Marino, Nadia; Armentano, Donatella; De Munno, Giovanni; Cano, Joan; Lloret, Francesc; Julve, Miguel
2012-04-02
The preparation and X-ray crystal structure of four 2,2'-bipyrimidine (bpm)-containing copper(II) complexes of formula {[Cu(2)(μ-bpm)(H(2)O)(4)(μ-OH)(2)][Mn(H(2)O)(6)](SO(4))(2)}(n) (1), {[Cu(2)(μ-bpm)(H(2)O)(4)(μ-OH)(2)]SiF(6)}(n) (2), {Cu(2)(μ-bpm)(H(2)O)(2)(μ-F)(2)F(2)}(n) (3), and [Cu(bpm)(H(2)O)(2)F(NO(3))][Cu(bpm)(H(2)O)(3)F]NO(3)·2H(2)O (4) are reported. The structures of 1-3 consist of chains of copper(II) ions with regular alternation of bis-bidentate bpm and di-μ-hydroxo (1 and 2) or di-μ-fluoro (3) groups, the electroneutrality being achieved by either hexaaqua manganese(II) cations plus uncoordinated sulfate anions (1), uncoordinated hexafluorosilicate anions (2), or terminally bound fluoride ligands (3). Each copper(II) ion in 1-4 is six-coordinated in elongated octahedral surroundings. 1 and 2 show identical, linear chain motifs with two bpm-nitrogen atoms and two hydroxo groups building the equatorial plane at each copper(II) ion and the axial position being filled by water molecules. In the case of 3, the axial sites at the copper atom are occupied by a bpm-nitrogen atom and a bis-monodentate fluoride anion, producing a "step-like" chain motif. The values of the angle at the hydroxo and fluoro bridges are 94.11(6) (1), 94.75(4) (2), and 101.43(4)° (3). In each case, the copper-copper separation through the bis-bidentate bpm [5.428(1) (1), 5.449(1) (2), and 5.9250(4) Å (3)] is considerably longer than that through the di-μ-hydroxo [2.8320(4) (1) and 2.824(1) Å (2)] or di-μ-fluoro [3.3027(4) Å (3)] bridges. Compound 4 is a mononuclear species whose structure is made up of neutral [Cu(bpm)(H(2)O)(2)F(NO(3))] units, [Cu(bpm)(H(2)O)(3)F](+) cations, uncoordinated nitrate anions, and crystallization water molecules, giving rise to a pseudo-helical, one-dimensional (1D) supramolecular motif. The magnetic properties of 1-3 have been investigated in the temperature range 1.9-300 K. Relatively large, alternating antiferro- [J = -149 (1) and -141 cm(-1) (2) across bis-bidentate bpm] and ferromagnetic [αJ = +194 (1) and +176 cm(-1) (2) through the dihydroxo bridges] interactions occur in 1 and 2 [the Hamiltonian being defined as H = -J∑(i=1)(n/2) (S(2i)·S(2i-1) - αS(2i)·S(2i+1))]. These values compare well with those previously reported for parent examples. Two weak intrachain antiferromagnetic interactions [J = -0.30 and αJ = -8.1 cm(-1) across bpm and the di-μ-fluoro bridges, respectively] whose values were substantiated by density functional theory (DFT)-type calculations occur in 3.
Basallote, Manuel G; Martínez, Manuel; Vázquez, Marta
2014-07-28
In view of the relevance of the reactivity of inert tetraamine Co(III) complexes having two substitutionally active cis positions capable of interact with biologically relevant ligands, the study of the reaction of cis-[Co(cyclen)(H2O)2](3+) and [Co(tren)(H2O)2](3+) with chlorides, inorganic phosphate and 5'-CMP (5'-cytidinemonophosphate) has been pursued at physiological pH. The results indicate that, in addition to the actuation of the expected labilising conjugate-base mechanism, the formation of mono and inert bis hydroxo-bridged species is relevant for understanding their speciation and reactivity. The reactivity pattern observed also indicates the key role played by the "innocent" buffers frequently used in most in vitro studies, which can make the results unreliable in many cases. The differences between the reactivity of inorganic and biologically relevant phosphates has also been found to be remarkable, with outer-sphere hydrogen bonding interactions being a dominant factor for the process. While for the inorganic phosphate substitution process the formation of μ-η(2)-OPO2O represents the termination of the reactivity monitored, for 5'-CMP only the formation of η(1)-OPO3 species is observed, which evolve with time to the final dead-end bis hydroxo-bridged complexes. The promoted hydrolysis of the 5'-CMP phosphate has not been observed in any of the processes studied.
Methylene-bis[(aminomethyl)phosphinic acids]: synthesis, acid-base and coordination properties.
David, Tomáš; Procházková, Soňa; Havlíčková, Jana; Kotek, Jan; Kubíček, Vojtěch; Hermann, Petr; Lukeš, Ivan
2013-02-21
Three symmetrical methylene-bis[(aminomethyl)phosphinic acids] bearing different substituents on the central carbon atom, (NH(2)CH(2))PO(2)H-C(R(1))(R(2))-PO(2)H(CH(2)NH(2)) where R(1) = OH, R(2) = Me (H(2)L(1)), R(1) = OH, R(2) = Ph (H(2)L(2)) and R(1),R(2) = H (H(2)L(3)), were synthesized. Acid-base and complexing properties of the ligands were studied in solution as well as in the solid state. The ligands show unusually high basicity of the nitrogen atoms (log K(1) = 9.5-10, log K(2) = 8.5-9) if compared with simple (aminomethyl)phosphinic acids and, consequently, high stability constants of the complexes with studied divalent metal ions. The study showed the important role of the hydroxo group attached to the central carbon atom of the geminal bis(phosphinate) moiety. Deprotonation of the hydroxo group yields the alcoholate anion which tends to play the role of a bridging ligand and induces formation of polynuclear complexes. Solid-state structures of complexes [H(2)N=C(NH(2))(2)][Cu(2)(H(-1)L(2))(2)]CO(3)·10H(2)O and Li(2)[Co(4)(H(-1)L(1))(3)(OH)]·17.5H(2)O were determined by X-ray diffraction. The complexes show unexpected geometries forming dinuclear and cubane-like structures, respectively. The dinuclear copper(II) complex contains a bridging μ(2)-alcoholate group with the (-)O-P(=O)-CH(2)-NH(2) fragments of each ligand molecule chelated to the different central ion. In the cubane cobalt(II) complex, one μ(3)-hydroxide and three μ(3)-alcoholate anions are located in the cube vertices and both phosphinate groups of one ligand molecule are chelating the same cobalt(II) ion while each of its amino groups are bound to different neighbouring metal ions. All such three metal ions are bridged by the alcoholate group of a given ligand.
Undecametallic and hexadecametallic ferric oxo–hydroxo/ethoxo pivalate clusters
Baca, Svetlana G.; Speldrich, Manfred; van Leusen, Jan; ...
2015-03-27
The synthesis strategies for highly condensed {Fe 11} and {Fe 16} pivalate clusters have been developed based on archetypal geometrically frustrated triangular {Fe 3(μ 3-O)} motifs that are interlinked via oxo, hydroxo, ethoxo, and carboxylate groups.
