% of that in CDCl3. There is no steric effect of the C=O oxygen on the NH proton in an NH…O=C hydrogen bond. The observed deshielding is due to the electric field effect. The calculated chemical shifts agree well with the observed shifts (RMS error of 0.106 ppm for the data set of 257 entries). Copyright © 2014 John Wiley & Sons, Ltd.

SnO2 Quantum Dots@Graphene Oxide as a High-Rate and Long-Life Anode Material for Lithium-Ion Batteries.

Science.gov (United States)

Zhao, Kangning; Zhang, Lei; Xia, Rui; Dong, Yifan; Xu, Wangwang; Niu, Chaojiang; He, Liang; Yan, Mengyu; Qu, Longbin; Mai, Liqiang

2016-02-03

Tin-based electrode s offer high theoretical capacities in lithium ion batteries, but further commercialization is strongly hindered by the poor cycling stability. An in situ reduction method is developed to synthesize SnO2 quantum dots@graphene oxide. This approach is achieved by the oxidation of Sn(2+) and the reduction of the graphene oxide. At 2 A g(-1), a capacity retention of 86% is obtained even after 2000 cycles. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A practical pathway for the preparation of Fe{sub 2}O{sub 3} decorated TiO{sub 2} photocatalyst with enhanced visible-light photoactivity

Energy Technology Data Exchange (ETDEWEB)

Cheng, Li; Qiu, Shoufei [Institute of Polymer Materials, School of Materials Science and Engineering, Jiangsu University, Zhenjiang 212013 (China); Chen, Juanrong, E-mail: Juanrongchen@ujs.edu.cn [School of Environment and Safety Engineering, Jiangsu University, Zhenjiang 212013 (China); Shao, Jian [Institute of Polymer Materials, School of Materials Science and Engineering, Jiangsu University, Zhenjiang 212013 (China); Cao, Shunsheng, E-mail: sscaochem@hotmail.com [Institute of Polymer Materials, School of Materials Science and Engineering, Jiangsu University, Zhenjiang 212013 (China)

2017-04-01

Shifting the ultra-violet of titania to visible light driven photocatalysis can be realized by coupling with metallic or non-metallic elements. However, time-consuming multi-step process and significant loss of UV photocatalytic activity of such TiO{sub 2}-based photocatalysts severely hinder their practical applications. In this work, we explore the idea of creating a practical method for the preparation of Fe{sub 2}O{sub 3} decorated TiO{sub 2} (TiO{sub 2}/Fe{sub 2}O{sub 3}) photocatalyst with controlled visible-light photoactivity. This method only involves the calcination of the mixture (commercial P25 powders and magnetic Fe{sub 3}O{sub 4} nanoparticles) prepared by a mechanical process. The morphology and properties of TiO{sub 2}/Fe{sub 2}O{sub 3} composites were characterized by Transmission electron microscope, X-ray diffraction, UV–vis spectroscopy, and X-ray photoelectron spectroscopy. Results confirm the fusion of TiO{sub 2} and Fe{sub 2}O{sub 3}, which promotes photo-generated electrons/holes migration and separation. Because of the strong synergistic effect, the as-synthesized TiO{sub 2}/Fe{sub 2}O{sub 3} composites manifest an enhanced visible-light photocatalytic activity. Especially, the TiO{sub 2}/Fe{sub 2}O{sub 3} photocatalyst is very easy to be constructed via an one-step protocol that efficiently overcomes the time-consuming multi-step processes used in existed strategies for the preparation of Fe{sub 2}O{sub 3}/TiO{sub 2} photocatalysts, providing a new insight into the practical application of TiO{sub 2}/Fe{sub 2}O{sub 3} visible light photocatalyst. - Highlights: • We introduced a practical preparation of Fe{sub 2}O{sub 3} decorated TiO{sub 2} photocatalyst. • TiO{sub 2}/Fe{sub 2}O{sub 3} was developed using commercial precursors in a high efficient manner. • Visible-light activity of TiO{sub 2}/Fe{sub 2}O{sub 3} could be tuned by changing amount of Fe{sub 3}O{sub 4} precursor. • TiO{sub 2}/Fe{sub 2}O{sub 3} exhibited a higher

Origin of Capacity Fading in Nano-Sized Co3O4Electrodes: Electrochemical Impedance Spectroscopy Study

Directory of Open Access Journals (Sweden)

Kang Jin-Gu

2008-01-01

Full Text Available Abstract Transition metal oxides have been suggested as innovative, high-energy electrode materials for lithium-ion batteries because their electrochemical conversion reactions can transfer two to six electrons. However, nano-sized transition metal oxides, especially Co3O4, exhibit drastic capacity decay during discharge/charge cycling, which hinders their practical use in lithium-ion batteries. Herein, we prepared nano-sized Co3O4with high crystallinity using a simple citrate-gel method and used electrochemical impedance spectroscopy method to examine the origin for the drastic capacity fading observed in the nano-sized Co3O4anode system. During cycling, AC impedance responses were collected at the first discharged state and at every subsequent tenth discharged state until the 100th cycle. By examining the separable relaxation time of each electrochemical reaction and the goodness-of-fit results, a direct relation between the charge transfer process and cycling performance was clearly observed.

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)

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.

Recent progress on doped ZnO nanostructures for visible-light photocatalysis

International Nuclear Information System (INIS)

Samadi, Morasae; Zirak, Mohammad; Naseri, Amene; Khorashadizade, Elham; Moshfegh, Alireza Z.

2016-01-01

Global environmental pollution and energy supply demand have been regarded as important concerns in recent years. Metal oxide semiconductor photocatalysts is a promising approach to apply environmental remediation as well as fuel generation from water splitting and carbon dioxide reduction. ZnO nanostructures have been shown promising photocatalytic activities due to their non-toxic, inexpensive, and highly efficient nature. However, its wide band gap hinders photo-excitation for practical photocatalytic applications under solar light as an abundant, clean and safe energy source. To overcome this barrier, many strategies have been developed in the last decade to apply ZnO nanostructured photocatalysts under visible light. In this review, we have classified different approaches to activate ZnO as a photocatalyst in visible-light spectrum. Utilization of various nonmetals, transition metals and rare-earth metals for doping in ZnO crystal lattice to create visible-light-responsive doped ZnO photocatalysts is discussed. Generation of localized energy levels within the gap in doped ZnO nanostructures has played an important role in effective photocatalytic reaction under visible-light irradiation. The effect of dopant type, ionic size and its concentration on the crystal structure, electronic property and morphology of doped ZnO with a narrower band gap is reviewed systematically. Finally, a comparative study is performed to evaluate two classes of metals and nonmetals as useful dopants for ZnO nanostructured photocatalysts under visible light. - Highlights: • Metals and nonmetals used as a dopant to shift ZnO band gap toward visible-light. • Modification of electronic structure played a crucial role in doped ZnO activity. • Correlation between dopant's characteristics and ZnO visible activity was reviewed. • Photo-degradation of doped ZnO was studied and compared for different dopants.

Recent progress on doped ZnO nanostructures for visible-light photocatalysis

Energy Technology Data Exchange (ETDEWEB)

Samadi, Morasae; Zirak, Mohammad [Department of Physics, Sharif University of Technology, P.O. Box 11555-9161, Tehran (Iran, Islamic Republic of); Naseri, Amene [Institute for Nanoscience and Nanotechnology, Sharif University of Technology, P.O. Box 11365-8639, Tehran (Iran, Islamic Republic of); Khorashadizade, Elham [Department of Physics, Sharif University of Technology, P.O. Box 11555-9161, Tehran (Iran, Islamic Republic of); Moshfegh, Alireza Z., E-mail: moshfegh@sharif.edu [Department of Physics, Sharif University of Technology, P.O. Box 11555-9161, Tehran (Iran, Islamic Republic of); Institute for Nanoscience and Nanotechnology, Sharif University of Technology, P.O. Box 11365-8639, Tehran (Iran, Islamic Republic of)

2016-04-30

Global environmental pollution and energy supply demand have been regarded as important concerns in recent years. Metal oxide semiconductor photocatalysts is a promising approach to apply environmental remediation as well as fuel generation from water splitting and carbon dioxide reduction. ZnO nanostructures have been shown promising photocatalytic activities due to their non-toxic, inexpensive, and highly efficient nature. However, its wide band gap hinders photo-excitation for practical photocatalytic applications under solar light as an abundant, clean and safe energy source. To overcome this barrier, many strategies have been developed in the last decade to apply ZnO nanostructured photocatalysts under visible light. In this review, we have classified different approaches to activate ZnO as a photocatalyst in visible-light spectrum. Utilization of various nonmetals, transition metals and rare-earth metals for doping in ZnO crystal lattice to create visible-light-responsive doped ZnO photocatalysts is discussed. Generation of localized energy levels within the gap in doped ZnO nanostructures has played an important role in effective photocatalytic reaction under visible-light irradiation. The effect of dopant type, ionic size and its concentration on the crystal structure, electronic property and morphology of doped ZnO with a narrower band gap is reviewed systematically. Finally, a comparative study is performed to evaluate two classes of metals and nonmetals as useful dopants for ZnO nanostructured photocatalysts under visible light. - Highlights: • Metals and nonmetals used as a dopant to shift ZnO band gap toward visible-light. • Modification of electronic structure played a crucial role in doped ZnO activity. • Correlation between dopant's characteristics and ZnO visible activity was reviewed. • Photo-degradation of doped ZnO was studied and compared for different dopants.

Surface Plasmon Enhanced Photocatalysis of Au/Pt-decorated TiO2 Nanopillar Arrays

Science.gov (United States)

Shuang, Shuang; Lv, Ruitao; Xie, Zheng; Zhang, Zhengjun

2016-05-01

The low quantum yields and lack of visible light utilization hinder the practical application of TiO2 in high-performance photocatalysis. Herein, we present a design of TiO2 nanopillar arrays (NPAs) decorated with both Au and Pt nanoparticles (NPs) directly synthesized through successive ion layer adsorption and reaction (SILAR) at room temperature. Au/Pt NPs with sizes of ~4 nm are well-dispersed on the TiO2 NPAs as evidenced by electron microscopic analyses. The present design of Au/Pt co-decoration on the TiO2 NPAs shows much higher visible and ultraviolet (UV) light absorption response, which leads to remarkably enhanced photocatalytic activities on both the dye degradation and photoelectrochemical (PEC) performance. Its photocatalytic reaction efficiency is 21 and 13 times higher than that of pure TiO2 sample under UV-vis and visible light, respectively. This great enhancement can be attributed to the synergy of electron-sink function of Pt and surface plasmon resonance (SPR) of Au NPs, which significantly improves charge separation of photoexcited TiO2. Our studies demonstrate that through rational design of composite nanostructures one can harvest visible light through the SPR effect to enhance the photocatalytic activities initiated by UV-light, and thus realize more effectively utilization of the whole solar spectrum for energy conversion.

Photogeneration of H2O2 in Water-Swollen SPEEK/PVA Polymer Films.

Science.gov (United States)

Lockhart, PaviElle; Little, Brian K; Slaten, B L; Mills, G

2016-06-09

Efficient reduction of O2 took place via illumination with 350 nm photons of cross-linked films containing a blend of sulfonated poly(ether etherketone) and poly(vinyl alcohol) in contact with air-saturated aqueous solutions. Swelling of the solid macromolecular matrices in H2O enabled O2 diffusion into the films and also continuous extraction of the photogenerated H2O2, which was the basis for a method that allowed quantification of the product. Peroxide formed with similar efficiencies in films containing sulfonated polyketones prepared from different precursors and the initial photochemical process was found to be the rate-determining step. Generation of H2O2 was most proficient in the range of 4.9 ≤ pH ≤ 8 with a quantum yield of 0.2, which was 10 times higher than the efficiencies determined for solutions of the polymer blend. Increases in temperature as well as [O2] in solution were factors that enhanced the H2O2 generation. H2O2 quantum yields as high as 0.6 were achieved in H2O/CH3CN mixtures with low water concentrations, but peroxide no longer formed when film swelling was suppressed. A mechanism involving reduction of O2 by photogenerated α-hydroxy radicals from the polyketone in competition with second-order radical decay processes explains the kinetic features. Higher yields result from the films because cross-links present in them hinder diffusion of the radicals, limiting their decay and enhancing the oxygen reduction pathway.

Thermodynamics of mixtures containing amines. IX. Application of the concentration-concentration structure factor to the study of binary mixtures containing pyridines

Energy Technology Data Exchange (ETDEWEB)

Gonzalez, Juan Antonio, E-mail: jagl@termo.uva.es [G.E.T.E.F. Dpto Termodinamica y Fisica Aplicada, Facultad de Ciencias, Universidad de Valladolid, Valladolid 47071 (Spain); Cobos, Jose Carlos; Garcia de la Fuente, Isaias; Mozo, Ismael [G.E.T.E.F. Dpto Termodinamica y Fisica Aplicada, Facultad de Ciencias, Universidad de Valladolid, Valladolid 47071 (Spain)

2009-10-10

size effects are predominant over steric hindrances to the creation of the OH-N hydrogen bonds, which are expected to increase with the number of methyl groups in the aromatic amine. For a given 1-alkanol ({ne}methanol), S{sub CC}(0) varies in the sequence: pyridine > methyl pyridine {approx} 2,6-dimethylpyridine. For alkyl pyridines, stability seems to be independent of position and number of alkyl groups attached to the aromatic ring of the amine. Mixtures with isomeric 2-alkanols show lower heterocoordination, as the hydroxyl group is more sterically hindered than in 1-alkanols.

Interaction of Au with thin ZrO2 films: influence of ZrO2 morphology on the adsorption and thermal stability of Au nanoparticles.