Hermann, T; Auffinger, P; Scott, W G; Westhof, E
1997-01-01
In the presence of magnesium ions, cleavage by the hammerhead ribozyme RNA at a specific residue leads to 2'3'-cyclic phosphate and 5'-OH extremities. In the cleavage reaction an activated ribose 2'-hydroxyl group attacks its attached 3'-phosphate. Molecular dynamics simulations of the crystal structure of the hammerhead ribozyme, obtained after flash-freezing of crystals under conditions where the ribozyme is active, provide evidence that a mu-bridging OH-ion is located between two Mg2+ions close to the cleavable phosphate. Constrained simulations show further that a flip from the C3'- endo to the C2'- endo conformation of the ribose at the cleavable phosphate brings the 2'-hydroxyl in proximity to both the attacked phosphorous atom and the mu-bridging OH-ion. Thus, the simulations lead to a detailed new insight into the mechanism of hammerhead ribozyme cleavage where a mu-hydroxo bridged magnesium cluster, located on the deep groove side, provides an OH-ion that is able to activate the 2'-hydroxyl nucleophile after a minor and localized conformational change in the RNA. PMID:9254698
Harris, Travis V; Morokuma, Keiji
2013-08-05
Ferritins are cage-like proteins composed of 24 subunits that take up iron(II) and store it as an iron(III) oxide mineral core. A critical step is the ferroxidase reaction, in which oxygen reacts with a di-iron(II) site, proceeding through a peroxo intermediate, to form μ-oxo/hydroxo-bridged di-iron(III) products. The recent crystal structures of copper(II)- and iron(III)-bound frog M ferritin at 2.8 Å resolution [Bertini; et al. J. Am. Chem. Soc. 2012, 134, 6169-6176] provided an opportunity to theoretically investigate the detailed structures of the reactant state and products. In this study, the quantum mechanical/molecular mechanical ONIOM method is used to structurally optimize a series of single-subunit models with various hydration, protonation, and coordination states of the ferroxidase site. Calculated exchange coupling constants (J), Mössbauer parameters, and time-dependent density functional theoretical (TD-DFT) circular dichroism spectra with electronic embedding are compared with the available experimental data. The di-iron(II) model with the most experimentally consistent structural and spectroscopic parameters has 5-coordinate iron centers with Glu23, Glu58, His61, and two waters completing one coordination sphere, and His54, Glu58, Glu103, and Asp140 completing the other. In contrast to a previously proposed structure, Gln137 is not directly coordinated, but it is involved in hydrogen bonding with several iron ligands. For the di-iron(III) products, we find that a μ-oxo-bridged and two doubly bridged (μ-hydroxo and μ-oxo/hydroxo) species are likely coproduced. Although four quadrupole doublets were observed experimentally, we find that two doublets may arise from a single asymmetrically coordinated ferroxidase site. These proposed key structures will help to explore the pathway connecting the di-Fe(II) state to the peroxo intermediate and the branching mechanisms leading to the multiple products.
Molecular Recognition in the Oxidation of Catechols by Dicobalt-BISDIEN Dioxygen Complexes
1992-01-30
Recognition in the Oxidation of Catechols by Dicobalt-RISDIEN Dioxygen Complexes Lizete F S Cezar and Bruno Szpoganicz Departamento de Quimica ...bridged bi- nuclear Co(II)-BISDIEN dioxygen complexes; Co20 2 LCat2 + is the bivalent form, and Co20 2 (OH)LCat + and Co 20 2 (OH)2 Cat° are hydroxo
Dithiolato-bridged nickel-iron complexes as models for the active site of [NiFe]-hydrogenases.
Song, Li-Cheng; Yang, Xi-Yue; Cao, Meng; Gao, Xiu-Yun; Liu, Bei-Bei; Zhu, Liang; Jiang, Feng
2017-03-30
The structural and functional modeling of the active site of [NiFe]-hydrogenases has been proved to be challenging to a great extent. Herein, we report the synthesis, structures, and some properties of the NiFe-based dicarbonyl, terminal hydride, and μ-hydroxo models for the active site of [NiFe]-hydrogenases.
Papadakis, Raffaello; Rivière, Eric; Giorgi, Michel; Jamet, Hélène; Rousselot-Pailley, Pierre; Réglier, Marius; Simaan, A Jalila; Tron, Thierry
2013-05-20
A novel tetranuclear copper(II) complex (1) was synthesized from the self-assembly of copper(II) perchlorate and the ligand N-benzyl-1-(2-pyridyl)methaneimine (L(1)). Single-crystal X-ray diffraction studies revealed that complex 1 consists of a Cu4(OH)4 cubane core, where the four copper(II) centers are linked by μ3-hydroxo bridges. Each copper(II) ion is in a distorted square-pyramidal geometry. X-ray analysis also evidenced an unusual metal cation-π interaction between the copper ions and phenyl substituents of the ligand. Calculations based on the density functional theory method were used to quantify the strength of this metal-π interaction, which appears as an important stabilizing parameter of the cubane core, possibly acting as a driving parameter in the self-aggregation process. In contrast, using the ligand N-phenethyl-1-(2-pyridyl)methaneimine (L(2)), which only differs from L(1) by one methylene group, the same synthetic procedure led to a binuclear bis(μ-hydroxo)copper(II) complex (2) displaying intermolecular π-π interactions or, by a slight variation of the experimental conditions, to a mononuclear complex (3). These complexes were studied by X-ray diffraction techniques. The magnetic properties of complexes 1 and 2 are reported and discussed.
Wikstrom, Jeffrey P; Filatov, Alexander S; Mikhalyova, Elena A; Shatruk, Michael; Foxman, Bruce M; Rybak-Akimova, Elena V
2010-03-14
The tridentate aminopyridine ligand bearing a bulky tert-butyl substituent at the amine nitrogen, tert-butyl-dipicolylamine (tBuDPA), occupies three coordination sites in six-coordinate complexes of nickel(ii), leaving the remaining three sites available for additional ligand binding and activation. New crystallographically characterized complexes include two mononuclear species with 1:1 metal:ligand complexation: a trihydrate solvate (1.3H(2)O) and a monohydrate biacetonitrile solvate (1.H(2)O.2CH(3)CN). Complexation in the presence of sodium hydroxide results in a bis(mu-hydroxo) complex (2), the bridging hydroxide anions of which are labile and become displaced by methoxide anions in methanol solvent, affording bis-methoxo-bridged (4). Nickel(II) centers in 2 are five-coordinate and antiferromagnetically coupled (with J = -31.4(5) cm(-1), H = -2JS(1)S(2), in agreement with Ni-O-Ni angle of 103.7 degrees). Bridging hydroxide or alkoxide anions in coordinatively unsaturated dinuclear nickel(II) complexes with tBuDPA react as active nucleophiles. 2 readily performs carbon dioxide fixation, resulting in the formation of a bis(mu-carbonato) tetrameric complex (3), which features a novel binding geometry in the form of an inverted butterfly-type nickel-carbonate core. Temperature-dependent magnetic measurements of tetranuclear carbonato-bridged revealed relatively weak antiferromagnetic coupling (J(1) = -3.1(2) cm(-1)) between the two nickel centers in the core of the cluster, as well as weak antiferromagnetic pairwise interactions (J(2) = J(3) = -4.54(5) cm(-1)) between central and terminal nickel ions.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Platero-Prats, Ana E.; League, Aaron B.; Bernales, Varinia
2017-07-24
Metal-organic frameworks (MOFs), with their well-ordered pore networks and tunable surface chemistries, offer a versatile platform for preparing well-defined nanostructures wherein functionality such as catalysis can be incorporated. We resolved the atomic structure of Ni-oxo species deposited in the MOF NU-1000 through atomic layer deposition using local and long-range structure probes, including X-ray absorption spectroscopy, pair distribution function analysis and difference envelope density analysis, with electron microscopy imaging and computational modeling.
Abrahams, Brendan F; Haywood, Marissa G; Robson, Richard
2004-04-21
Addition of Co(NH3)6(3+) to aqueous solutions of Cu(II) in excess carbonate promotes the assembly of a new highly charged carbonato-copper(II) anion, [Cu4(OH)(CO3)8](9-), which contains an unusual mu4 hydroxo-bridged square Cu4 arrangement, stabilised in the crystal by no less than forty hydrogen bonds (< 3 Angstrom) to hexammine cations.
Graham, B; Hearn, M T; Junk, P C; Kepert, C M; Mabbs, F E; Moubaraki, B; Murray, K S; Spiccia, L
2001-03-26
Hydroxo- and methoxo-bridged tetranuclear copper(II) complexes of the tetramacrocyclic ligand 1,2,4,5-tetrakis(1,4,7-triazacyclonon-1-ylmethyl)benzene (Ldur), have been prepared from [Cu4Ldur(H2O)8](ClO4)8.9H2O (1). Addition of base to an aqueous solution of 1 gave [Cu4Ldur(mu2-OH)4](ClO4)4 (2). Diffusion of MeOH into a DMF solution of 2 produces [Cu4Ldur(mu2-OMe)4](ClO4)4.HClO4.2/3MeOH (3), a complex which hydrolyzes on exposure to moisture regenerating 2. The structurally related azido-bridged complex, [Cu4Ldur(mu2-N3)4](PF6)4.4H2O.6CH3CN (4), was produced by reaction of Ldur with 4 molar equiv of Cu(OAc)2.H2O and NaN3 in the presence of excess KPF6. Compounds 2-4 crystallize in the triclinic space group P1 (No. 2) with a = 10.248(1) A, b = 12.130(2) A, c = 14.353(2) A, alpha = 82.23(1) degrees, beta = 80.79(1) degrees, gamma = 65.71(1) degrees, and Z = 1 for 2, a = 10.2985(4) A, b = 12.1182(4) A, c = 13.9705(3) A, alpha = 89.978(2) degrees, beta = 82.038(2) degrees, gamma = 65.095(2) degrees, and Z = 1 for 3, and a = 12.059(2) A, b = 12.554(2) A, c = 14.051(2) A, alpha = 91.85(1) degrees, beta = 98.22(1) degrees, gamma = 105.62(1) degrees, and Z = 1 for 4. The complexes feature pairs of isolated dibridged copper(II) dimers with "roof-shaped" Cu2(mu2-X)2 cores (X = OH-, OMe-, N3-), as indicated by the dihedral angle between the two CuX2 planes (159 degrees for 2, 161 degrees for 3, and 153 degrees for 4). This leads to Cu.Cu distances of 2.940(4) A for 2, 2.962(1) A for 3, and 3.006(5) A for 4. Variable-temperature magnetic susceptibility measurements indicate weak antiferromagnetic coupling (J = -27 cm(-1)) for the hydroxo-bridged copper(II) centers in 2 and very strong antiferromagnetic coupling (J = -269 cm(-1)) for the methoxo-bridged copper(II) centers in 3. Pairs of copper(II) centers in 4 display the strongest ferromagnetic interaction (J = 94 cm(-1)) reported thus far for bis(mu2-1,1-azido)-bridged dicopper units. Spectral measurements on a neat powdered sample of 4 at 33.9 GHz or 90 Ghz confirm the spin-triplet ground state for the azido-bridged copper(II) pairs.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Tsang, B.W.; Reibenspies, J.; Martell, A.E.
1993-03-17
The complexes of ReO[sub 2][sup +] and ReO(OH)[sup 2+] with 1,4,8,11-tetraazacyclotetradecane (cyclam) and 1,4,8,11-tetraazacyclotetradecan-2-one (O[sub 1]cyclam) have been synthesized and characterized. The complexes were prepared by ligand exchange reactions of the macrocycles with a variety of starting compounds including ReOCl[sub 3](PPh[sub 3])[sub 2] and ReO[sub 2](en)[sub 2]Cl. The ReO(OH)[sup 2+] complexes have been structurally characterized. ReO(OH)(H[sub [minus]1]O[sub 1]cyclam)ReO[sub 4] crystallizes in the monoclinic P2[sub 1]/n space group with a = 10.308(3) [Angstrom], b = 9.527(2) [Angstrom], c = 17.808(3) [Angstrom], and [beta] = 106.57(2)[degrees]. ReO(OH)(cyclam)(ClO[sub 4])[sub 2] crystallizes in the monoclinic C2/c space group with a = 9.734(4) [Angstrom], bmore » = 16.999(5) [Angstrom], c = 12.187(5) [Angstrom], and [beta] = 106.36[degrees]. The complex ReO(OH)(H[sub [minus]1]O[sub 1]cyclam)ReO[sub 4] has a distorted octahedral structure with one short ReO(oxo) bond and one long ReO(hydroxo) bond (1.685(8) vs 1.970(8) [Angstrom]). The deprotonated amide ReN(sp[sup 2]) bond is shorter than the other three ReN(sp[sup 3]) bond lengths (1.98(1) vs 2.13(3) [Angstrom] (average)). The structure of the ReO(OH)(cyclam)(ClO[sub 4])[sub 2] complex shows no distinction between the lengths of the two ReO(oxo and hydroxo) bonds (1.766(5) [Angstrom]) due to disorder of the oxo and hydroxo groups. Spectroscopic evidence is reported to confirm the presence of both oxo and hydroxo groups coordinated to rhenium. 38 refs., 7 figs., 6 tabs.« less
Kato, Merii; Sah, Ajay Kumar; Tanase, Tomoaki; Mikuriya, Masahiro
2006-08-21
Tetranuclear copper(II) complexes containing alpha-D-glucose-1-phosphate (alpha-D-Glc-1P), [Cu4(mu-OH){mu-(alpha-D-Glc-1P)}2(bpy)4(H2O)2]X3 [X = NO3 (1a), Cl (1b), Br (1c)], and [Cu4(mu-OH){mu-(alpha-D-Glc-1P)}2(phen)4(H2O)2](NO3)3 (2) were prepared by reacting the copper(II) salt with Na2[alpha-D-Glc-1P] in the presence of diimine ancillary ligands, and the structure of 2 was characterized by X-ray crystallography to comprise four {Cu(phen)}2+ fragments connected by the two sugar phosphate dianions in 1,3-O,O' and 1,1-O mu4-bridging fashion as well as a mu-hydroxo anion. The crystal structure of 2 involves two chemically independent complex cations in which the C2 enantiomeric structure for the trapezoidal tetracopper(II) framework is switched according to the orientation of the alpha-D-glucopyranosyl moieties. Temperature-dependent magnetic susceptibility data of 1a indicated that antiferromagnetic spin coupling is operative between the two metal ions joined by the hydroxo bridge (J = -52 cm(-1)) while antiferromagnetic interaction through the Cu-O-Cu sugar phosphate bridges is weak (J = -13 cm(-1)). Complex 1a readily reacted with carboxylic acids to afford the tetranuclear copper(II) complexes, [Cu4{mu-(alpha-D-Glc-1P)}2(mu-CA)2(bpy)4](NO3)2 [CA = CH3COO (3), o-C6H4(COO)(COOH) (4)]. Reactions with m-phenylenediacetic acid [m-C6H4(CH2COOH)2] also gave the discrete tetracopper(II) cationic complex [Cu4{mu-(alpha-D-Glc-1P)}2(mu-m-C6H4(CH2COO)(CH2COOH))2(bpy)4](NO3)2 (5a) as well as the cluster polymer formulated as {[Cu4{mu-(alpha-D-Glc-1P)}2(mu-m-C6H4(CH2COO)2)(bpy)4](NO3)2}n (5b). The tetracopper structure of 1a is converted into a symmetrical rectangular core in complexes 3, 4, and 5b, where the hydroxo bridge is dissociated and, instead, two carboxylate anions bridge another pair of Cu(II) ions in a 1,1-O monodentate fashion. The similar reactions were applied to incorporate sugar acids onto the tetranuclear copper(II) centers. Reactions of 1a with delta-D-gluconolactone, D-glucuronic acid, or D-glucaric acid in dimethylformamide resulted in the formation of discrete tetracopper complexes with sugar acids, [Cu4{mu-(alpha-D-Glc-1P)}2(mu-SA)2(bpy)4](NO3)2 [SA = D-gluconate (6), D-glucuronate (7), D-glucarateH (8a)]. The structures of 6 and 7 were determined by X-ray crystallography to be almost identical with that of 3 with additional chelating coordination of the C-2 hydroxyl group of D-gluconate moieties (6) or the C-5 cyclic O atom of D-glucuronate units (7). Those with D-glucaric acid and D-lactobionic acid afforded chiral one-dimensional polymers, {[Cu4{mu-(alpha-D-Glc-1P)}2(mu-D-glucarate)(bpy)4](NO3)2}n (8b) and {[Cu4{mu-(alpha-D-Glc-1P)}2(mu-D-lactobionate)(bpy)4(H2O)2](NO3)3}n (9), respectively, in which the D-Glc-1P-bridged tetracopper(II) units are connected by sugar acid moieties through the C-1 and C-6 carboxylate O atoms in 8b and the C-1 carboxylate and C-6 alkoxy O atoms of the gluconate chain in 9. When complex 7 containing d-glucuronate moieties was heated in water, the mononuclear copper(II) complex with 2-dihydroxy malonate, [Cu(mu-O2CC(OH)2CO2)(bpy)] (10), and the dicopper(II) complex with oxalate, [Cu2(mu-C2O4)(bpy)2(H2O)2](NO3)2 (11), were obtained as a result of oxidative degradation of the carbohydrates through C-C bond cleavage reactions.