Science.gov (United States)

Pan, Yonghe; Gao, Yan; Kong, Dandan; Wang, Guodong; Hou, Jianbo; Hu, Shanwei; Pan, Haibin; Zhu, Junfa

2012-04-10

The model catalysts of ZrO(2)-supported Au nanoparticles have been prepared by deposition of Au atoms onto the surfaces of thin ZrO(2) films with different morphologies. The adsorption and thermal stability of Au nanoparticles on thin ZrO(2) films have been investigated using synchrotron radiation photoemission spectroscopy (SRPES) and X-ray photoelectron spectroscopy (XPS). The thin ZrO(2) films were prepared by two different methods, giving rise to different morphologies. The first method utilized wet chemical impregnation to synthesize the thin ZrO(2) film through the procedure of first spin-coating a zirconium ethoxide (Zr(OC(2)H(5))(4)) precursor onto a SiO(2)/Si(100) substrate at room temperature followed by calcination at 773 K for 12 h. Scanning electron microscopy (SEM) investigations indicate that highly porous "sponge-like nanostructures" were obtained in this case. The second method was epitaxial growth of a ZrO(2)(111) film through vacuum evaporation of Zr metal onto Pt(111) in 1 × 10(-6) Torr of oxygen at 550 K followed by annealing at 1000 K. The structural analysis with low energy electron diffraction (LEED) of this film exhibits good long-range ordering. It has been found that Au forms smaller particles on the porous ZrO(2) film as compared to those on the ordered ZrO(2)(111) film at a given coverage. Thermal annealing experiments demonstrate that Au particles are more thermally stable on the porous ZrO(2) surface than on the ZrO(2)(111) surface, although on both surfaces, Au particles experience significant sintering at elevated temperatures. In addition, by annealing the surfaces to 1100 K, Au particles desorb completely from ZrO(2)(111) but not from porous ZrO(2). The enhanced thermal stability for Au on porous ZrO(2) can be attributed to the stronger interaction of the adsorbed Au with the defects and the hindered migration or coalescence resulting from the porous structures. © 2012 American Chemical Society

/sup 13/C, /sup 17/O, and /sup 33/S NMR spectra of alkyl phenyl sulfones C/sub 6/H/sub 5/SO/sub 2/Alk

Energy Technology Data Exchange (ETDEWEB)

Bzhezovskii, V.M.; Valeev, R.B.; Kalabin, G.A.; Aliev, I.A.

1987-06-20

The /sup 13/C, /sup 17/O, and /sup 33/S NMR spectra of alkyl phenyl sulfones C/sub 6/H/sub 5/SO/sub 2/Alk were obtained. The changes in the screening of the /sup 13/C, /sup 17/O, and /sup 33/S nuclei in these compounds are determined by the effect of the alkyl substituents, which alternates in sign and decreases along the chain of atoms in the order: CH/sub 3/, C/sub 2/H/sub 5/, iso-C/sub 3/H/sub 7/, and tert-C/sub 4/H/sub 9/. In the alkyl phenyl sulfides C/sub 6/H/sub 5/SAlk the additional effect of disruption in the p,..pi.. interaction between the sulfur atom and the benzene ring as a result of conformational changes is superimposed on the screening of the /sup 13/C/sup ortho/ nuclei. For the changes in the screening of the /sup 13/C/sup para/ nuclei in C/sub 6/H/sub 5/SAlk the steric disruption of the p,..pi.. conjugation by the alkyl substituents is determining.

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

Efeitos sobre o tecido ósseo e cartilagem articular provocados pela imobilização e remobilização em ratos Wistar Effects of immobilization and remobilization on bone tissue and cartilage in Wistar rats

Directory of Open Access Journals (Sweden)

Danielle Portinho

2008-10-01

Full Text Available Longos períodos de imobilização conduzem à perda óssea e de propriedades do osso, e sua recuperação depende de vários fatores; além disso, a imobilização pode causar ulcerações no tecido cartilaginoso articular devido a alterações como perda de proteoglicanas, de massa e volume totais da cartilagem. O objetivo deste estudo foi verificar alterações histológicas, do tecido ósseo periarticular e da cartilagem articular, provocadas pela imobilização e remobilização de membros posteriores de ratos Wistar. Foram utilizados 12 ratos Wistar, divididos em dois grupos: GI - (n = 6: 15 dias com o membro posterior esquerdo imobilizado em plantiflexão, sendo o membro direito o controle; GR - (n = 6: período de 15 dias de remobilização livre na gaiola, associado a três séries diárias de alongamento do músculo sóleo esquerdo por 30 segundos. Foram avaliados no tecido ósseo as medidas de espessura do osso cortical, diâmetro do canal medular e número de osteócitos; no tecido cartilaginoso, foram mensurados a espessura média da cartilagem e o número de condrócitos. Como resultado, observou-se que para GI não houve alterações significativas na espessura do osso (p = 0,1156 nem no diâmetro do canal medular (p = 0,5698, mas diminuição significativa dos osteócitos em relação ao contralateral (p = 0,0005; em GR também houve decréscimo no número de osteócitos (p = 0,0001, mas as diferenças na espessura (p = 0,1343 e diâmetro do canal medular (p = 0,6456 mantiveram-se não significantes. Para os dados de cartilagem articular não houve diferenças significativas para as amostras, tanto na espessura da cartilagem para GI (p = 0,6640 e GR (p = 0,1633, quanto no número de condrócitos em GI (p = 0,9429 e GR (p = 0,1634. Conclui-se que duas semanas de imobilização e remobilização produziram apenas diminuição significativa no número de osteócitos nos ratos imobilizados; esse número continuou a diminuir mesmo nos

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.

Diphenylcarbene Protected by Four ortho-Iodine Groups: An Unusually Persistent Triplet Carbene

Directory of Open Access Journals (Sweden)

Katsuyuki Hirai

2016-11-01

Full Text Available Diphenyldiazomethane with four iodine groups at the ortho positions and two tert-butyl groups at the para positions, i.e., bis(4-tert-butyl-2,6-diiodophenyldiazomethane (1a-N2, was synthesized as a sterically hindered triplet carbene precursor. Irradiation of 1a-N2 in solution effectively generated the corresponding triplet diphenylcarbene 31a, which was characterized by UV-vis spectroscopy at low temperature, along with laser flash photolysis techniques at room temperature. The UV-vis spectrum of 31a was obtained by irradiating 1a-N2 in a 2-methyltetrahydrofuran matrix at 77 K. The ESR spectrum showed no triplet carbene signals, while a radical species was observed at the anticipated temperature of the decomposition of triplet carbene 31a. Transient absorption bands ascribable to 31a were observed by laser flash photolysis of 1a-N2 in a degassed benzene solution and decayed very slowly with a second-order rate constant (2k/εl of 5.5 × 10−3·s−1. Steady-state irradiation of 1a-N2 in degassed benzene afforded 9,10-diarylphenanthrene derivative 2a in a 31% yield. Triplet carbene 31a was also trapped by either oxygen (kO2 = 6.5 × 105 M−1·s−1 or 1,4-cyclohexadiene (kCHD = 1.5 M−1·s−1 to afford the corresponding ketone 1a-O or the diarylmethane 1a-H2. The carbene was shown to be much less reactive than the triplet diphenylcarbene that is protected by two ortho-iodo and two ortho-bromo groups, 31b.

Reactivity of uranium(IV) bridged chalcogenido complexes UIV–E–UIV (E = S, Se) with elemental sulfur and selenium: synthesis of polychalcogenido-bridged uranium complexes

OpenAIRE

Franke, Sebastian M.; Heinemann, Frank W.; Meyer, Karsten

2014-01-01

We report the syntheses, electronic properties, and molecular structures of a series of polychalcogenido-bridged dinuclear uranium species. These complexes are supported by the sterically encumbering but highly flexible, single N-anchored tris(aryloxide) chelator (AdArO)3N3−. Reaction of an appropriate uranium precursor, either the U(III) starting material, [((AdArO)3N)U(DME)], or the dinuclear mono-chalcogenido-bridged uranium(IV/IV) compounds [{((AdArO)3N)U(DME)}2(μ-E)] (E = S, Se), with el...

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.

From Single Atoms to Nanoparticles: Autocatalysis and Metal Aggregation in Atomic Layer Deposition of Pt on TiO2 Nanopowder.

Science.gov (United States)

Grillo, Fabio; Van Bui, Hao; La Zara, Damiano; Aarnink, Antonius A I; Kovalgin, Alexey Y; Kooyman, Patricia; Kreutzer, Michiel T; van Ommen, Jan Rudolf

2018-05-10

A fundamental understanding of the interplay between ligand-removal kinetics and metal aggregation during the formation of platinum nanoparticles (NPs) in atomic layer deposition of Pt on TiO 2 nanopowder using trimethyl(methylcyclo-pentadienyl)platinum(IV) as the precursor and O 2 as the coreactant is presented. The growth follows a pathway from single atoms to NPs as a function of the oxygen exposure (P O2 × time). The growth kinetics is modeled by accounting for the autocatalytic combustion of the precursor ligands via a variant of the Finke-Watzky two-step model. Even at relatively high oxygen exposures ( 120 mbar s. The deposition of more Pt leads to the formation of NPs that can be as large as 6 nm. Crucially, high P O2 (≥5 mbar) hinders metal aggregation, thus leading to narrow particle size distributions. The results show that ALD of Pt NPs is reproducible across small and large surface areas if the precursor ligands are removed at high P O2 . © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Hydrogenated TiO{sub 2} nanobelts as highly efficient photocatalytic organic dye degradation and hydrogen evolution photocatalyst

Energy Technology Data Exchange (ETDEWEB)

Tian, Jian [School of Materials Science and Engineering, Shandong University of Science and Technology, Qingdao 266590 (China); State key Laboratory of Crystal Materials, Shandong University, Jinan 250100 (China); Leng, Yanhua [State key Laboratory of Crystal Materials, Shandong University, Jinan 250100 (China); Cui, Hongzhi, E-mail: cuihongzhi1965@163.com [School of Materials Science and Engineering, Shandong University of Science and Technology, Qingdao 266590 (China); Liu, Hong, E-mail: hongliu@sdu.edu.cn [State key Laboratory of Crystal Materials, Shandong University, Jinan 250100 (China)

2015-12-15

Highlights: • A facile synthesis of hydrogenated TiO{sub 2} nanobelts is reported. • Utilizing UV and visible light in photocatalytic degradation and H{sub 2} production. • The improved photocatalytic property is owe to Ti{sup 3+} ions and oxygen vacancies. - Abstract: TiO{sub 2} nanobelts have gained increasing interest because of its outstanding properties and promising applications in a wide range of fields. Here we report the facile synthesis of hydrogenated TiO{sub 2} (H-TiO{sub 2}) nanobelts, which exhibit excellent UV and visible photocatalytic decomposing of methyl orange (MO) and water splitting for hydrogen production. The improved photocatalytic property can be attributed to the Ti{sup 3+} ions and oxygen vacancies in TiO{sub 2} nanobelts created by hydrogenation. Ti{sup 3+} ions and oxygen vacancies can enhance visible light absorption, promote charge carrier trapping, and hinder the photogenerated electron–hole recombination. This work offers a simple strategy for the fabrication of a wide solar spectrum of active photocatalysts, which possesses significant potential for more efficient photodegradation, photocatalytic water splitting, and enhanced solar cells using sunlight as light source.

The Solar and Southern Oscillation Components in the Satellite Altimetry Data

DEFF Research Database (Denmark)

Howard, Daniel; Shaviv, Nir J.; Svensmark, Henrik

2015-01-01

altimetry data can be explained as the combined effect of both the solar forcing and the El Niño-Southern Oscillation (ENSO). The phase of the solar component can be used to derive the different steric and eustatic contributions. We find that the peak to peak radiative forcing associated with the solar...

Ground- and excited-state pinched cone equilibria in calix[4]arenes bearing two perylene bisimide dyes

NARCIS (Netherlands)

Hippius, C.; van Stokkum, I.H.M.; Zangrando, E.; Williams, R.M.; Wykes, M.; Beljonne, D.; Wurthner, F.

2008-01-01

We report on a series of bis-chromophoric compounds o2c, g2c, and r2c, afforded by linking two identical orange, green, or red perylene bisimide (PBI) units, respectively, through a calix[4]arene spacer unit. The PBI units are characterized by their increasing sterical demand from a planar

Ground- and excited-state pinched cone equilibria in calix[4]arenes bearing two perylene bisimide dyes

NARCIS (Netherlands)

Hippius, C.; van Stokkum, I.H.M.; Zangrando, E.; Williams, R.M.; Wykes, M.; Beljonne, D.; Würthner, F.

2008-01-01

We report oil a series of bis-chromophoric compounds o2c, g2c, and r2c, afforded by linking two identical orange, green, or red perylene bisimide (PBI) units, respectively, through a calix[4]arene spacer unit. The PBI units are characterized by their increasing sterical demand from a planar

The role of nanoparticulate agglomerates in TiO{sub 2} photocatalysis: degradation of oxalic acid

Energy Technology Data Exchange (ETDEWEB)

Ivanova, Irina [Leibniz Universitaet Hannover, Institut fuer Technische Chemie (Germany); Mendive, Cecilia B., E-mail: cbmendive@mdp.edu.ar [Universidad Nacional de Mar del Plata, Facultad de Ciencias Exactas y Naturales, Departamento de Química (Argentina); Bahnemann, Detlef [Leibniz Universitaet Hannover, Institut fuer Technische Chemie (Germany)

2016-07-15

The simultaneous bimodal study of the photocatalytic oxalic acid degradation by aqueous TiO{sub 2} suspensions revealed that particular systems possess the capacity to protect a certain amount of oxalic acid from oxidation, thus hindering, to some extent, the photocatalytic reaction. While measurements of the oxalic acid concentration in the bulk liquid phase indicated full photocatalytic degradation; in situ pH-stat measurements allowed the quantification of the amount of oxalic acid remaining in the part of the nanoparticulate agglomerates where light could apparently not access. An explanation for this phenomenon takes into account the possibility of the formation of TiO{sub 2} agglomerates in which these molecules are hidden from the effect of the light, thus being protected from photocatalytic degradation. Studies of different TiO{sub 2} materials with different particle sizes allowed a deeper exploration of this phenomenon. In addition, because this property of encapsulating pollutant molecules by photocatalytic systems is found to be a reversible phenomenon, P25 appears to be more convenient and advantageous as compared to the use of large surface area photocatalysts.Graphical AbstractFig.: Deaggregation of TiO{sub 2} particle agglomerates upon UV illumination.