Manganese-Oxygen Intermediates in O-O Bond Activation and Hydrogen-Atom Transfer Reactions.
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 step in designing Mn III -peroxo complexes that convert cleanly to high-valent Mn-oxo species. Although some synthetic Mn IV -oxo complexes show great potential for oxidizing substrates with strong C-H bonds, most Mn IV -oxo species are sluggish oxidants. Both two-state reactivity and thermodynamic arguments have been put forth to explain these observations. To address these issues, we generated a series of Mn IV -oxo complexes supported by neutral, pentadentate ligands with systematically perturbed equatorial donation. Kinetic investigations of these complexes revealed a correlation between equatorial ligand-field strength and hydrogen-atom and oxygen-atom transfer reactivity. While this trend can be understood on the basis of the two-state reactivity model, the reactivity trend also correlates with variations in Mn III/IV reduction potential caused by changes in the ligand field. This work demonstrates the dramatic influence simple ligand perturbations can have on reactivity but also illustrates the difficulties in understanding the precise basis for a change in reactivity. In the enzyme manganese lipoxygenase, an active-site Mn III -hydroxo adduct initiates substrate oxidation by abstracting a hydrogen atom from a C-H bond. Precedent for this chemistry from synthetic Mn III -hydroxo centers is rare. To better understand hydrogen-atom transfer by Mn III centers, we developed a pair of Mn III -hydroxo complexes, formed in high yield from dioxygen oxidation of Mn II precursors, capable of attacking weak O-H and C-H bonds. Kinetic and computational studies show a delicate interplay between thermodynamic and steric influences in hydrogen-atom transfer reactivity, underscoring the potential of Mn III -hydroxo units as mild oxidants.
Borghi, Elena; Solari, Pier Lorenzo; Beltramini, Mariano; Bubacco, Luigi; Di Muro, Paolo; Salvato, Benedetto
2002-01-01
The binuclear copper sites of the met and met-azido derivatives of Octopus vulgaris and Carcinus aestuarii hemocyanins at pH 7.5 were characterized by high-resolution x-ray absorption spectroscopy in the low energy region (XANES) and in the higher region (EXAFS). The accuracy of the analysis of the data was tested with two mononuclear and six binuclear copper(II) complexes of the poly(benzimidazole) ligand systems 2-BB, L-5,5 and L-6,6 (Casella et al., 1993, Inorg. Chem. 32:2056-2067; 1996, Inorg. Chem. 35:1101-1113). Their structural and reactivity properties are related to those of the protein's derivatives. The results obtained for those models with resolved x-ray structure (the 2-BB-aquo and azido mononuclear complexes, and the binuclear L-5,5 Cu(II)-bis(hydroxo) (Casella et al., unpublished)), extends the validity of our approach to the other poly(benzimidazole)-containing complexes and to the hemocyanin derivatives. Comparison between the protein's and the complexes' data, support a description of the met-derivatives as a five-coordinated O-bridged binuclear copper(II) center and favors, for both species, a bis(hydroxo) structure with a 3-A Cu-Cu distance. For O. vulgaris met-azido derivative a mu-1,3 bridging mode for the ligand appears the most likely. The structural situation of C. aestuarii met-azido-derivative is less clear: a mu-1,1 mode is favored, but a terminal mode cannot be excluded. PMID:12023249
Thermodynamics of complexation in an aqueous solution of Tb(III) nitrate at 298 K
NASA Astrophysics Data System (ADS)
Lobacheva, O. L.; Berlinskii, I. V.; Dzhevaga, N. V.
2017-01-01
The pH of the formation of hydroxo complexes and hydrates in an aqueous solution of terbium Tb(III) is determined using combined means of potentiometric and conductometric titration. The stability constants of the hydroxo complexes, the products of hydroxide solubility, and the Gibbs energy of terbium hydroxo complex formation are calculated.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Nekhamkin, L.G.; Kondrashova, I.A.; Kerina, V.R.
1987-08-20
The reactivity of zirconium basic sulfate is determined by the possibility of replacement of oxo- and hydroxo-ligands and decreases with increasing temperature of its precipitation. The interaction of the less reactive zirconium basic sulfate with carbonate and oxalate reagents occurs at 25/sup 0/C without any change in basicity and that with phosphate reagents occurs with a decrease in it, up to the formation of a monophosphate with basicity about 20%. In the interaction of the more reactive zirconium basic sulfate, obtained without heating, oxo- and hydroxo groups can be entirely replaced by acido-ligands with the formation of unhydrolyzed compounds.
Speciation of platinum(IV) in nitric acid solutions.
Vasilchenko, Danila; Tkachev, Sergey; Baidina, Iraida; Korenev, Sergey
2013-09-16
The speciation of platinum(IV) ions in nitric acid (6-15.8 M) solutions of H2[Pt(OH)6] has been studied by (195)Pt NMR and Raman spectroscopy. Series of aqua-hydroxo-nitrato complexes [Pt(L)(x)(NO3)(6-x)] (L = H2O or OH(-); x = 0, ..., 6) were found to exist in such solutions. The pair additivity model of chemical shifts and statistical theory were used to assign signals in NMR spectra to particular [Pt(L)(x)(NO3)(6-x)] species. Mononuclear hexanitratoplatinates(IV) have been isolated in solid state in substantial yield as pyridinium salt (PyH)2[Pt(NO3)6] and characterized by single-crystal X-ray diffraction. Aging of the platinum nitric acid solutions for more than 5-6 h results in oligomerization of [Pt(L)(x)(NO3)(6-x)] species and the formation of oligonuclear aqua-hydroxo-nitrato complexes with OH(-) and NO3(-) bridging ligands. Oligomeric platinum(IV) complexes with two and four nuclei were unambiguously detected by NMR on (195)Pt -enriched samples. Oligomers with even higher nuclearity were also detected. Dimeric anions [Pt2(μ-OH)2(NO3)8](2-) have been isolated as single crystals of tetramethylammonium salt and characterized by X-ray diffraction.
Castro, Isabel; Calatayud, M Luisa; Barros, Wdeson P; Carranza, José; Julve, Miguel; Lloret, Francesc; Marino, Nadia; De Munno, Giovanni
2014-06-02
A novel series of heteroleptic copper(II) compounds of formulas {[Cu2(μ-H2O)(μ-pz)2(μ-bpm)(ClO4)(H2O)]ClO4·2H2O}n (1), {[Cu2(μ-H2O)(μ-3-Mepz)2(μ-bpm)](ClO4)2·2H2O}n (2), and {[Cu2(μ-OH)(μ-3,5-Me2pz)(μ-bpm)(H-3,5-Me2pz)2](ClO4)2}n (3) [bpm = 2,2'-bipyrimidine, Hpz = pyrazole, H-3-Mepz = 3-methylpyrazole, and H-3,5-Me2pz = 3,5-dimethylpyrazole] have been synthesized and structurally characterized by X-ray diffraction methods. The crystal structures of 1 and 2 consist of copper(II) chains with regular alternating bpm and bis(pyrazolate)(aqua) bridges, whereas that of 3 is made up of copper(II) chains with regular alternating bpm and (pyrazolate)(hydroxo) bridges. The copper centers are six- (1) or five-coordinate (2) in axially elongated, octahedral (1) or square-pyramidal (2) environments in 1 and 2, whereas they are five-coordinate in distorted trigonal-bipyramidal surroundings in 3. The values of the copper-copper separations across the bpm/pyrazolate bridges are 5.5442(7)/3.3131(6) (1), 5.538(1)/3.235(1) (2), and 5.7673(7)/3.3220(6) Å (3). The magnetic properties of 1-3 have been investigated in the temperature range of 25-300 K. The analysis of their magnetic susceptibility data through the isotropic Hamiltonian for an alternating antiferromagnetic copper(II) chain model [H = -J∑i=1-n/2 (S2i·S2i-1 + αS2i·S2i+1), with α = J'/J and Si = SCu = 1/2] reveals the presence of a strong to moderate antiferromagnetic coupling through the bis(pyrazolate)(aqua) [-J = 217 (1) and 215 cm(-1) (2)] and (pyrazolate)(hydroxo) bridges [-J = 153 cm(-1) (3)], respectively, whereas a strong to weak antiferromagnetic coupling occurs through the bis-bidentate bpm [-J' = 211 (1), 213 (2), and 44 cm(-1) (3)]. A simple orbital analysis of the magnetic exchange interaction within the bpm- and pyrazolate-bridged dicopper(II) fragments of 1-3 visualizes the σ-type pathways involving the (dx(2)-y(2)) (1 and 2) or d(z(2)) (3) magnetic orbitals on each metal ion, which account for the variation of the magnetic properties in these three novel examples of one-dimensional copper(II) compounds with regular alternating intrachain antiferromagnetic interactions.
Khenkin, Alexander M; Vedichi, Madhu; Shimon, Linda J W; Cranswick, Matthew A; Klein, Johannes E M N; Que, Lawrence; Neumann, Ronny
2017-11-01
The iron(II) triflate complex ( 1 ) of 1,2-bis(2,2'-bipyridyl-6-yl)ethane, with two bipyridine moieties connected by an ethane bridge, was prepared. Addition of aqueous 30% H 2 O 2 to an acetonitrile solution of 1 yielded 2 , a green compound with λ max =710 nm. Moessbauer measurements on 2 showed a doublet with an isomer shift (δ) of 0.35 mm/s and a quadrupole splitting (Δ E Q ) of 0.86 mm/s, indicative of an antiferromagnetically coupled diferric complex. Resonance Raman spectra showed peaks at 883, 556 and 451 cm -1 that downshifted to 832, 540 and 441 cm -1 when 1 was treated with H 2 18 O 2 . All the spectroscopic data support the initial formation of a (μ-hydroxo)(μ-1,2-peroxo)diiron(III) complex that oxidizes carbon-hydrogen bonds. At 0°C 2 reacted with cyclohexene to yield allylic oxidation products but not epoxide. Weak benzylic C-H bonds of alkylarenes were also oxidized. A plot of the logarithms of the second order rate constants versus the bond dissociation energies of the cleaved C-H bond showed an excellent linear correlation. Along with the observation that oxidation of the probe substrate 2,2-dimethyl-1-phenylpropan-1-ol yielded the corresponding ketone but no benzaldehyde, and the kinetic isotope effect, k H /k D , of 2.8 found for the oxidation of xanthene, the results support the hypothesis for a metal-based H-atom abstraction mechanism. Complex 2 is a rare example of a (μ-hydroxo)(μ-1,2-peroxo)diiron(III) complex that can elicit the oxidation of carbon-hydrogen bonds.
Mukherjee, Jhumpa; Lucas, Robie L.; Zart, Matthew K.; Powell, Douglas R.; Day, Victor W.; Borovik, A. S.
2013-01-01
Mononuclear iron(III) complexes with terminal hydroxo ligands are proposed to be important species in several metalloproteins, but they have been difficult to isolate in synthetic systems. Using a series of amidate/ureido tripodal ligands, we have prepared and characterized monomeric FeIIIOH complexes with similar trigonal-bipyramidal primary coordination spheres. Three anionic nitrogen donors define the trigonal plane, and the hydroxo oxygen atom is trans to an apical amine nitrogen atom. The complexes have varied secondary coordination spheres that are defined by intramolecular hydrogen bonds between the FeIIIOH unit and the urea NH groups. Structural trends were observed between the number of hydrogen bonds and the Fe–Ohydroxo bond distances: the more intramolecular hydrogen bonds there were, the longer the Fe–O bond became. Spectroscopic trends were also found, including an increase in the energy of the O–H vibrations with a decrease in the number of hydrogen bonds. However, the FeIII/II reduction potentials were constant throughout the series (∼2.0 V vs [Cp2Fe]0/+1), which is ascribed to a balancing of the primary and secondary coordination-sphere effects. PMID:18498155
NASA Astrophysics Data System (ADS)
Sadeghi Googheri, Motahare; Abolhassani, Mohammad Reza; Mirzaei, Mahmoud
2018-05-01
Designing and introducing novel wheel-shaped supramolecular as host complexes with new magnetic properties is the theme of the day. So in this study, new eight binuclear chromium (III) complexes, as models of real chromium-wheel host complexes, were designed based on changing of bridged-ligands and exchange coupling constants (J) of them were calculated using the broken symmetry density functional theory approach. Substitution of fluorine ligand in fluoro-bridged model [Cr2F(tBuCO2)2(H2O)2(OH)4]-1 by halogen anions (Cl-, Br- and I- ) decreased the antiferromagnetic exchange coupling between Cr(III) centres such that by going from F- to I- the J values became more positive. In the case of hydroxo-bridged model [Cr2OH(tBuCO2)2(H2O)2(OH)4]-1, replacement of hydroxyl by methoxy anion (OMe-) strengthened the antiferromagnetic property of the complex but substitution by sulfanide (SH-) and amide (NH2-) anions weakened it and changed the nature of complexes to ferromagnetic. Because of their different magnetic properties, these new investigated complexes can be suggested as interesting synthetic targets. Also, the J value changes due to ligand substitution were evaluated and it was found that the Cr-X bond strength and partial charges of involved atoms were the most effective factors on it.
Theoretical investigation on the dimerization of the deprotonated aquo ion of Al(III) in water.
Qian, Zhaosheng; Feng, Hui; Zhang, Zhenjiang; Yang, Wenjing; Jin, Jing; Miao, Qiang; He, Lina; Bi, Shuping
2009-01-21
Reaction pathways, solvent effects and energy barriers have been investigated for the dimerization of the deprotonated aquo ion of Al(III) in aqueous solution by performing supramolecule density functional theory calculations. Two competing reaction pathways were investigated, sharing a common first step and third step, i.e. the formation of the aggregate II of two aluminium monomers and the doubly bridged dimer. One pathway involves a nucleophilic attack to undercoordinated metal center in the first step and then the loss of a coordinated water molecule. Another pathway involves a water exchange reaction in the first step and then the formation of the hydroxo bridge. The calculated results indicate that both pathways I and II are possible in aqueous solution. The direct participation of the solvent water molecule facilitates the dimerization, but the extremely large solvent shifts of the energy barriers for each reaction are attributed mainly to the bulk effect. The computed activation energies for the water exchange reactions are in good agreement with the available experimental values, namely, the calculated value 37.5 kJ mol(-1) compared to the experimental value 36.4 (+/-5) kJ mol(-1). In agreement with experimental observations in aqueous solution, the calculated results favor the transformation of singly-bridged to doubly-bridged aluminium ion, which is helpful to understand the complicated hydrolytic polymerizaiton of Al(III).