Electrocatalytic activity of lithium polysulfides adsorbed into porous TiO2 coated MWCNTs hybrid structure for lithium-sulfur batteries

Science.gov (United States)

He, Xiulin; Hou, Huijie; Yuan, Xiqing; Huang, Long; Hu, Jingping; Liu, Bingchuan; Xu, Jingyi; Xie, Jia; Yang, Jiakuan; Liang, Sha; Wu, Xu

2017-01-01

Lithium-sulfur batteries have attracted great attention because of their high energy density, environmental friendliness, natural abundance and intrinsically low cost of sulfur. However, their commercial applications are greatly hindered by rapid capacity decay due to poor conductivity of electrode, fast dissolution of the intermediate polysulfides into the electrolyte, and the volume expansion of sulfur. Herein, we report a novel composite MWCNTs@TiO2-S nanostructure by grafting TiO2 onto the surface of MWCNTs, followed by incorporating sulfur into the composite. The inner MWCNTs improved the mechanical strength and conductivity of the electrode and the outer TiO2 provided the adsorption sites to immobilize polysulfides due to bonding interaction between TiO2 and polysulfides. The MWCNTs@TiO2-S composite with a mass ratio of 50% (MWCNTs in MWCNTs@TiO2) exhibited the highest electrochemistry performance among all compositing ratios of MWCNTs/TiO2. The performance improvement might be attributed to the downward shift of the apparent Fermi level to a more positive potential and electron rich space region at the interface of MWCNTs-TiO2 that facilitates the reduction of lithium polysulfide at a higher potential. Such a novel hybrid structure can be applicable for electrode design in other energy storage applications. PMID:28098167

Base catalyzed decomposition of toxic and hazardous chemicals

International Nuclear Information System (INIS)

Rogers, C.J.; Kornel, A.; Sparks, H.L.

1991-01-01

There are vast amounts of toxic and hazardous chemicals, which have pervaded our environment during the past fifty years, leaving us with serious, crucial problems of remediation and disposal. The accumulation of polychlorinated biphenyls (PCBs), polychlorinated dibenzo-p-dioxins (PCDDs), ''dioxins'' and pesticides in soil sediments and living systems is a serious problem that is receiving considerable attention concerning the cancer-causing nature of these synthetic compounds.US EPA scientists developed in 1989 and 1990 two novel chemical Processes to effect the dehalogenation of chlorinated solvents, PCBs, PCDDs, PCDFs, PCP and other pollutants in soil, sludge, sediment and liquids. This improved technology employs hydrogen as a nucleophile to replace halogens on halogenated compounds. Hydrogen as nucleophile is not influenced by steric hinderance as with other nucleophile where complete dehalogenation of organohalogens can be achieved. This report discusses catalyzed decomposition of toxic and hazardous chemicals

Modulation of allogeneic stimulation in man. I. Characterization of an in vitro induced suppressor macrophage population

International Nuclear Information System (INIS)

Stux, S.V.; Dubey, D.P.; Yunis, E.J.

1981-01-01

Cultured human peripheral blood mononuclear cells suppressed the allogeneic response of fresh autologous lymphocytes. This suppressor activity developed gradually over a period of one week. The cells primarily responsible for this effect were enriched by Ficoll density gradient centrifugation. It was found that the suppressor cell is a large, low density nylon wool adherent, radioresistant, phagocytic, and nonspecific esterase positive mononuclear cell. Moreover, these cells did not form E rosettes and were Fc positive. Electron microscopy confirmed that suppressor cells were macrophage like. Suppressor activity was not due to cytotoxicity, crowding, or steric hinderance by the cultured cells. The suppressor macrophage population did not appear to inhibit the allogeneic response via prostaglandin or arginase release, or interfere with the tritiated thymidine uptake by release of endogenous thymidine. The above system is viewed as an in vitro model of immune regulation by suppressor macrophages, in the context of allogeneic response

Arabidopsis ATP A2 peroxidase. Expression and high-resolution structure of a plant peroxidase with implications for lignification

DEFF Research Database (Denmark)

Ostergaard, L; Teilum, K; Mirza, O

2000-01-01

Lignins are phenolic biopolymers synthesized by terrestrial, vascular plants for mechanical support and in response to pathogen attack. Peroxidases have been proposed to catalyse the dehydrogenative polymerization of monolignols into lignins, although no specific isoenzyme has been shown...... to be involved in lignin biosynthesis. Recently we isolated an extracellular anionic peroxidase, ATP A2, from rapidly lignifying Arabidopsis cell suspension culture and cloned its cDNA. Here we show that the Atp A2 promoter directs GUS reporter gene expression in lignified tissues of transgenic plants. Moreover......-coumaryl and coniferyl alcohols are preferred by ATP A2, while the oxidation of sinapyl alcohol will be sterically hindered in ATP A2 as well as in all other plant peroxidases due to an overlap with the conserved Pro-139. We suggest ATP A2 is involved in a complex regulation of the covalent cross-linking in the plant...

Crystallite growth kinetics of TiO2 surface modification with 9 mol% ZnO prepared by a coprecipitation process

International Nuclear Information System (INIS)

Ko, Horng-Huey; Hsi, Chi-Shiung; Wang, Moo-Chin; Zhao, Xiujian

2014-01-01

Highlights: • TiO 2 powder surface modification with 9 mol% ZnO was obtained. • Phase transformation from anatase to rutile was hindered by ZnO added. • Growth kinetic of anatase TiO 2 nanocrystallites in T-9Z powders was described as: D A,9 2 =2.42×10 5 ×exp(-39.9×10 3 /RT). • Growth kinetic of rutile TiO 2 nanocrystallites in T-9Z powders was described as: D R,9 2 =8.49×10 5 ×exp(-47.6×10 3 /RT) rutile TiO 2 . -- Abstract: The nanocrystallite growth of TiO 2 surface modification with 9 mol% ZnO prepared by a coprecipitation process has been studied. Thermogravimetric and differential thermal analysis (TG/DTA), X-ray diffraction (XRD), transmission electron microscopy (TEM), selected area electron diffraction (SAED) and UV–VIS–NIR spectrophotometry have been utilized to characterize the TiO 2 nanocrystallites surface modification with 9 mol% ZnO (denoted by T-9Z). The DTA result shows that the anatase TiO 2 first formed at 533 K and the completion of anatase TiO 2 crystallization occurred at 745 K for the T-9Z freeze-dried precursor powders. XRD results reveal that the anatase and rutile TiO 2 coexist when the T-9Z freeze-dried precursor powders were calcined at 523–973 K for 2 h. When the T-9Z freeze-dried precursor powders were calcined at 973 K for 2 h, rutile TiO 2 was the major phase, and the minor phases were anatase TiO 2 and Zn 2 Ti 3 O 8 . The phase was composed of the rutile TiO 2 and Zn 2 TiO 4 for the T-9Z freeze-dried precursor powders after calcination at 1273 K for 2 h. The growth kinetics of TiO 2 nanocrystallites in T-9Z powders were described as: D A,9 2 =2.42×10 5 ×exp(-39.9×10 3 /RT)and D R,9 2 =8.49×10 5 ×exp(-47.6×10 3 /RT) for anatase and rutile TiO 2 nanocrystallites respectively. The analysis results of UV/VIS/NIR spectra reveal that the T-9Z freeze-dried precursor powders after calcination have a red-shifted effect with increasing calcination temperature and can be used as a UVA-attenuating agent

Evidence for a different electronic configuration as a primary effect during compression of orthorhombic perovskites: The case of Nd M3 +O3 (M =Cr ,Ga )

Science.gov (United States)

Ardit, M.; Dondi, M.; Merli, M.; Cruciani, G.

2018-02-01

(Mg ,Fe ) Si O3 perovskite is the most abundant mineral of the Earth's lower mantle, and compounds with the perovskite structure are perhaps the most widely employed ceramics. Hence, they attract both geophysicists and material scientists. Several investigations attempted to predict their structural evolution at high pressure, and recent advancements highlighted that perovskites having ions with the same formal valence at both polyhedral sites (i.e., 3 +:3 + ) define different compressional patterns when transition metal ions (TMI) are involved. In this study, in situ high-pressure synchrotron XRD measurements coupled with ab initio simulations of the electronic population of NdCr O3 perovskite are compared with the compressional feature of NdGa O3 . Almost identical from a steric point of view (C r3 + and G a3 + have almost the same ionic radius), the different electronic configuration of octahedrally coordinated ions - which leads to a redistribution of electrons at the 3 d orbitals for C r3 + - allows the crystal field stabilization energy (CFSE) to act as a vehicle of octahedral softening in NdCr O3 or it turns octahedra into rigid units when CFSE is null as in NdGa O3 . Besides to highlight that different electronic configurations can act as a primary effect during compression of perovskite compounds, our findings have a deep repercussion on the way the compressibility of perovskites have to be modeled.

2-Methyl-3-(2-methylphenyl-4-oxo-3,4-dihydroquinazolin-8-yl 4-bromobenzene-1-sulfonate

Directory of Open Access Journals (Sweden)

Edward R. T. Tiekink

2012-03-01

Full Text Available The title molecule, C22H17BrN2O4S, has a twisted U shape, the dihedral angle between the quinazolin-4-one and bromobenzene ring systems being 46.25 (8°. In order to avoid steric clashes with adjacent substituents on the quinazolin-4-one ring, the N-bound tolyl group occupies an orthogonal position [dihedral angle = 89.59 (8°]. In the crystal, molecules are connected into a three-dimensional architecture by C—H...O interactions, with the ketone O atom accepting two such bonds and a sulfonate O atom one.

Evaluation of the efficiency of Pd/H2 -catalyzed benzylic H/D exchange of dehydroabietinal with D(2) O and synthesis of a tritium-labeled analogue.

Science.gov (United States)

Petros, Robby A; Shah, Jyoti

2014-01-01

Dehydroabietinal (DA) has been identified as an important signaling molecule in systemic acquired resistance in plants. Deuterium and tritium-labeled DA were synthesized to confirm its role in signaling and to further elucidate the mechanism by which DA induces systemic acquired resistance. Pd/H2 -catalyzed exchange of benzylic hydrogen atoms of DA with (2) H-H2 O or (3) H-H2 O was conducted with >97% label incorporation for (2) H-DA and a specific activity of 12.6 mCi/mmol for (3) H-DA synthesized from 90 mCi/mmol (3) H-H2 O. The extent of deuterium labeling at each benzylic position was determined via an inverse-gated (13) C NMR experiment. C7 and C15 were 87% and 81% labeled, respectively. Isotope-induced chemical shift changes at C6 were used to approximate the amount of singly (66%) and doubly (17%) labeled (2) H-DA at C7. Results also indicated that two of the three benzylic protons in DA underwent facile exchange. Exchange at the remaining position was likely hampered by steric interactions of nearby methyl groups at the surface of the Pd catalyst. Copyright © 2013 John Wiley & Sons, Ltd.

Influência de estabilizantes na degradação foto-oxidativa de filmes de compósitos de SWy-1/poli(óxido de etileno

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Patrícia Coelho Lombardo

2015-02-01

Full Text Available Compósitos de poli(óxido de etileno (PEO com argila montmorilonita SWy-1 e estabilizantes (2-hidroxibenzofenona e tinuvin 770 foram preparados pelo método de intercalação em solução. Os filmes obtidos foram expostos a irradiação UV, e os produtos da fotodegradação foram monitorados por FTIR (Fourier Transform Infrared Spectroscopy, ou Espectroscopia no infravermelho por transformada de Fourier e SEC (Size Exclusion Chromatography, ou cromatografia de exclusão por tamanho. O PEO puro apresentou maior coeficiente de degradação, kd, comparado com as demais amostras. O sistema que apresentou o menor valor para o coeficiente de degradação (kd = 1,9×10–6 mol g–1 h-1 foi o compósito de PEO/5%SWy-1 com 0,25% de tinuvin 770. Nesse caso, a estabilização da matriz de PEO pode ser atribuída à argila juntamente com o tinuvin 770. A argila dispersa e absorve a irradiação UV, e o tinuvin age como estabilizante do tipo HALS (do inglês hindered amine light stabilizer, ou estabilizantes à luz tipo aminas impedidas.

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

Development of a generic seed crystal for the fabrication of large grain (RE)-Ba-Cu-O bulk superconductors

International Nuclear Information System (INIS)

Shi, Y; Babu, N Hari; Cardwell, D A

2005-01-01

The critical current density, J c , irreversibility field, B irr , and magnetic field trapping ability of (LRE)-Ba-Cu-O bulk superconductors, where LRE is a light rare earth element such as Nd, Sm, Eu and Gd, are generally superior to those of the more common melt-processed Y-Ba-Cu-O (YBCO). The lack of availability of a suitable seed crystal to grow large, single grain (LRE)-Ba-Cu-O superconductors with controlled orientation, however, has hindered severely the development of these materials for engineering applications over the past ten years. In this communication we report for the first time the development of a generic seed crystal that can be used to fabricate any rare earth (RE) based (RE)-Ba-Cu-O ((RE)BCO) superconductor in the form of a large single grain with controlled orientation. The new seed crystal will potentially enable large grain (LRE)-Ba-Cu-O bulk superconductors to be fabricated routinely, as is the case for YBCO. This will enable the field trapping and current-carrying characteristics of these materials to be explored in more detail than has been possible to date. (rapid communication)

Optimization of o-phtaldialdehyde/2-mercaptoethanol postcolumn reaction for the hydrophilic interaction liquid chromatography determination of memantine utilizing a silica hydride stationary phase.