Di Pasqua, Anthony J; Centerwall, Corey R; Kerwood, Deborah J; Dabrowiak, James C
2009-02-02
The second-generation Pt(II) anticancer drug carboplatin is here shown to react with carbonate, which is present in blood, interstitial fluid, cytosol, and culture medium, to produce platinum-carbonato and -hydroxo complexes. Using [(1)H-(15)N] HSQC NMR and (15)N-labeled carboplatin, we observe that cis-[Pt(CBDCA-O)(OH)(NH(3))(2)](-), cis-[Pt(OH)(2)(NH(3))(2)], cis-[Pt(CO(3))(OH)(NH(3))(2)](-), and what may be cis-[Pt(CO(3))(NH(3))(2)] are produced when 1 is allowed to react in 23.8 mM carbonate buffer. When (15)N-labeled carboplatin is allowed to react in 0.5 M carbonate buffer, these platinum species, as well as other hydroxo and carbonato species, some of which may be dinuclear complexes, are produced. Furthermore, we show that the carbonato species cis-[Pt(CO(3))(OH)(NH(3))(2)](-) is also produced when cisplatin is allowed to react in carbonate buffer. The study outlines the conditions under which carboplatin and cisplatin form carbonato and aqua/hydroxo species in carbonate media.
Zimmermann, Iwan; Johnsson, Mats
2013-10-21
Three new cobalt selenite hydroxo-phosphates laying in the solid solution Co3(SeO3)3-x(PO3OH)x(H2O), with x = 0.8, x = 1.0, and x = 1.2 are reported. Single crystals were obtained by hydrothermal synthesis and the crystal structure was determined by single crystal X-ray diffraction. The structure can be described as a 3D framework having selenite and hydroxo-phosphate groups protruding into channels in the crystal structure. Se(4+) and P(5+) share a split position in the structure so that either SeO3 groups having a stereochemically active lone pair or tetrahedrally coordinated PO3OH groups are present. The OH-group is thus only present when the split position is occupied by P(5+). The crystal water is coordinated to a cobalt atom and TG and IR measurements show that the water and hydroxyl groups leave the structure at unusually high temperatures (>450 °C). Magnetic susceptibility measurements show antiferromagnetic coupling below 16 K and a magnetic moment of 4.02(3) μB per Co atom was observed.
Wickramasinghe, Lasantha A; Sharp, Paul R
2014-11-17
Photolysis (380 nm) of trans,cis-Pt(PEt3)2(Cl)2(OH)(4-tft) (4-tft = 4-trifluoromethylphenyl) at 77 K in 2-methyltetrahydrofuran gives triplet emission, platinum(III), and a hydroxo radical. Benzyl radical emission is observed in toluene from the reaction of a portion of the OH radicals with toluene. Warming the photolyzed solutions gives platinacycle trans-Pt(CH2CH2PEt2)(PEt3)(Cl)2(4-tft) by hydrogen-atom abstraction from a PEt3 ligand and trans-Pt(PEt3)2(Cl)(4-tft) from net HOCl photoelimination. The platinacycle undergoes thermal reductive elimination at 298 K or photolytic reductive elimination, even at 77 K.
Structural differences between the ready and unready oxidized states of [NiFe] hydrogenases.
Volbeda, Anne; Martin, Lydie; Cavazza, Christine; Matho, Michaël; Faber, Bart W; Roseboom, Winfried; Albracht, Simon P J; Garcin, Elsa; Rousset, Marc; Fontecilla-Camps, Juan C
2005-05-01
[NiFe] hydrogenases catalyze the reversible heterolytic cleavage of molecular hydrogen. Several oxidized, inactive states of these enzymes are known that are distinguishable by their very different activation properties. So far, the structural basis for this difference has not been understood because of lack of relevant crystallographic data. Here, we present the crystal structure of the ready Ni-B state of Desulfovibrio fructosovorans [NiFe] hydrogenase and show it to have a putative mu-hydroxo Ni-Fe bridging ligand at the active site. On the other hand, a new, improved refinement procedure of the X-ray diffraction data obtained for putative unready Ni-A/Ni-SU states resulted in a more elongated electron density for the bridging ligand, suggesting that it is a diatomic species. The slow activation of the Ni-A state, compared with the rapid activation of the Ni-B state, is therefore proposed to result from the different chemical nature of the ligands in the two oxidized species. Our results along with very recent electrochemical studies suggest that the diatomic ligand could be hydro-peroxide.
Schreiber, Roy E; Cohen, Hagai; Leitus, Gregory; Wolf, Sharon G; Zhou, Ang; Que, Lawrence; Neumann, Ronny
2015-07-15
Manganese(IV,V)-hydroxo and oxo complexes are often implicated in both catalytic oxygenation and water oxidation reactions. Much of the research in this area is designed to structurally and/or functionally mimic enzymes. On the other hand, the tendency of such mimics to decompose under strong oxidizing conditions makes the use of molecular inorganic oxide clusters an enticing alternative for practical applications. In this context it is important to understand the reactivity of conceivable reactive intermediates in such an oxide-based chemical environment. Herein, a polyfluoroxometalate (PFOM) monosubstituted with manganese, [NaH2(Mn-L)W17F6O55](q-), has allowed the isolation of a series of compounds, Mn(II, III, IV and V), within the PFOM framework. Magnetic susceptibility measurements show that all the compounds are high spin. XPS and XANES measurements confirmed the assigned oxidation states. EXAFS measurements indicate that Mn(II)PFOM and Mn(III)PFOM have terminal aqua ligands and Mn(V)PFOM has a terminal hydroxo ligand. The data are more ambiguous for Mn(IV)PFOM where both terminal aqua and hydroxo ligands can be rationalized, but the reactivity observed more likely supports a formulation of Mn(IV)PFOM as having a terminal hydroxo ligand. Reactivity studies in water showed unexpectedly that both Mn(IV)-OH-PFOM and Mn(V)-OH-PFOM are very poor oxygen-atom donors; however, both are highly reactive in electron transfer oxidations such as the oxidation of 3-mercaptopropionic acid to the corresponding disulfide. The Mn(IV)-OH-PFOM compound reacted in water to form O2, while Mn(V)-OH-PFOM was surprisingly indefinitely stable. It was observed that addition of alkali cations (K(+), Rb(+), and Cs(+)) led to the aggregation of Mn(IV)-OH-PFOM as analyzed by electron microscopy and DOSY NMR, while addition of Li(+) and Na(+) did not lead to aggregates. Aggregation leads to a lowering of the entropic barrier of the reaction without changing the free energy barrier. The observation that O2 formation is fastest in the presence of Cs(+) and ∼fourth order in Mn(IV)-OH-PFOM supports a notion of a tetramolecular Mn(IV)-hydroxo intermediate that is viable for O2 formation in an oxide-based chemical environment. A bimolecular reaction mechanism involving a Mn(IV)-hydroxo based intermediate appears to be slower for O2 formation.
Reversible insertion of carbon dioxide into Pt(II)-hydroxo bonds.
Lohr, Tracy L; Piers, Warren E; Parvez, Masood
2013-10-01
The reactivity of three monomeric diimine Pt(II) hydroxo complexes, (NN)Pt(OH)R (NN = bulky diimine ligand; R = OH, ; R = C6H5, ; R = CH3, ) towards carbon dioxide has been investigated. Insertion into the Pt-OH bonds was found to be facile and reversible at low temperature for all compounds; the reaction with bis-hydroxide gives an isolable κ(2)-carbonato compound , with elimination of water.
Peng, Dungeng; Ogura, Hiroshi; Zhu, Wenfeng; Ma, Li-Hua; Evans, John P.; Ortiz de Montellano, Paul R.; La Mar, Gerd N.
2010-01-01
Mammalian heme oxygenase, HO, possesses catalytically implicated distal ordered water molecules within an extended H-bond network, with one of the ordered water molecules (#1) providing a bridge between the iron-coordinated ligand and the catalytically critical Asp140, that, in turn, serves as an acceptor for the Tyr58 OH H-bond. The degree of H-bonding by the ligated water molecule and the coupling of this water molecule to the H-bond network are of current interest and are herein investigated by 1H NMR. 2D NMR allowed sufficient assignments to provide both the H-bond strength and hyperfine shifts, the latter of which were used to quantify the magnetic anisotropy in both the ferric high-spin aquo and low-spin hydroxo complexes. The anisotropy in the aquo complex indicates that the H-bond donation to water #1 is marginally stronger than in a bacterial HO, while the anisotropy for the hydroxo complex reveals a conventional (dxz, dyz)1 ground state indicative of only moderate to weak H-bond acceptance by the ligated hydroxide. Mapping out the changes of the H-bond strengths in the network during the ligated water → hydroxide conversion by correcting for the effects of magnetic anisotropy, reveals a very substantial change in H-bond strength for Tyr58 OH, and lesser effects on nearby H-bonds. The effect of pH on the H-bonding network in human HO is much larger and transmitted much further from the iron than in a pathogenic bacterial HO. The implications for the HO mechanism of the H-bond of Tyr58 to Asp140 are discussed. PMID:19842713
DOE Office of Scientific and Technical Information (OSTI.GOV)
Platero-Prats, Ana E.; League, Aaron B.; Bernales, Varinia
Metal-organic frameworks (MOFs), with their well-ordered pore networks and tunable surface chemistries, offer a versatile platform for preparing well-defined nanostructures wherein functionality such as catalysis can be incorporated. Notably, atomic layer deposition (ALD) in MOFs has recently emerged as a versatile approach to functionalize MOF surfaces with a wide variety of catalytic metal-oxo species. Understanding the structure of newly deposited species and how they are tethered within the MOF is critical to understanding how these components couple to govern the active material properties. By combining local and long-range structure probes, including X-ray absorption spectroscopy, pair distribution function analysis and differencemore » envelope density analysis, with electron microscopy imag-ing and computational modeling, we resolve the precise atomic structure of metal-oxo species deposited in the MOF NU-1000 through ALD. These analyses demonstrate that deposition of NiO xH y clusters occurs selectively within the smallest pores of NU-1000, between the zirconia nodes, serving to connect these nodes along the c-direction to yield hetero-bimetallic metal-oxo nanowires. Finally, this bridging motif perturbs the NU-1000 framework structure, drawing the zirconia nodes closer together, and also underlies the sintering-resistance of these clusters during the hydrogenation of light olefins.« less
Platero-Prats, Ana E; League, Aaron B; Bernales, Varinia; Ye, Jingyun; Gallington, Leighanne C; Vjunov, Aleksei; Schweitzer, Neil M; Li, Zhanyong; Zheng, Jian; Mehdi, B Layla; Stevens, Andrew J; Dohnalkova, Alice; Balasubramanian, Mahalingam; Farha, Omar K; Hupp, Joseph T; Browning, Nigel D; Fulton, John L; Camaioni, Donald M; Lercher, Johannes A; Truhlar, Donald G; Gagliardi, Laura; Cramer, Christopher J; Chapman, Karena W
2017-08-02
Metal-organic frameworks (MOFs), with their well-ordered pore networks and tunable surface chemistries, offer a versatile platform for preparing well-defined nanostructures wherein functionality such as catalysis can be incorporated. Notably, atomic layer deposition (ALD) in MOFs has recently emerged as a versatile approach to functionalize MOF surfaces with a wide variety of catalytic metal-oxo species. Understanding the structure of newly deposited species and how they are tethered within the MOF is critical to understanding how these components couple to govern the active material properties. By combining local and long-range structure probes, including X-ray absorption spectroscopy, pair distribution function analysis, and difference envelope density analysis, with electron microscopy imaging and computational modeling, we resolve the precise atomic structure of metal-oxo species deposited in the MOF NU-1000 through ALD. These analyses demonstrate that deposition of NiO x H y clusters occurs selectively within the smallest pores of NU-1000, between the zirconia nodes, serving to connect these nodes along the c-direction to yield heterobimetallic metal-oxo nanowires. This bridging motif perturbs the NU-1000 framework structure, drawing the zirconia nodes closer together, and also underlies the sintering resistance of these clusters during the hydrogenation of light olefins.
Platero-Prats, Ana E.; League, Aaron B.; Bernales, Varinia; ...
2017-07-11
Metal-organic frameworks (MOFs), with their well-ordered pore networks and tunable surface chemistries, offer a versatile platform for preparing well-defined nanostructures wherein functionality such as catalysis can be incorporated. Notably, atomic layer deposition (ALD) in MOFs has recently emerged as a versatile approach to functionalize MOF surfaces with a wide variety of catalytic metal-oxo species. Understanding the structure of newly deposited species and how they are tethered within the MOF is critical to understanding how these components couple to govern the active material properties. By combining local and long-range structure probes, including X-ray absorption spectroscopy, pair distribution function analysis and differencemore » envelope density analysis, with electron microscopy imag-ing and computational modeling, we resolve the precise atomic structure of metal-oxo species deposited in the MOF NU-1000 through ALD. These analyses demonstrate that deposition of NiO xH y clusters occurs selectively within the smallest pores of NU-1000, between the zirconia nodes, serving to connect these nodes along the c-direction to yield hetero-bimetallic metal-oxo nanowires. Finally, this bridging motif perturbs the NU-1000 framework structure, drawing the zirconia nodes closer together, and also underlies the sintering-resistance of these clusters during the hydrogenation of light olefins.« less
Georgieva, Ivelina; Danchova, Nina; Gutzov, Stoyan; Trendafilova, Natasha
2012-06-01
Theoretical and spectroscopic studies of a series of monomeric and dimeric complexes formed through the modification of a zirconium butoxide precursor with acetylacetone and subsequent hydrolysis and/or condensation have been performed by applying DFT/B3LYP/6-31++G(d) and highly accurate RI-ADC(2) methods as well as IR and UV-Vis transmittance and diffuse reflectance spectroscopies. Based on DFT model calculations and simulated and experimental UV-Vis and IR spectra of all the studied structures, the most probable building units of the Zr(IV)-AcAc gel were predicted: the dimeric double hydroxo-bridged complex Zr(2)(AcAc)(2)(OH)(4)(OH)(2br) 9 and the monooxo-bridged complex Zr(2)(AcAc)(2)(OH)(4)O(br)·2H(2)O 12. In both structures, the two AcAc ligands are coordinated to one Zr atom. It was shown that building units 9 and 12 determine the photophysical and vibrational properties of the gel material. The observed UV-Vis and IR spectra of Zr(IV)-AcAc gel were interpreted and a relation between the spectroscopic and structural data was derived. The observed UV-Vis bands at 315 nm and 298/288 nm were assigned to partial ligand-metal transitions and to intra-/inter-AcAc ligand transitions, respectively.
Coggins, Michael K.; Toledo, Santiago; Kovacs, Julie A.