Science.gov (United States)

Douša, Michal; Pivoňková, Veronika; Sýkora, David

2016-08-01

A rapid procedure for the determination of memantine based on hydrophilic interaction chromatography with fluorescence detection was developed. Fluorescence detection after postcolumn derivatization with o-phtaldialdehyde/2-mercaptoethanol was performed at excitation and emission wavelengths of 345 and 450 nm, respectively. The postcolumn reaction conditions such as reaction temperature, derivatization reagent flow rate, and reagents concentration were studied due to steric hindrance of amino group of memantine. The derivatization reaction was applied for the hydrophilic interaction liquid chromatography method which was based on Cogent Silica-C stationary phase with a mobile phase consisting of a mixture of 10 mmol/L citric acid and 10 mmol/L o-phosphoric acid (pH 6.0) with acetonitrile using an isocratic composition of 2:8 v/v. The benefit of the reported approach consists in a simple sample pretreatment and a quick and sensitive hydrophilic interaction chromatography method. The developed method was validated in terms of linearity, accuracy, precision, and selectivity according to the International Conference on Harmonisation guidelines. The developed method was successfully applied for the analysis of commercial memantine tablets. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis strategies for improving the performance of doped-BaZrO 3 materials in solid oxide fuel cell applications

KAUST Repository

Bi, Lei

2013-08-07

Solid oxide fuel cells (SOFCs) offer an efficient energy conversion technology for alleviating current energy problems. High temperature proton-conducting (HTPC) oxides are promising electrolytes for this technology, since their activation energy is lower than that of conventional oxygen-ion conductors, enabling the operating temperature reduction at 600 °C. Among HTPC oxides, doped BaZrO3 materials possess high chemical stability, needed for practical applications. Though, poor sinterability and the resulting large volume of highly resistive grain boundaries hindered their deployment for many years. Nonetheless, the recently demonstrated high proton conductivity of the bulk revived the attention on doped BaZrO3, stimulating research on solving the sintering issues. The proper selection of dopants and sintering aids was demonstrated to be successful for improving the BaZrO3 electrolyte sinterability. We here briefly review the synthesis strategies proposed for preparing BaZrO3-based nanostructured powders for electrolyte and electrodes, with the aim to improve the SOFC performance. © Materials Research Society 2013.

Reduced sintering of mass-selected Au clusters on SiO2 by alloying with Ti: an aberration-corrected STEM and computational study

DEFF Research Database (Denmark)

Niu, Yubiao; Schlexer, Philomena; Sebök, Béla

2018-01-01

Au nanoparticles represent the most remarkable example of a size effect in heterogeneous catalysis. However, a major issue hindering the use of Au nanoparticles in technological applications is their rapid sintering. We explore the potential of stabilizing Au nanoclusters on SiO2 by alloying them...... in the Au/Ti clusters, but in line with the model computational investigation, Au atoms were still present on the surface. Thus size-selected, deposited nanoalloy Au/Ti clusters appear to be promising candidates for sustainable gold-based nanocatalysis....

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 P^EtP^NRR' (P^EtP^NRR' = 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(P^EtP^NRR') is described. In situ IR and multinuclear NMR spectroscopic studies monitoring the stepwise addition of (HOTf) to trans-Mo(N₂)₂(PMePh₂)₂(P^EtP^NRR') 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(P^EtP^NRR') complexes provides further insight into the proton affinity values of the metal center, N�

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

Core-shell structured MnSiO3 supported with CNTs as a high capacity anode for lithium-ion batteries.

Science.gov (United States)

Feng, Jing; Li, Qin; Wang, Huijun; Zhang, Min; Yang, Xia; Yuan, Ruo; Chai, Yaqin

2018-04-17

Metal silicates are good candidates for use in lithium ion batteries (LIBs), however, their electrochemical performance is hindered by their poor electrical conductivity and volume expansion during Li+ insertion/desertion. In this work, one-dimensional core-shell structured MnSiO3 supported with carbon nanotubes (CNTs) (referred to as CNT@MnSiO3) with good conductivity and electrochemical performance has been successfully synthesized using a solvothermal process under moderate conditions. In contrast to traditional composites of CNTs and nanoparticles, the CNT@MnSiO3 composite in this work is made up of CNTs with a layer of MnSiO3 on the surface. The one-dimensional CNT@MnSiO3 nanotubes provide a useful channel for transferring Li+ ions during the discharge/charge process, which accelerates the Li+ diffusion speed. The CNTs inside the structure not only enhance the conductivity of the composite, but also prevent volume expansion. A high reversible capacity (920 mA h g-1 at 500 mA g-1 over 650 cycles) and good rate performance were obtained for CNT@MnSiO3, showing that this strategy of synthesizing coaxial CNT@MnSiO3 nanotubes offers a promising method for preparing other silicates for LIBs or other applications.

Autoestima e alfabetização: o que há nessa relação? Self-esteem and literacy: what may be in this relationship?

Directory of Open Access Journals (Sweden)

Clarice Salete Traversini

2009-08-01

Full Text Available Este artigo tem como objetivo analisar um conjunto de práticas utilizadas para alfabetizar jovens e adultos, as quais têm no resgate da autoestima seu foco central. O estudo utilizou uma parcela dos discursos do Programa Alfabetização Solidária registrados em um conjunto de publicações periódicas editadas entre 1997 e 2002, cuja circulação tinha abrangência nacional. Inspirada nos estudos de Michel Foucault, a análise contou com as noções de governamento e discurso. O argumento desenvolvido no texto pretende mostrar que a ênfase na elevação da autoestima funciona como uma das estratégias de governamento do Programa Alfabetização Solidária. As estratégias são operacionalizadas por meio: da produção da baixa autoestima como um problema para efetivar o processo de alfabetização; do desenvolvimento da autoconfiança pelo disciplinamento de corpos e mentes; e da produtividade da estratégia de valorização da autoestima evidenciada na mudança de conduta dos alfabetizandos. Essas práticas investem na elevação da autoestima e da estima aos outros, apostando no envolvimento, na persistência e na permanência do aluno nos programas de alfabetização para operar as mudanças desejadas nos indivíduos e nos locais com elevados índices de analfabetismo.This paper aims at analyzing a group of practices that have been used to alphabetize youths and adults, which have the recovery of self-esteem as their central focus. This study has employed part of discourses of the Solidary Literacy Program (Programa Alfabetização Solidária, recorded in a series of periodical publications, from 1997 to 2002, which were nationally distributed. From studies carried out by Michel Foucault, this analysis has considered the notions of government and discourse. The argument developed in this text intends to show that the emphasis on raising self-esteem has functioned as one of the governing strategies of the Solidary Literacy Program. The

General and efficient one-pot synthesis of novel sugar/heterocyclic(aryl) 1,2-diketones from sugar terminal alkynes by Sonogashira/tetra-n- butylammonium permanganate oxidation.

Science.gov (United States)

Zhang, Fuyi; Wu, Xiaopei; Wang, Liming; Liu, Hong; Zhao, Yufen

2015-11-19

A new approach for one-pot synthesis of novel sugar/heterocyclic(aryl) 1,2-diketones has been achieved by the reaction of various sugar terminal alkynes with heterocyclic(aryl) iodides at room temperature. This one-pot protocol includes Sonogashira coupling and mild n-Bu4NMnO4 oxidation reaction. This method is mild, general and efficient. Fifty-six examples have been given and the sugar/heterocyclic(aryl) 1,2-diketones were obtained in 71-94% yields. The sugar terminal alkynes include 9 structurally different sugars in pyranose, furanose, and acyclic form which have various protecting groups, sensitive groups, and sterically bulky substituents. The heterocyclic(aryl) iodides include sterically bulky heterocyclic compounds and iodobenzenes with electron-donating, electron-neutral, and electron-withdrawing substituents. Copyright © 2015 Elsevier Ltd. All rights reserved.

Interdispersed amorphous MnO{sub x}-carbon nanocomposites with superior electrochemical performance as lithium-storage material

Energy Technology Data Exchange (ETDEWEB)

Guo, Juchen; Wang, Chunsheng [Department of Chemical and Biomolecular Engineering, University of Maryland, College Park, MD (United States); Liu, Qing; Zachariah, Michael R. [Department of Chemistry and Biochemistry, University of Maryland, College Park, MD (United States)

2012-02-22

The realization of manganese oxide anode materials for lithium-ion batteries is hindered by inferior cycle stability, rate capability, and high overpotential induced by the agglomeration of manganese metal grains, low conductivity of manganese oxide, and the high stress/strain in the crystalline manganese oxide structure during the repeated lithiation/delithiation process. To overcome these challenges, unique amorphous MnO{sub x}-C nanocomposite particles with interdispersed carbon are synthesized using aerosol spray pyrolysis. The carbon filled in the pores of amorphous MnO{sub x} blocks the penetration of liquid electrolyte to the inside of MnO{sub x}, thus reducing the formation of a solid electrolyte interphase and lowering the irreversible capacity. The high electronic and lithium-ion conductivity of carbon also enhances the rate capability. Moreover, the interdispersed carbon functions as a barrier structure to prevent manganese grain agglomeration. The amorphous structure of MnO{sub x} brings additional benefits by reducing the stress/strain of the conversion reaction, thus lowering lithiation/delithiation overpotential. As the result, the amorphous MnO{sub x}-C particles demonstrated the best performance as an anode material for lithium-ion batteries to date. (Copyright copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

Enhancement removal of tartrazine dye using HCl-doped polyaniline and TiO2-decorated PANI particles

Science.gov (United States)

Elsayed, M. A.; Gobara, Mohamed

2016-08-01

HCl-doped polyaniline (HCl-PANI) and titanium dioxide decorated with polyaniline (TiO2-decorated PANI) with different TiO2:PANI ratios were chemically prepared and utilized for the removal of tartrazine (TZ) dye from a synthetic aqueous solution. The mechanism of preparation of the sample suggested that aniline was adsorbed on the TiO2 surface before the polymerization process took place. Samples were characterized using Fourier transform infrared spectroscopy, scanning electron microscopy, energy dispersive x-ray spectroscopy and x-ray diffraction. The results showed that HCl-PANI and TiO2-decorated PANI have an amorphous structure. The thermal stability of the prepared samples was characterized using thermo-gravimetric (TG) analysis. HCl-PANI is stable up to 200 °C and the relative weight per cent of PANI in the TiO2-decorated PANI was 20, 25, 40 and 45%. The removal activity of TiO2-decorated PANI via TZ azo dye was investigated under UV light irradiations and compared with HCl-PANI and TiO2 particles. The results indicated the superiority of the TiO2-decorated PANI over pure HCl-PANI and TiO2. However, the excessive PANI percentage tends to form a relatively thick layer, and even aggregates on the surface of TiO2. This hinders the migration of excited electrons from the outer PANI layer to the inner TiO2 particles, which consequently leads to a decrease in the removal efficiency. A possible mechanism for the removal oxidative degradation is also mentioned.

First-Principles Studies on Deoxidizing Mechanism of V2O5 via Hydrogen

Science.gov (United States)

Zhang, Yanning; Jin, Mengting

With its high melting point, good plasticity and good corrosion resistance at low temperatures, vanadium has been widely used in the industries of iron and steel, aviation, energy storage, etc. However, the traditional manufacturing technologies of pure vanadium are usually connected with complex manufacturing processes, high costs and serious environment pollution, which more or less hindered its further applications. Recently, hydrogen gas has been considered as a promising reducing agent of V2O5, but experimental studies of deoxidization process of V2O5 single crystal surfaces were found to be extremely difficult. In this work, we perform extensive ab initio studies on the structural and electronic properties of different V2O5 surfaces, as well as the adsorption sites, diffusion and desorption processes of H on these surfaces as a dependence of depth. We found that H atoms adsorb at oxygen site to form surface hydroxyl (OH-) and further to form H2O on V2O5(010) surfaces, and the latter is easier to be desorbed compared with the former. But the desorption of H2O causes significant surface reconstructions, which makes the further deoxidization of V2O5 difficult, particularly on the V2O5 single-layer. Our theoretical results are instructive for understandings of the reduction mechanism of V2O5 by using a green agent of H2, and furthermore for the design of new experiments. Work was supported by the startup fund of China Thousand Young Talents, and National Basic Research Program of China (973 program, No: 2013CB934700). The calculations were supported by Tianhe2-JK in Beijing Computational Science Research Center.

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.

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.

Effect of Fe{sub 3}O{sub 4} nanoparticles on positive streamer propagation in transformer oil

Energy Technology Data Exchange (ETDEWEB)

Lv, Yuzhen, E-mail: yzlv@ncepu.edu.cn [Beijing Key Laboratory of High Voltage and EMC, School of Electric and Electronic Engineering, North China Electric Power University, Beijing, 102206 (China); School of Energy, Power and Mechanical Engineering, North China Electric Power University, Beijing, 102206 (China); Wang, Qi; Ge, Yang [Beijing Key Laboratory of High Voltage and EMC, School of Electric and Electronic Engineering, North China Electric Power University, Beijing, 102206 (China); Zhou, You [Hunan Province Key Laboratory of Smart Grids Operation and Control, Changsha University of Science and Technology, Changsha, 410076 (China); Li, Chengrong, E-mail: lcr@ncepu.edu.cn; Qi, Bo [Beijing Key Laboratory of High Voltage and EMC, School of Electric and Electronic Engineering, North China Electric Power University, Beijing, 102206 (China); State Key Laboratory of Alternate Electrical Power System with Renewable Energy Sources, North China Electric Power University, Beijing, 102206 (China)

2016-03-15

Fe{sub 3}O{sub 4} nanoparticles with an average diameter of 10 nm were prepared and used to modify streamer characteristic of transformer oil. It was found that positive streamer propagation velocity in transformer oil-based Fe{sub 3}O{sub 4} nanofluid is greatly reduced by 51% in comparison with that in pure oil. The evolution of streamer shape is also dramatically affected by the presence of nanoparticles, changing from a tree-like shape with sharp branches in pure oil to a bush-like structure with thicker and denser branches in nanofluid. The TSC results reveal that the modification of Fe{sub 3}O{sub 4} nanoparticle can greatly increase the density of shallow trap and change space charge distribution in nanofluid by converting fast electrons into slow electrons via trapping and de-trapping process in shallow traps. These negative space charges induced by nanoparticles greatly alleviate the electric field distortion in front of the positive streamer tip and significantly hinder the propagation of positive streamer.

Preparation of heteropolyacid/TiO{sub 2}/fly-ash-cenosphere photocatalyst for the degradation of ciprofloxacin from aqueous solutions

Energy Technology Data Exchange (ETDEWEB)

Wu Di; Huo Pengwei; Lu Ziyang; Gao Xun [School of Chemistry and Chemical Engineering, Jiangsu University, Zhenjiang 212013 (China); Liu Xiaolin [School of Biology and Chemical Engineering, Jiangsu University of Science and Technology, Zhenjiang 212013 (China); Shi Weidong [School of Chemistry and Chemical Engineering, Jiangsu University, Zhenjiang 212013 (China); Yan Yongsheng, E-mail: huopw@ujs.edu.cn [School of Chemistry and Chemical Engineering, Jiangsu University, Zhenjiang 212013 (China)

2012-07-01

The TiO{sub 2}/fly-ash cenosphere photocatalysts modified with heteropolyacid were synthesized by sol-gel followed solvothermal method at 40 Degree-Sign C. Their chemical composition and optical absorption were characterized by X-ray diffraction (XRD), UV-vis diffuse reflectance spectra (UV-vis DRS), Fourier Transform Infra Red spectroscopy (FTIR) and Scanning electron microscopy (SEM). It was found that heteropolyacid modification could facilitate the absorption edge of TiO{sub 2}/fly-ash cenosphere photocatalyst to shift the visible light region. Heteropolyoxanion could be loaded on the titanium dioxide surface, by which could hinder the recombination rate of excited electron holes. The photocatalytic activity of TiO{sub 2}/fly-ash cenospheres modified with heteropolyacid was observed for the degradation of ciprofloxacin (CPFX) under visible light irradiation. The result from degradation of CPFX suggested that the photocatalytic activity of TiO{sub 2}/fly-ash cenospheres modified with silicotungstic acid was superior. The synergistic effects of heteropolyacid in modified TiO{sub 2}/fly-ash cenospheres photocatalyst particles were responsible for improving visible light photocatalytic activity. Besides, the novel photocatalyst was easy to recycle during post treatment because the fly-ash cenosphere was adopted for carrier.

Journal of Chemical Sciences | Indian Academy of Sciences

Indian Academy of Sciences (India)

Also, formation constants of the complexes have been determined by UV-Vis absorption spectroscopy through titration of the ligands with the metal ions at constant ionic strength (0.1 M NaClO4) and at 25°C. According to the thermodynamic studies, as the steric character of the ligand increases, the complexation tendency ...

Influence of pH and media composition on suspension stability of silver, zinc oxide, and titanium dioxide nanoparticles and immobilization of Daphnia magna under guideline testing conditions

DEFF Research Database (Denmark)

Cupi, Denisa; Hartmann, Nanna B.; Baun, Anders

2016-01-01

sterically stabilized, test suspensions of silver (Ag) ENPs formed large agglomerates in both VS EPA and M7 media; and toxicity was found to be higher in VS EPA medium due to increased dissolution. Low-agglomerate suspensions for zinc oxide (ZnO) could be obtained at pH 7 in VS EPA medium, but the increase...

Atomistic Modeling of Cation Diffusion in Transition Metal Perovskites La1-xSrxMnO3+/-δfor Solid Oxide Fuel Cell Cathodes Applications

Science.gov (United States)

Lee, Yueh-Lin; Duan, Yuhua; Morgan, Dane; Sorescu, Dan; Abernathy, Harry

Cation diffusion in La1-xSrxMnO3+/-δ (LSM) and in related perovskite materials play an important role in controlling long term performance and stability of solid oxide fuel cell (SOFCs) cathodes. Due to sluggish rates of cation diffusion and complex coupling between defect chemistry and cation diffusion pathways, currently there is still lack of quantitative theoretical model predictions on cation diffusivity vs. T and P(O2) to describe experimental cation tracer diffusivities. In this work, based on ab initio modeling of LSM defect chemistry and migration barriers of the possible cation diffusion pathways, we assess the rates of A-site and B-site cation diffusion in a wide range of T and P(O2) at x =0.0 and 0.2 for SOFC applications. We demonstrate the active cation diffusion pathways in LSM involve cation defect clusters as cation transport carriers, where reduction in the cation migration barriers, which are governed by the steric effect associated with the metal-oxygen cage in the perovskite lattice, is much greater than the penalty of repulsive interaction in the A-site and B-site cation vacancy clusters, leading to higher cation diffusion rates as compared to those of single cation vacancy hopping mechanisms. The predicted Mn and La/Sr cation self-diffusion coefficients of LSM at at x =0.0 and 0.2 along with their 1/T and P(O2) dependences, are in good agreement with the experimental tracer diffusion coefficients.

Minimized thermal conductivity in highly stable thermal barrier W/ZrO{sub 2} multilayers

Energy Technology Data Exchange (ETDEWEB)

Doering, Florian; Major, Anna; Eberl, Christian; Krebs, Hans-Ulrich [University of Goettingen, Institut fuer Materialphysik, Goettingen (Germany)

2016-10-15

Nanoscale thin-film multilayer materials are of great research interest since their large number of interfaces can strongly hinder phonon propagation and lead to a minimized thermal conductivity. When such materials provide a sufficiently small thermal conductivity and feature in addition also a high thermal stability, they would be possible candidates for high-temperature applications such as thermal barrier coatings. For this article, we have used pulsed laser deposition in order to fabricate thin multilayers out of the thermal barrier material ZrO{sub 2} in combination with W, which has both a high melting point and high density. Layer thicknesses were designed such that bulk thermal conductivity is governed by the low value of ZrO{sub 2}, while ultrathin W blocking layers provide a high number of interfaces. By this phonon scattering, reflection and shortening of mean free path lead to a significant reduction in overall thermal conductivity even below the already low value of ZrO{sub 2}. In addition to this, X-ray reflectivity measurements were taken showing strong Bragg peaks even after annealing such multilayers at 1300 K. Those results identify W/ZrO{sub 2} multilayers as desired thermally stable, low-conductivity materials. (orig.)

Electrochemical performance of SnO{sub 2}/modified graphite composite material as anode of lithium ion battery

Energy Technology Data Exchange (ETDEWEB)

Wang, Hong-Qiang [Guangxi Key Laboratory of Low Carbon Energy Materials, School of Chemical and Pharmaceutical Sciences, Guangxi Normal University, Guilin 541004 (China); Hubei Key Laboratory for Processing and Application of Catalytic Materials, Huanggang Normal University, Huanggang 438000 (China); Yang, Guan-Hua; Huang, You-Guo; Zhang, Xiao-Hui; Yan, Zhi-Xiong [Guangxi Key Laboratory of Low Carbon Energy Materials, School of Chemical and Pharmaceutical Sciences, Guangxi Normal University, Guilin 541004 (China); Li, Qing-Yu, E-mail: liqingyu62@126.com [Guangxi Key Laboratory of Low Carbon Energy Materials, School of Chemical and Pharmaceutical Sciences, Guangxi Normal University, Guilin 541004 (China)

2015-11-01

In this report, we synthesized SnO{sub 2}/modified graphite anode composite material by a simple reflux method using SnCl{sub 4}·5H{sub 2}O as tin source and modified graphite as carbon source. The as-obtained composite was investigated with the help of X-ray diffraction (XRD), scanning electron microscopy (SEM) and galvanostatic cycling tests. The results show that the composite has a wave-shaped fold structure and the SnO{sub 2} nanoparticles on it have an average size of about 50 nm. Compared to pure modified graphite, the SnO{sub 2}/modified graphite exhibits a better electrochemical performance with a reversible specific capacity of 581.7 mAh g{sup −1} after 80 cycles, owing to high mechanical stress and elasticity of modified graphite could hinder the volume effect of SnO{sub 2} nanoparticles during the Li{sup +} insertion/extraction process. All these favourable characters reveal that the composite is a great potential anode material in high-performance lithium ion batteries. - Highlights: • A simple synthetic method of SnO{sub 2}/modified graphite composite as anode. • The as-prepared composite with layered structure alleviates the huge reunion of SnO{sub 2}. • The composite exhibits a good capacity retention rate of 85.8% after 25 cycles.

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.

On the relationship between rutile/anatase ratio and the nature of defect states in sub-100 nm TiO2 nanostructures: experimental insights

KAUST Repository

Soliman, Moamen M.

2018-02-02

Black TiO2 is being widely investigated due to its superior optical activity and potential applications in photocatalytic hydrogen generation. Herein, the limitations of the hydrogenation process of TiO2 nanostructures are unraveled by exploiting the fundamental tradeoffs affecting the overall efficiency of the water splitting process. To control the nature and concentration of defect states, different reduction rates are applied to sub-100 nm TiO2 nanotubes, chosen primarily for their superiority over their long counterparts. X-Ray Photoelectron Spectroscopy disclosed changes in the stoichiometry of TiO2 with the reduction rate. UV-vis and Raman spectra showed that high reduction rates promote the formation of the rutile phase in TiO2, which is inactive towards water splitting. Furthermore, electrochemical analysis revealed that such high rates induce a higher concentration of localized electronic defect states that hinder the water splitting performance. Finally, incident photon-to-current conversion efficiency (IPCE) highlighted the optimum reduction rate that attains a relatively lower defect concentration as well as lower rutile content, thereby achieving the highest conversion efficiency.

Unravelling the surface chemistry of metal oxide nanocrystals, the role of acids and bases.

Science.gov (United States)

De Roo, Jonathan; Van den Broeck, Freya; De Keukeleere, Katrien; Martins, José C; Van Driessche, Isabel; Hens, Zeger

2014-07-09

We synthesized HfO2 nanocrystals from HfCl4 using a surfactant-free solvothermal process in benzyl alcohol and found that the resulting nanocrystals could be transferred to nonpolar media using a mixture of carboxylic acids and amines. Using solution (1)H NMR, FTIR, and elemental analysis, we studied the details of the transfer reaction and the surface chemistry of the resulting sterically stabilized nanocrystals. As-synthesized nanocrystals are charge-stabilized by protons, with chloride acting as the counterion. Treatment with only carboxylic acids does not lead to any binding of ligands to the HfO2 surface. On the other hand, we find that the addition of amines provides the basic environment in which carboxylic acids can dissociate and replace chloride. This results in stable, aggregate-free dispersions of HfO2 nanocrystals, sterically stabilized by carboxylate ligands. Moreover, titrations with deuterated carboxylic acid show that the charge on the carboxylate ligands is balanced by coadsorbed protons. Hence, opposite from the X-type/nonstoichiometric nanocrystals picture prevailing in literature, one should look at HfO2/carboxylate nanocrystals as systems where carboxylic acids are dissociatively adsorbed to bind to the nanocrystals. Similar results were obtained with ZrO2 NCs. Since proton accommodation on the surface is most likely due to the high Brønsted basicity of oxygen, our model could be a more general picture for the surface chemistry of metal oxide nanocrystals with important consequences on the chemistry of ligand exchange reactions.

Cooperativity effect involving drug-DNA/RNA intermolecular interaction: A B3LYP-D3 and MP2 theoretical investigation on ketoprofen⋯cytosine⋯H2O system.

Science.gov (United States)

Zhen, Jun-Ping; Wei, Xiao-Chun; Shi, Wen-Jing; Huang, Zhu-Yuan; Jin, Bo; Zhou, Yu-Kun

2017-11-14

In order to examine the origin of the drug action and design new DNA/RNA-targeted drugs, the cooperativity effect involving drug-DNA/RNA intermolecular interaction in ketoprofen⋯cytosine⋯H 2 O ternary system were investigated by the B3LYP, B3LYP-D3, and MP2 methods with the 6-311++G(2d,p) basis set. The thermodynamic cooperativity was also evaluated at 310.15 K. The N-H⋯O, O-H⋯O, O-H⋯N, C-H⋯N, and C-H⋯O H bonds coexist in ternary complexes. The intermolecular interactions obtained by B3LYP-D3 are close to those calculated by MP2. The steric effects and van der Waals interactions have little influence on the cooperativity effects. The anti-cooperativity effect in ket⋯cyt⋯H 2 O is far more notable than the cooperativity effect, and the stability of the cyclic structure with anti-cooperativity effect is higher than that of the linear structure with cooperativity effect, as is confirmed by the AIM (atoms in molecules) and RDG (reduced density gradient) analysis. Thus, it can be inferred that, in the presence of H 2 O, the anti-cooperativity effect plays a dominant role in the drug-DNA/RNA interaction, and the nature of the hydration in the binding of drugs to DNA/RNA bases is the H-bonding anti-cooperativity effect. Furthermore, the drug always links simultaneously with DNA/RNA base and H 2 O, and only in this way can the biological activity of drugs play a role. In most cases, the enthalpy change is the major factor driving the cooperativity, as is different from most of biomacromolecule complexes.

Development and evaluation of N-naphthyl-N,O-succinyl chitosan micelles containing clotrimazole for oral candidiasis treatment.

Science.gov (United States)

Tonglairoum, Prasopchai; Woraphatphadung, Thisirak; Ngawhirunpat, Tanasait; Rojanarata, Theerasak; Akkaramongkolporn, Prasert; Sajomsang, Warayuth; Opanasopit, Praneet

2017-03-01

Clotrimazole (CZ)-loaded N-naphthyl-N,O-succinyl chitosan (NSCS) micelles have been developed as an alternative for oral candidiasis treatment. NSCS was synthesized by reductive N-amination and N,O-succinylation. CZ was incorporated into the micelles using various methods, including the dropping method, the dialysis method, and the O/W emulsion method. The size and morphology of the CZ-loaded micelles were characterized using dynamic light scattering measurements (DLS) and a transmission electron microscope (TEM), respectively. The drug entrapment efficiency, loading capacity, release characteristics, and antifungal activity against Candida albicans were also evaluated. The CZ-loaded micelles prepared using different methods differed in the size of micelles. The micelles ranged in size from 120 nm to 173 nm. The micelles prepared via the O/W emulsion method offered the highest percentage entrapment efficiency and loading capacity. The CZ released from the CZ-loaded micelles at much faster rate compared to CZ powder. The CZ-loaded NSCS micelles can significantly hinder the growth of Candida cells after contact. These CZ-loaded NSCS micelles offer great antifungal activity and might be further developed to be a promising candidate for oral candidiasis treatment.

Optimized adsorption of sulfonated phthalocyanines on ZnO electrodes and their characterization in dye- sensitized solar cells

Energy Technology Data Exchange (ETDEWEB)

Falgenhauer, Jane; Loewenstein, Thomas; Schlettwein, Derck [Institute of Applied Physics, Justus-Liebig-University Giessen (Germany)

2010-07-01

Phthalocyanines belong to the most stable industrial dyes and show some of the highest molar extinction coefficients in the visible range. ZnO is known as a wide band gap semiconductor material which can be conveniently prepared as a porous electrode from solution-based processes. Sulfonated phthalocyanines were adsorbed at such electrodeposited porous ZnO thin films to work as a photosensitizer in a dye sensitized solar cell (DSSC). The adsorption solution of the phthalocyanine was modified in its composition and by adding different detergents in different concentrations. The adsorption solutions and the sensitized ZnO films were investigated by UV/Vis spectroscopy to characterize the aggregation of the dye molecules. Most of the detergents used could minimize the aggregation of the dye molecules in the adsorption solution without hindering the adsorption of the phthalocyanine on the ZnO surface. The photoelectrochemical characteristics of the resulting test cells were determined using a standard liquid electrolyte. The efficiency of the cells did not reach the expected level and reasons for this are discussed based on film morphology, amount of adsorbed dye molecules, competition by detergent adsorption, the optical absorbance of the dyes in the film and aggregate formation.

Administração rural: o planejamento da empresa agropecuária

Directory of Open Access Journals (Sweden)

Oswaldo Calzavara

1985-11-01

Full Text Available A rural property is administred by formulating programs, coordinating its execution, evaluating the results and proposing changes with the objective of increasing the production and reducing the costs. A series of endogenous and exogenous variables interfere in rural production process. Administering these variables is considered a dynamic context and risk. Administration of these variables requires a simple and systamatic instrument that can be used easyly by rural farmer to facilitate the identification of critical points in the system function and presents alternative proposals. The proposed instrument was already tested in thirty rural properties with appropriate changes. Fundamentally it consists the following steps: lsf Step: Survey of agricultural capital; to scrutinize capital hindered as land, improvement, instalattions, machinery, livestock and circulating capital. 2n^ Step: Survey of administrative resources. 3r Step: Survey of present productive process: consider the actual use of land, land management, technologies used in the production of animals and crops. 4tn Step: Survey of present economic situation: Scrutinization of receipts and costs in a period, financial and economic indixes.. 5tn Step: Analysis of Results. 6tn Step: Defining the problem 7th Step: Propose productive system. 8tn Step: Marketing study. 9tn Step: Project engineering. 10th Step: Budget forecasting: Estimates of receipts, costs and movement of cash box. lltn Step: Evaluation of system proposed: economics, risk factor and comparative analysis of systems. 12tn Step: Conclusions and recommendations.Administrar uma propriedade rural ê formular programas, coordenar sua execução, avaliar resultados e propor mudanças. É combinar os recursos objetivando o aumento de produtividade com diminuição de custos. Uma série de variáveis endógenas interfere no processo produtivo rural. Assim, administrar é manejar essas variáveis consideradas num contexto din

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

Concepções de professores sobre inclusão escolar e interações em ambiente inclusivo: uma revisão da literatura Conceptions of teachers on school inclusion and inclusive environment interactions: a review of the literature

Directory of Open Access Journals (Sweden)

Kelly Ambrosio Silveira

2012-12-01

Full Text Available A educação inclusiva tem sido um desafio para diferentes profissionais que trabalham na promoção do desenvolvimento de alunos com deficiência. Estes têm a escola como um espaço fundamental para promover o desenvolvimento social, emocional e acadêmico, a partir de oportunidades de vivências estimuladoras da interação e mediação para a aprendizagem de significados e sentidos e que contribuem para processos de resiliência. Este estudo analisou o conteúdo de publicações nacionais da última década (2000-2010 sobre concepções de professores a respeito da inclusão de alunos com alguma necessidade educativa especial (NEE e interações no contexto educacional inclusivo, também identificando fatores facilitadores e impeditivos da efetivação das diretrizes educacionais existentes. Após busca sistemática na Biblioteca Virtual em Saúde - Psicologia (BVS-PSI, com as palavras-chave: professor, educação inclusiva, interação, educação especial, escola, aprendizagem, concepções, deficiência intelectual, mediação, desenvolvimento e relacionamento, 29 artigos foram recuperados e lidos na íntegra. Verificou-se um predomínio de autores da área da Psicologia e de coletas de dados realizadas via entrevista e questionário. Os estudos apresentaram concepções sobre deficiência ligadas a características individuais que causam limitações. A falta de apoio de equipe especializada, de materiais didáticos e assistivos, de formação e preparo foram apontados como principais fatores que dificultam a efetivação dos princípios inclusivos. A literatura mostra a necessidade de capacitação dos professores. Diante disso, sugerem-se novos estudos sobre a saúde do professor e suas concepções sobre a inclusão escolar, além da necessidade de intervenções escolares baseadas na problematização dos determinantes sociais e históricos associados às deficiências apresentadas e ao mal-estar docente.Inclusive education has been

Comparative study of water reactivity with Mo{sub 2}O{sub y}{sup −} and W{sub 2}O{sub y}{sup −} clusters: A combined experimental and theoretical investigation

Energy Technology Data Exchange (ETDEWEB)

Ray, Manisha; Waller, Sarah E.; Saha, Arjun; Raghavachari, Krishnan; Jarrold, Caroline Chick, E-mail: cjarrold@indiana.edu [Department of Chemistry, Indiana University, Bloomington, Indiana 47405 (United States)

2014-09-14

A computational investigation of the Mo{sub 2}O{sub y}{sup −} + H{sub 2}O (y = 4, 5) reactions as well as a photoelectron spectroscopic probe of the deuterated Mo{sub 2}O{sub 6}D{sub 2}{sup −} product have been carried out to understand a puzzling question from a previous study: Why is the rate constant determined for the Mo{sub 2}O{sub 5}{sup −} + H{sub 2}O/D{sub 2}O reaction, the terminal reaction in the sequential oxidation of Mo{sub 2}O{sub y}{sup −} by water, higher than the W{sub 2}O{sub 5}{sup −} + H{sub 2}O/D{sub 2}O reaction? This disparity was intriguing because W{sub 3}O{sub y}{sup −} clusters were found to be more reactive toward water than their Mo{sub 3}O{sub y}{sup −} analogs. A comparison of molecular structures reveals that the lowest energy structure of Mo{sub 2}O{sub 5}{sup −} provides a less hindered water addition site than the W{sub 2}O{sub 5}{sup −} ground state structure. Several modes of water addition to the most stable molecular and electronic structures of Mo{sub 2}O{sub 4}{sup −} and Mo{sub 2}O{sub 5}{sup −} were explored computationally. The various modes are discussed and compared with previous computational studies on W{sub 2}O{sub y}{sup −} + H{sub 2}O reactions. Calculated free energy reaction profiles show lower barriers for the initial Mo{sub 2}O{sub y}{sup −} + H{sub 2}O addition, consistent with the higher observed rate constant. The terminal Mo{sub 2}O{sub y}{sup −} sequential oxidation product predicted computationally was verified by the anion photoelectron spectrum of Mo{sub 2}O{sub 6}D{sub 2}{sup −}. Based on the computational results, this anion is a trapped dihydroxide intermediate in the Mo{sub 2}O{sub 5}{sup −} + H{sub 2}O/D{sub 2}O → Mo{sub 2}O{sub 6}{sup −} + H{sub 2}/D{sub 2} reaction.

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

Molecular engineering of D-A-π-A dyes with 2-(1,1-dicyanomethylene)rhodanine as an electron-accepting and anchoring group for dye-sensitized solar cells

International Nuclear Information System (INIS)

Mao, Jiangyi; Zhang, Xiaoyu; Liu, Shih-Hung; Shen, Zhongjin; Li, Xing; Wu, Wenjun; Chou, Pi-Tai; Hua, Jianli

2015-01-01

Graphical abstract: We designed and synthesized two new D-A-π-A dyes (RD-III and RD-IV) with 2-(1,1-dicyanomethylene) rhodanine (DCRD) as an electron-accepting and anchoring group. The theoretical calculation of dye/(TiO 2 ) 38 displayed that the angle between the molecule of RD-III and the surface of TiO 2 was only 31.84 0 in contrast to 97.16 0 for CA-III. This adsorption state can facilitate dye aggregation and charge recombination, resulting in a decrease of short circuit current density (J sc ) and open circuit voltage (V oc ). Further improvement has been successfully made by adding long alkoxy chains with large steric hindrance. After introducing the alkoxy chains of the benzothiadiazole unit, the dihedral angle between RD-IV and TiO 2 increased to 42.61 0 and the steric hindrance can inhibit dye aggregation and charge recombination. Therefore, higher photoelectric conversion efficiency of 5.53% was obtained with RD-IV in DSSC devices compared with 4.51% for DSSC based on RD-III. - Highlights: • We obtained two D-A-π-A dyes with 2-(1,1-dicyanomethylene) rhodanine as acceptor. • Introduction of octyloxy groups can increase the angle of dye/TiO 2 . • Octyloxy groups can inhibit dye aggregation and charge recombination effectively. • Higher power conversion efficiency of 5.53% was obtained with dye octyloxy group. - Abstract: The electron-accepting and anchoring group plays a significant role on the optical and electrochemical properties of an organic dye. They also affect the intramolecular charge transfer, the electron injection processes and the adsorption mode, hence the photostability of the dye on TiO 2 films. In this study, we have designed and synthesized two new D-A-π-A dyes (RD-III and RD-IV) with 2-(1,1-dicyanomethylene) rhodanine (DCRD) as electron-accepting and anchoring group. For comparison, an analogue of RD-III, namely CA-III, with cyanoacrylic acid (CA) as the acceptor was also prepared. We have carefully examined their optical and

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.

Determining oxide trapped charges in Al2O3 insulating films on recessed AlGaN/GaN heterostructures by gate capacitance transients measurements

Science.gov (United States)

Fiorenza, Patrick; Greco, Giuseppe; Schilirò, Emanuela; Iucolano, Ferdinando; Lo Nigro, Raffaella; Roccaforte, Fabrizio

2018-05-01

This letter presents time-dependent gate-capacitance transient measurements (C–t) to determine the oxide trapped charges (N ot) in Al2O3 films deposited on recessed AlGaN/GaN heterostructures. The C–t transients acquired at different temperatures under strong accumulation allowed to accurately monitor the gradual electron trapping, while hindering the re-emission by fast traps that may affect conventional C–V hysteresis measurements. Using this method, an increase of N ot from 2 to 6 × 1012 cm‑2 was estimated between 25 and 150 °C. The electron trapping is ruled by an Arrhenius dependence with an activation energy of 0.12 eV which was associated to points defects present in the Al2O3 films.

Mechanism of Enhancing Extraction of Vanadium from Stone Coal by Roasting with MgO

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Fang Chen

2017-02-01

Full Text Available In this paper, the extraction of vanadium from stone coal by roasting with MgO and leaching with sulfuric acid has been investigated, and the mechanism analysis of stone coal roasting with MgO was studied. The results indicated that under the conditions that the mass fraction of the particles with grain size of 0–0.074 mm in raw ore was 75%, the roasting temperature was 500 °C, the roasting time was 1 h, MgO addition was 3 wt %, the sulfuric acid concentration was 20 vol %, the liquid-to-solid ratio was 1.5 mL/g, the leaching temperature was 95 °C, and leaching time was 2 h, resulting in a vanadium leaching efficiency of 86.63%, which increased by 7.73% compared with that of blank roasting. The mechanism analysis showed that the degree of calcite decomposition was low and, thus, magnesium vanadate was more easily formed than calcium vanadate below 500 °C. Moreover, magnesium vanadate was easier to dissolve than calcium vanadate during the sulfuric acid leaching process. Thus, the vanadium leaching efficiency was enhanced by using MgO as a roasting additive below 500 °C. Additionally, at high temperature the formation of tremolite would consume calcium oxide produced from the decomposition of calcite, thus, the formation of calcium vanadate was hindered, and V2O5 would react with MgO to form magnesium vanadate. Therefore, the vanadium leaching efficiency of roasting with MgO was higher than that of blank roasting at high temperature.

Theoretical study of hydration in Y{sub 2}Mo{sub 3}O{sub 12}: Effects on structure and negative thermal expansion

Energy Technology Data Exchange (ETDEWEB)

Wu, Ming-Yi; Wang, Lei; Jia, Yu; Sun, Qiang, E-mail: qsun@zzu.edu.cn [International Laboratory for Quantum Functional Materials of Henan, and School of Physics and Engineering, Zhengzhou University, Zhengzhou, 450001 (China); Guo, Zheng-Xiao [Department of Chemistry, University College London, London WC1H 0AJ (United Kingdom)

2015-02-15

We report ab-initio calculations of water absorption in Y{sub 2}Mo{sub 3}O{sub 12}. The absorption geometry of H{sub 2}O in Y{sub 2}Mo{sub 3}O{sub 12} and the binding property between H{sub 2}O and Y{sub 2}Mo{sub 3}O{sub 12} have been first identified. Our calculated results show that water is chemisorbed in Y{sub 2}Mo{sub 3}O{sub 12} with O of the water binding to the Y{sup 3+} cation, which is further strengthened by hydrogen bonding between each of the hydrogen atoms of H{sub 2}O and the bridge O in Y{sub 2}Mo{sub 3}O{sub 12}, shared by polyhedrons YO{sub 6} and MoO{sub 4}. The absorption of water leads to a reduced angle of Y-O-Mo and shortened Y-Mo distance, and consequently volume contraction of the material, almost linearly with the increasing number of water molecules per unit cell, up to eight in total. In addition, our phonon calculation show that the transverse vibration of Y-O-Mo is restricted due to water absorption, which in turn hinders the NTE, as it is mainly originated from this vibrational mode. Our results clarify further the fundamental mechanisms of the large volume shrinkage and the lost NTE of the framework oxide due to water absorption.

The Effect of H2O2 Interference in Chemical Oxygen Demand Removal During Advanced Oxidation Processes

Directory of Open Access Journals (Sweden)

Afsane Chavoshani

2016-07-01

Full Text Available Hydrogen peroxide (H2O2 is one of the most oxidants in AOPs. By H2O2 dissociation, hydroxyl radical with a standard oxidation potential of 2.7 is produced. It is reported H2O¬ residual in AOPs has been led to interference in chemical oxygen demand (COD test and it is able to hinder biological treatment of waste water. Because of high mixed organic load of solid waste leachate, this study investigated effect of H2O2 interference in COD removal from solid waste leachate. In this study effect of parameters such as pH (3,5,7,12, H2O2 dose (0.01, 0.02, 0.03, 0.04 mol l-1, and time reaction(10,20,30,40,50,60 min evaluated on H2O2 interference in COD removal from solid waste leachate. Optimum pH and concentration were 3 and 0.02 moll-1 respectively. With increasing reaction time, COD removal was increased. The false COD obtained between 0.49mg per 1mg of H2O2. The average of COD removal by H2O2 for 60 min was 6.57%. Also reaction rate of this process was 0.0029 min-1. The presence of H2O2 leads to overestimation of COD values after reaction time because it consumes the oxidation agent. The extent of H2O2 interference in COD analysis was proportional to the remaining H2O2 concentration at the moment of sampling.

Preparation, isolation and identification of non-conjugated C18:2 fatty acid isomers.

Science.gov (United States)

Fardin-Kia, Ali Reza

2016-12-01

Non-conjugated geometric/positional isomers of linoleic acid (c9,c12-18:2) are often present in processed foods and oils. The following work presents a simple addition/elimination reaction for preparation of non-conjugated 18:2 fatty acid isomers. A mixture containing positional and geometric isomers of C18:2 fatty acids was produced by addition of hydrobromic acid to the fatty acid double bonds, followed by its elimination with a strong sterically hindered base. Pure 8,12-, 8,13-, 9,12-, and 9,13-18:2 fatty acid methyl esters were isolated from the synthetic mixture by a combination of sub-ambient RP-HPLC and Ag + -HPLC. The determination of the double bond position was achieved by GC-MS using picolinyl esters derivatives. The determination of the fatty acid double bond geometric configuration was obtained by partial hydrogenation of the isolated isomer with hydrazine, followed by the GC-FID analysis. Published by Elsevier Ireland Ltd.

Design concept for α-hydrogen-substituted nitroxides.

Science.gov (United States)

Amar, Michal; Bar, Sukanta; Iron, Mark A; Toledo, Hila; Tumanskii, Boris; Shimon, Linda J W; Botoshansky, Mark; Fridman, Natalia; Szpilman, Alex M

2015-02-06

Stable nitroxides (nitroxyl radicals) have many essential and unique applications in chemistry, biology and medicine. However, the factors influencing their stability are still under investigation, and this hinders the design and development of new nitroxides. Nitroxides with tertiary alkyl groups are generally stable but obviously highly encumbered. In contrast, α-hydrogen-substituted nitroxides are generally inherently unstable and rapidly decompose. Herein, a novel, concept for the design of stable cyclic α-hydrogen nitroxides is described, and a proof-of-concept in the form of the facile synthesis and characterization of two diverse series of stable α-hydrogen nitroxides is presented. The stability of these unique α-hydrogen nitroxides is attributed to a combination of steric and stereoelectronic effects by which disproportionation is kinetically precluded. These stabilizing effects are achieved by the use of a nitroxide co-planar substituent in the γ-position of the backbone of the nitroxide. This premise is supported by a computational study, which provides insight into the disproportionation pathways of α-hydrogen nitroxides.

A Coordination Chemistry Approach to Fine-Tune the Physicochemical Parameters of Lanthanide Complexes Relevant to Medical Applications.

Science.gov (United States)

Le Fur, Mariane; Molnár, Enikő; Beyler, Maryline; Kálmán, Ferenc K; Fougère, Olivier; Esteban-Gómez, David; Rousseaux, Olivier; Tripier, Raphaël; Tircsó, Gyula; Platas-Iglesias, Carlos

2018-03-02

The geometric features of two pyclen-based ligands possessing identical donor atoms but different site organization have a profound impact in their complexation properties toward lanthanide ions. The ligand containing two acetate groups and a picolinate arm arranged in a symmetrical fashion (L1) forms a Gd 3+ complex being two orders of magnitude less stable than its dissymmetric analogue GdL2. Besides, GdL1 experiences a much faster dissociation following the acid-catalyzed mechanism than GdL2. On the contrary, GdL1 exhibits a lower exchange rate of the coordinated water molecule compared to GdL2. These very different properties are related to different strengths of the Gd-ligand bonds associated to steric effects, which hinder the coordination of a water molecule in GdL2 and the binding of acetate groups in GdL1. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Improvement of the cycling performance of LiCoO2 with assistance of cross-linked PAN for lithium ion batteries

International Nuclear Information System (INIS)

Yang, Xinhe; Shen, Lanyao; Wu, Bin; Zuo, Zicheng; Mu, Daobin; Wu, Borong; Zhou, Henghui

2015-01-01

Highlights: • Cross-linked PAN coating was prepared without damaging the surface of LiCoO 2 . • The coating layer owns good electronic conductivity and mechanical strength. • The cross-linked PAN coating layer is more sufficient than Al 2 O 3 coating. • It shows much improved cyclability than that of bare and Al 2 O 3 coated LiCoO 2 . - Abstract: LiCoO 2 has been widely used in lithium ion batteries for digital electronic products. However, the limited cycling performance under high cut-off voltage hinders its commercial application. Many metal oxides and/or phosphorus coating have been reported to improve the cycling performance of LiCoO 2 . In this paper, we report on cross-linked PAN coated LiCoO 2 composite as a cathode material for lithium ion batteries. The coating layer was obtained by intermolecular crosslinking of PAN polymer chain by heat treatment at high temperature in air. The air heating process avoids the possible damage arising from the carbon thermal reduction to the surface structure of LiCoO 2 . Electrochemical test indicates that the LiCoO 2 with the cross-linked PAN coating layer shows much improved cycle performance compared with that of bare and Al 2 O 3 coated LiCoO 2 . These findings might also open new avenues to explore polymer coating for other cathode materials of lithium ion batteries

Efficient dye-sensitized solar cells from curved silicate microsheet caged TiO2 photoanodes. An avenue of enhancing light harvesting

International Nuclear Information System (INIS)

Wang, Zubin; Tang, Qunwei; He, Benlin; Chen, Haiyan; Yu, Liangmin

2015-01-01

Graphical abstract: - Highlights: • Curved silicate microsheets are incorporated with TiO 2 for light harvesting in DSSC • The optical matching between silicate and TiO 2 is superior to light reflection. • The curved silicate can hinder the recombination reaction of electrons with I 3 − . • The DSSC with TiO 2 /curved silicate photoanode shows an efficiency of 9.22% - Abstract: Enhancement of light harvesting has been a persistent objective for elevating dye excitation and therefore power conversion efficiency of dye-sensitized solar cells (DSSCs). Here we launch a strategy of markedly enhancing light harvesting by caging TiO 2 nanoparticles with curved silica microsheets. The results show that the strategy is versatile in suppressing the recombination reaction of electrons with I 3 − species in liquid electrolyte. Due to the superior reflective behaviors of curved silica microsheets, an optimal efficiency of 9.22% is recorded under simulated air mass 1.5 global sunlight on the DSSC in comparison with 6.51% and 7.51% from pristine TiO 2 and planar silicate microsheet incorporated TiO 2 photoanode based solar cells, respectively. This strategy is also believed to be applicable to other solar cells such as perovskite solar cells and quantum dot-sensitized solar cells.

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...

Crystallite growth kinetics of TiO{sub 2} surface modification with 9 mol% ZnO prepared by a coprecipitation process

Energy Technology Data Exchange (ETDEWEB)

Ko, Horng-Huey [Department of Fragrance and Cosmetic Science, Kaohsiung Medical University, 100 Shih-Chuan 1st Road, Kaohsiung 80708, Taiwan (China); Hsi, Chi-Shiung [Department of Materials Science and Engineering, National United University, 1 Lein-Da, Kung-Ching Li, Miao-Li 36003, Taiwan (China); Wang, Moo-Chin, E-mail: mcwang@kmu.edu.tw [Department of Fragrance and Cosmetic Science, Kaohsiung Medical University, 100 Shih-Chuan 1st Road, Kaohsiung 80708, Taiwan (China); Zhao, Xiujian, E-mail: opluse@whut.edu.cn [State Key Laboratory of Silicate Materials for Architectures, Wuhan University of Technology, Wuhan 430070 (China)

2014-03-05

Highlights: • TiO{sub 2} powder surface modification with 9 mol% ZnO was obtained. • Phase transformation from anatase to rutile was hindered by ZnO added. • Growth kinetic of anatase TiO{sub 2} nanocrystallites in T-9Z powders was described as: D{sub A,9}{sup 2}=2.42×10{sup 5}×exp(-39.9×10{sup 3}/RT). • Growth kinetic of rutile TiO{sub 2} nanocrystallites in T-9Z powders was described as: D{sub R,9}{sup 2}=8.49×10{sup 5}×exp(-47.6×10{sup 3}/RT) rutile TiO{sub 2}. -- Abstract: The nanocrystallite growth of TiO{sub 2} surface modification with 9 mol% ZnO prepared by a coprecipitation process has been studied. Thermogravimetric and differential thermal analysis (TG/DTA), X-ray diffraction (XRD), transmission electron microscopy (TEM), selected area electron diffraction (SAED) and UV–VIS–NIR spectrophotometry have been utilized to characterize the TiO{sub 2} nanocrystallites surface modification with 9 mol% ZnO (denoted by T-9Z). The DTA result shows that the anatase TiO{sub 2} first formed at 533 K and the completion of anatase TiO{sub 2} crystallization occurred at 745 K for the T-9Z freeze-dried precursor powders. XRD results reveal that the anatase and rutile TiO{sub 2} coexist when the T-9Z freeze-dried precursor powders were calcined at 523–973 K for 2 h. When the T-9Z freeze-dried precursor powders were calcined at 973 K for 2 h, rutile TiO{sub 2} was the major phase, and the minor phases were anatase TiO{sub 2} and Zn{sub 2}Ti{sub 3}O{sub 8}. The phase was composed of the rutile TiO{sub 2} and Zn{sub 2}TiO{sub 4} for the T-9Z freeze-dried precursor powders after calcination at 1273 K for 2 h. The growth kinetics of TiO{sub 2} nanocrystallites in T-9Z powders were described as: D{sub A,9}{sup 2}=2.42×10{sup 5}×exp(-39.9×10{sup 3}/RT)and D{sub R,9}{sup 2}=8.49×10{sup 5}×exp(-47.6×10{sup 3}/RT) for anatase and rutile TiO{sub 2} nanocrystallites respectively. The analysis results of UV/VIS/NIR spectra reveal that the T-9Z freeze

Hydration effects on the photoionization energy of 2‧-deoxyguanosine 5‧-phosphate and activation barriers for guanine methylation by carcinogenic methane diazonium ions

Science.gov (United States)

Eichler, Daniel R.; Hamann, Haley A.; Harte, Katherine A.; Papadantonakis, George A.

2017-07-01

Results from DFT calculations indicate that states originating from gas-phase ionization of the phosphate and the base are degenerate in syn-5‧-dGMP- and that bulk hydration lowers the base-localized ionization energy by diazonium ions are lower at the N7 than at the O6 sites and they are influenced by local ionization energy and steric interference.

QSAR for cholinesterase inhibition by organophosphorus esters and CNDO/2 calculations for organophosphorus ester hydrolysis

Science.gov (United States)

Johnson, H.; Kenley, R. A.; Rynard, C.; Golub, M. A.

1985-01-01

Quantitative structure-activity relationships were derived for acetyl- and butyrylcholinesterase inhibition by various organophosphorus esters. Bimolecular inhibition rate constants correlate well with hydrophobic substituent constants, and with the presence or absence of catonic groups on the inhibitor, but not with steric substituent constants. CNDO/2 calculations were performed on a separate set of organophosphorus esters, RR'P(O)X, where R and R' are alkyl and/or alkoxy groups and X is fluorine, chlorine or a phenoxy group. For each subset with the same X, the CNDO-derived net atomic charge at the central phosphorus atom in the ester correlates well with the alkaline hydrolysis rate constant. For the whole set of esters with different X, two equations were derived that relate either charge and leaving group steric bulk, or orbital energy and bond order to the hydrogen hydrolysis rate constant.

Copper Promoted Synthesis of Diaryl Ethers

OpenAIRE

Ghosh, Rajshekhar; Samuelson, Ashoka G

2004-01-01

An efficient protocol using copper based reagents for the coupling of aryl halides with phenols to generate diaryl ethers is described. Acopper( I) complex, [ Cu( CH3CN) (4)] ClO4, or the readily available copper( II) source, CuCO3 . Cu( OH) (2) . H2O ( in combination with potassium phosphate), can be used. Aryl halides and phenols with different steric and electronic demands have been used to assess the efficiency of the procedure. The latter source of copper gives better yields under all co...

Estudo do solo-cimento-autoadensável produzido com solos da região do Porto-PT. PARTE II: avaliação da resistência e desempenho mecânico por meio da medição da resistividade elétrica e velocidade de propagação de ondas de ultrassom.

Directory of Open Access Journals (Sweden)

Marco Antônio Morais Alcantara

2014-09-01

Full Text Available (D.O.I.: 10.5216/reec.V9i1.29946 RESUMO: O artigo apresenta um estudo do solo-cimento autoadensável, sobre utilização da medição das propriedades relativas à resistividade elétrica e da velocidade de propagação de ondas de ultrassom, como meios de se buscar subsídios para esclarecer o processo de estabilização, bem como de se encontrar um meio indireto para a estimativa do valor da resistência e do desempenho mecânico. Para tanto, foi realizado um experimento a partir da utilização de um solo residual da região do Porto-Pt, cimento Portland, água, e aditivo de atuação estérica e eletrostática. A proporção dos materiais foi adotada a partir do peso seco do solo, conforme teores que variaram de 20, 25, e 30% de cimento, 41, 44 e 47% para a água, e 0,66, 0,80 e 0,93% para a variação do teor do superplastificante. Os ensaios no realizados no estado fresco procuraram seguir os protocolos de avaliação utilizados para os casos de argamassas e de concretos autoadensáveis; e, no estado endurecido, foram realizados os ensaios de resistência à compressão simples, resistência à flexão, e a avaliação dos valores da resistividade elétrica e da velocidade da propagação de ondas ultrassom. Os resultados indicaram haver aproximação entre o solo-cimento-auto-adensável e os concretos e argamassas; bem como, a variação dos valores da resistividade elétrica e da velocidade de propagação de ondas de ultrassom se apresentaram coerentes com a idade de cura e com os valores de resistência mecânica alcançados. ABSTRACT: The article presents a study of the soil-cement self-compacting, on the feasibility of using the measurement of the properties on the electrical resistivity and the speed of propagation of ultrasound waves as a means of seeking information to clarify the stabilization process as well as to find an indirect means for estimating the value of resistance and mechanical performance. Therefore, an experiment

Isotopic exchange between deuterium and neohexane on supported platinum and palladium catalysts

International Nuclear Information System (INIS)

Eskinazi, V.

1979-01-01

The isotopic exchange reaction between neohexane and deuterium on supported Pt/SiO 2 and Pd/SiO 2 catalysts has been investigated in the temperature range 86.5 to 110 0 C. Rates of exchange were studied as functions of percentage of metal atoms exposed, the conditions of catalyst pretreatment, and the reaction temperature. The rates of exchange were not strongly dependent upon percentage exposed; however, the relative yields of d 1 through d 5 in the ethyl moiety or neohexane were dependent on the percentage metal atoms exposed. The Pt/SiO 2 catalysts were found to be more active for exchange than the Pd/SiO 2 catalysts by an order of magnitude. Both the turnover frequencies and the exchange pattern were observed to be influenced by the pretreatment of the catalyst. Maxima in the exchange pattern occurred at d 3 and d 5 in the case of Pt/SiO 2 and at d 5 only in the case of the Pd/SiO 2 catalysts. In order to account for the d 3 maximum observed for Pt catalysts, some extension of the Horiuti-Polanyi mechanism is required. Mechanisms by which the d 3 species might be formed are proposed and discussed. On Pd/SiO 2 catalysts exchange occurs preferentially in the ethyl substituent of the quaternary carbon atom rather than on the three methyl substituents of the quaternary carbon atom. Such preference is not observed on Pt/SiO 2 catalysts; in fact, in some cases, this preference is reversed. Whenever exchange occurs in the three methyl substituents, mostly the d 1 product is obtained. For Pt/SiO 2 catalysts, the exchange pattern appears to be influenced by steric effects, but the data suggest that factors other than steric effects are important on Pd

Multicomponent synthesis of unsymmetrical unsaturated N-heterocyclic carbene precursors and their related transition-metal complexes

KAUST Repository

Queval, Pierre

2013-12-04

A low-cost, modular, and easily scalable multicomponent procedure affording access in good yields and excellent selectivity (up to 93 %) to a wide range of (a)chiral unsymmetrical 1-aryl-3-cycloalkyl-imidazolium salts is disclosed. Electronic and steric properties of the corresponding unsymmetrical unsaturated N-heterocyclic carbene (U2-NHC) ligands were evaluated and evidenced strong electron donor ability, high steric discrimination, and modular steric demand. A low-cost, modular, and easily scalable multicomponent procedure, affording access to a wide range of (a)chiral unsymmetrical 1-aryl-3-cycloalkyl- imidazolium salts in good yields and excellent selectivities, is disclosed. Electronic and steric properties of the corresponding unsymmetrical unsaturated N-heterocyclic carbene (U2-NHC) ligands were evaluated and evidenced strong electron-donor ability, high steric discrimination, and modular steric demand. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Improvement of structural and electrochemical properties of commercial LiCoO2 by coating with LaF3

International Nuclear Information System (INIS)

Yang Zhanxu; Qiao Qingdong; Yang Wensheng

2011-01-01

Highlights: → LaF 3 has been introduced as a new coating material for the LiCoO 2 cathode. → The LaF 3 -coated LiCoO 2 showed an excellent overcharge tolerance and structure stability. → The thermal stability of the LaF 3 -coated cathode is significantly enhanced. Therefore, LaF 3 is a probably potential coating material. - Abstract: Commercial LiCoO 2 has been modified with LaF 3 as a new coating material. The surface modified materials were characterized by X-ray diffraction (XRD), transmission electronic microscopy (TEM), field emission scanning electron microscopy (FE-SEM), auger electron spectroscopy (AES) and galvanostatic charge-discharge cycling. The LaF 3 -coated LiCoO 2 had an initial discharge specific capacity of 177.4 mAh g -1 within the potential ranges 2.75-4.5 V (vs. Li/Li + ), and showed a good capacity retention of 90.9% after 50 cycles. It was found that the overcharge tolerance of the coated cathode was significantly better than that of the pristine LiCoO 2 under the same conditions - the capacity retention of the pristine LiCoO 2 was 62.3% after 50 cycles. The improvement could be attributed to the LaF 3 coating layer that hinders interaction between LiCoO 2 and electrolyte and stabilizes the structure of LiCoO 2 . Moreover, DSC showed that the coated LiCoO 2 had a higher thermal stability than the pristine LiCoO 2 .

Green and facile synthesis of graphene nanosheets/K{sub 3}PW{sub 12}O{sub 40} nanocomposites with enhanced photocatalytic activities

Energy Technology Data Exchange (ETDEWEB)

Yang, Hongxun, E-mail: yhongxun@126.com [School of Environmental & Chemical Engineering, Jiangsu University of Science and Technology, Zhenjiang 212003 (China); State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fujian, Fuzhou 350002 (China); Liu, Xiaoyan; Sun, Shengnan; Nie, Yu; Wu, Huipeng; Yang, Tongyi; Zheng, Shaojun [School of Environmental & Chemical Engineering, Jiangsu University of Science and Technology, Zhenjiang 212003 (China); Lin, Shengling, E-mail: linshl5757@sina.com [School of Environmental & Chemical Engineering, Jiangsu University of Science and Technology, Zhenjiang 212003 (China)

2016-06-15

Highlights: • A new graphene/K{sub 3}PW{sub 12}O{sub 40} (GPW) composite was synthesized via photoreduction method. • Graphene in the GPW could reduce the recombination of electron-hole pairs. • Graphene in the GPW could increase adsorptive property. • GPW hybrid shows an enhancement photocatalytic activity. - Abstract: K{sub 3}PW{sub 12}O{sub 40} is a promising polyoxometalate photocatalyst for the removal of organic pollutants from water. However, two main disadvantages of poor adsorptive performance and high recombination rate of photogenerated electron-hole pair hinder its practical applications. In this paper, a new graphene nanosheets/K{sub 3}PW{sub 12}O{sub 40} nanocomposite has been synthesized via a green photoreduction strategy, being low-cost and scalable production. Characterizations show that K{sub 3}PW{sub 12}O{sub 40} nanoparticles with 60 nm or so have been successfully deposited on the graphene nanosheets. As a kind of photocatalyst, the binary graphene nanosheets/K{sub 3}PW{sub 12}O{sub 40} nanocomposite displays improved photocatalytic activity compared to pure K{sub 3}PW{sub 12}O{sub 40}. This improvement is ascribed to the introduction of graphene nanosheets in the nanocomposite, which could increase adsorptive property and reduce the recombination of electron-hole pairs.

Chromenoquinoline-based thiol probes: a study on the quencher position for controlling fluorescent Off-On characteristics.

Science.gov (United States)

Kand, Dnyaneshwar; Kalle, Arunasree Marasanapalli; Talukdar, Pinaki

2013-02-13

The design, synthesis and thiol sensing ability of chromenoquinoline-based fluorescent probes 4, 5 and 6 and are reported here. The relative position of the maleimide moiety was varied along the chromenoquinoline fluorophore to decrease the background fluorescence. Lower background fluorescence in probes 4 and 6 was rationalized by the smaller k(r)/k(nr) values compared to that of probe 5. An intramolecular charge transfer (ICT) mechanism was proposed for quenching and the extent was dependent on the position of the maleimide quencher. Fluorescent Off-On characteristics were evaluated by theoretical calculations. All probes were selective only towards thiol containing amino acids. Thiol sensing by probes 4 and 6 were much better compared to 5. Probe 4 displayed a better fluorescence response for less hindered thiol (185-, 223- and 156-fold for Hcy, Cys and GSH, respectively), while for probe 6, a higher enhancement in fluorescence was observed with more hindered thiols (180-, 205- and 245-fold for Hcy, Cys and GSH, respectively). The better response to bulkier thiol, GSH by probe 6 was attributed to the steric crowding at the C-4 position and bulkiness of the GSH group which force the succinimide unit to be in a nearly orthogonal conformation. This spatial arrangement was important in reducing the fluorescence quenching ability of the succinimide moiety. The application of probes 4, 5 and 6 was demonstrated by naked eye detection thiols using a 96-well plate system as well as by live-cell imaging.

Integral Parameters of the Thermal Neutron Scattering Law

International Nuclear Information System (INIS)

Purohit, S.N.

1964-09-01

Integral parameters of the thermal neutron scattering law - the thermalization binding parameter (M 2 ), the Placzek's moments of the generalized frequency spectrum of dynamical modes and the energy transfer moments of the scattering law - are theoretically discussed. A detailed study of the variation of M 2 , the thermalization time constant and the effective temperature of the vibrating atoms, with the relative weight between intra-molecular vibrations and hindered rotations for H 2 O, is presented. Theoretical results for different scattering models of H 2 O are compared with the measurements of integral experiments. A set of integral parameters for D 2 O, using Butler's model, have been obtained. Importance of the structure of hindered rotations of H 2 O and D 2 O in the study of integral parameters has also been discussed

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.

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.

Using a Fluorescent Cytosine Analogue tC[superscript o] To Probe the Effect of the Y567 to Ala Substitution on the Preinsertion Steps of dNMP Incorporation by RB69 DNA Polymerase

Energy Technology Data Exchange (ETDEWEB)

Xia, Shuangluo; Beckman, Jeff; Wang, Jimin; Konigsberg, William H. (Yale)

2012-10-10

Residues in the nascent base pair binding pocket (NBP) of bacteriophage RB69 DNA polymerase (RB69pol) are responsible for base discrimination. Replacing Tyr567 with Ala leads to greater flexibility in the NBP, increasing the probability of misincorporation. We used the fluorescent cytosine analogue, 1,3-diaza-2-oxophenoxazine (tC{sup o}), to identify preinsertion step(s) altered by NBP flexibility. When tC{sup o} is the templating base in a wild-type (wt) RB69pol ternary complex, its fluorescence is quenched only in the presence of dGTP. However, with the RB69pol Y567A mutant, the fluorescence of tC{sup o} is also quenched in the presence of dATP. We determined the crystal structure of the dATP/tC{sup o}-containing ternary complex of the RB69pol Y567A mutant at 1.9 {angstrom} resolution and found that the incoming dATP formed two hydrogen bonds with an imino-tautomerized form of tC{sup o}. Stabilization of the dATP/tC{sup o} base pair involved movement of the tC{sup o} backbone sugar into the DNA minor groove and required tilting of the tC{sup o} tricyclic ring to prevent a steric clash with L561. This structure, together with the pre-steady-state kinetic parameters and dNTP binding affinity, estimated from equilibrium fluorescence titrations, suggested that the flexibility of the NBP, provided by the Y567 to Ala substitution, led to a more favorable forward isomerization step resulting in an increase in dNTP binding affinity.

Electrochemically active MnO{sub 2} coated Li{sub 1.2}Ni{sub 0.18}Co{sub 0.04}Mn{sub 0.58}O{sub 2} cathode with highly improved initial coulombic efficiency

Energy Technology Data Exchange (ETDEWEB)

Jin, Yanling; Xu, Youlong, E-mail: ylxu@mail.xjtu.edu.cn; Sun, Xiaofei; Xiong, Lilong; Mao, Shengchun

2016-10-30

Highlights: • MnO{sub 2} was used to coat lithium-rich layered oxide Li{sub 1.2}Ni{sub 0.18}Co{sub 0.04}Mn{sub 0.58}O{sub 2}. • MnO{sub 2} is electrochemically active and became spinel phase after cycles. • MnO{sub 2}-coated material shows noticeably improved initial coulombic efficiency. • Specific capacities and rate performances could also be enhanced by MnO{sub 2} coating. - Abstract: Lithium-rich layered oxide is known to be one of the most promising positive electrode materials for lithium ion batteries due to its large capacity and high energy density. However, low initial coulombic efficiency is currently an urgent problem hindering its practical application. In this work, electrochemically active MnO{sub 2} coating was used to improve the coulombic efficiency of Li{sub 1.2}Ni{sub 0.18}Co{sub 0.04}Mn{sub 0.58}O{sub 2}. Firstly, the pristine material was synthesized via co-precipitation following by solid-state calcination. Then MnO{sub 2}-coated Li{sub 1.2}Ni{sub 0.18}Co{sub 0.04}Mn{sub 0.58}O{sub 2} was prepared by heat treatment of the mixture of pristine powder and manganese nitrate. During first discharging, lithium ions can intercalate into not only the delithiated Li{sub 1.2}Ni{sub 0.18}Co{sub 0.04}Mn{sub 0.58}O{sub 2} but also the MnO{sub 2} coating, thus noticeably improves the coulombic efficiency and discharge capacity. The initial efficiency is enhanced from 61.2% (pristine) to 84.4%, 88.8% and 95.4%, respectively, for 10 wt.%, 15 wt.% and 20 wt.% MnO{sub 2} coated Li{sub 1.2}Ni{sub 0.18}Co{sub 0.04}Mn{sub 0.58}O{sub 2} at 20 mA g{sup −1}. Furthermore, the 15 wt.% MnO{sub 2} coated sample delivers an initial discharge capacity as high as 294.4 mAh g{sup −1}.

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

Photoactive layered nanocomposites obtained by direct transferring of anodic TiO{sub 2} nanotubes to commodity thermoplastics