2013-01-01
Dioxygen addition to coordinatively unsaturated [Fe(II)(OMe2N4(6-Me-DPEN))](PF6) (1) is shown to afford a complex containing a dihydroxo-bridged Fe(III)2(μ-OH)2 diamond core, [FeIII(OMe2N4(6-Me-DPEN))]2(μ-OH)2(PF6)2•(CH3CH2CN)2 (2). The diamond core of 2 resembles the oxidized methane monooxygenase (MMOox) resting state, as well as the active site product formed following H-atom abstraction from Tyr-OH by ribonucleotide reductase (RNR). The Fe-OH bond lengths of 2 are comparable with those of the MMOHox suggesting that MMOHox contains a Fe(III)2(μ-OH)2 as opposed to Fe(III)2(μ-OH)(μ-OH2) diamond core as had been suggested. Isotopic labeling experiments with 18O2 and CD3CN indicate that the oxygen and proton of the μ-OH bridges of 2 are derived from dioxygen and acetonitrile. Deuterium incorporation (from CD3CN) suggests that an unobserved intermediate capable of abstracting a H-atom from CH3CN forms en route to 2. Given the high C–H bond dissociation energy (BDE= 97 kcal/mol) of acetonitrile, this indicates that this intermediate is a potent oxidant, possibly a high-valent iron oxo. Consistent with this, iodosylbenzene (PhIO) also reacts with 1 in CD3CN to afford the deuterated Fe(III)2(μ-OD)2 derivative of 2. Intermediates are not spectroscopically observed in either reaction (O2 and PhIO) even at low-temperatures (−80 °C), indicating that this intermediate has a very short life-time, likely due to its highly reactive nature. Hydroxo-bridged 2 was found to stoichiometrically abstract hydrogen atoms from 9,10-dihydroanthracene (C-H BDE= 76 kcal/mol) at ambient temperatures. PMID:24229319
Groysman, Stanislav; Majumdar, Amit; Zheng, Shao-Liang; Holm, R H
2010-02-01
Reactions directed at the synthesis of structural analogues of the active site of molybdenum-containing carbon monoxide dehydrogenase have been investigated utilizing [WO(2)S(bdt)](2-) (1) and [WOS(2)(bdt)](2-) (2) and sterically hindered [Cu(R)L] or [Cu(SSiR'(3))(2)](-) as reactants. All successful reactions of 2 afford the binuclear W(VI)/Cu(I) products [WO(bdt)(mu(2)-S)(2)Cu(L)](2-/-) with L = carbene (3), Ar*S (4), Ar* (7), SSiR(3) (R = Ph (5), Pr(i) (6)). Similarly, [W(bdt)(OSiPh(3))S(2)](-) leads to [W(bdt)(OSiPh(3))(mu(2)-S)(2)Cu(SAr*)](-) (8). These complexes, with apical oxo and basal dithiolato and sulfido coordination (excluding 8), terminal thiolate ligation at Cu(I) (4-6, 8), and W-(mu(2)-S)-Cu bridging, bear a structural resemblance to the enzyme site. Differences include two bridges instead of one and the absence of basal oxo/hydroxo ligation. Complex 8 differs from the others by utilizing apical and basal sulfido ligands in bridge formation. Related reaction systems based on 1 gave 4 in small yield or product mixtures in which the desired monobridged complex [WO(2)(bdt)(mu(2)-S)Cu(R)](2-) was not detected. Mass spectrometric analysis of the reaction system with L = carbene suggests that any monobridged species forms may converted to the dibridged form by disproportionation. In these experiments, the use of W(VI) preserves the structural integrity of Mo(VI), whose analogues of 1 and 2 have not been isolated. (Ar* = 2,6-bis(2,4,6-triisopropylphenyl)phenyl, bdt = benzene-1,2-dithiolate(2-)).
Energetics of proton release on the first oxidation step in the water-oxidizing enzyme.
Saito, Keisuke; Rutherford, A William; Ishikita, Hiroshi
2015-10-07
In photosystem II (PSII), the Mn4CaO5 cluster catalyses the water splitting reaction. The crystal structure of PSII shows the presence of a hydrogen-bonded water molecule directly linked to O4. Here we show the detailed properties of the H-bonds associated with the Mn4CaO5 cluster using a quantum mechanical/molecular mechanical approach. When O4 is taken as a μ-hydroxo bridge acting as a hydrogen-bond donor to water539 (W539), the S0 redox state best describes the unusually short O4-OW539 distance (2.5 Å) seen in the crystal structure. We find that in S1, O4 easily releases the proton into a chain of eight strongly hydrogen-bonded water molecules. The corresponding hydrogen-bond network is absent for O5 in S1. The present study suggests that the O4-water chain could facilitate the initial deprotonation event in PSII. This unexpected insight is likely to be of real relevance to mechanistic models for water oxidation.
Park, Young Jun; Ziller, Joseph W.; Borovik, A. S.
2011-01-01
Rate enhancements for the reduction of dioxygen by a MnII complex were observed in the presence of redox inactive Group 2 metal ions. The rate changes correlated with an increase in the Lewis acidity of the Group 2 metal ions. These studies led to the isolation of heterobimetallic complexes that contain MnIII-(μ-OH)-MII cores (MII = CaII, BaII), in which the hydroxo oxygen atom is derived from O2. This type of core structure has relevance to the oxygen evolving complexes within photosystem II. PMID:21595481
Spectral reflectance properties of minerals exposed to simulated Mars surface conditions
NASA Astrophysics Data System (ADS)
Cloutis, E. A.; Craig, M. A.; Kruzelecky, R. V.; Jamroz, W. R.; Scott, A.; Hawthorne, F. C.; Mertzman, S. A.
2008-05-01
A number of mineral species were exposed to martian surface conditions of atmospheric pressure and composition, temperature, and UV light regime, and their evolution was monitored using reflectance spectroscopy. The stabilities for different groups varied widely. Phyllosilicate spectra all showed measurable losses of interlayer H 2O, with some structural groups showing more rapid H 2O loss than others. Loss of OH from the phyllosilicates is not always accompanied by a change in metal-OH overtone absorption bands. OH-bearing sulfates, such as jarosite and alunite, show no measurable change in spectral properties, suggesting that they should be spectrally detectable on Mars on the basis of diagnostic absorption bands in the 0.4-2.5 μm region. Fe 3+- and H 2O-bearing sulfates all showed changes in the appearance and/or reduction in depths of hydroxo-bridged Fe 3+ absorption bands, particularly at 0.43 μm. The spectral changes were often accompanied by visible color changes, suggesting that subsurface sulfates exposed to the martian surface environment may undergo measurable changes in reflectance spectra and color over short periods of time (days to weeks). Organic-bearing geological materials showed no measurable change in C sbnd H related absorption bands, while carbonates and hydroxides also showed no systematic changes in spectral properties. The addition of ultraviolet irradiation did not seem to affect mineral stability or rate of spectral change, with one exception (hexahydrite). In some cases, spectral changes could be related to the formation of specific new phases. The data also suggest that hydrated minerals detected on Mars to date retain their diagnostic spectral properties that allow their unique identification.
Volpe, Angela; Pagano, Michele; Pastore, Carlo; Cuocci, Corrado; Milella, Antonella
2016-11-09
Titanates may be selectively used as inorganic adsorbents for heavy metal ions owing to their stability and fast adsorption kinetics. Nevertheless, the synthesis of such materials usually requires extreme reaction conditions. In this work, a new titanium-based material was rapidly synthesized under mild laboratory conditions. The obtained amorphous hydroxo titanate was tested for heavy metal sorption through kinetic and equilibrium batch tests, which indicated that the new material had high adsorption rates and adsorption capacities towards Cu(2+), Ni(2+) and Pb(2) ions. Adsorption kinetics were pseudo-second order, and equilibrium data fitted the Langmuir isotherm model. The calculated maximum adsorption capacities of Cu(2+), Ni(2+) and Pb(2+) in deionized water were around 1 mmol g(-1), and they decreased for Cu(2+) and Ni(2+) in the presence of Na(+), Ca(2+) and Mg(2+) ions, whereas the alkali metal ions did not influence Pb(2+) uptake. The efficiency of adsorption and recovery of lead ions were evaluated through column dynamic tests, by feeding the column with groundwater and tap water spiked with Pb(2+). The high performance of the hydroxo titanate over several cycles of retention and elution suggested that the product is potentially useful for the solid phase extraction of lead at trace levels in natural water samples, with potential use in metal pre-concentration for analytical applications.
NASA Astrophysics Data System (ADS)
Ozer, Demet; Köse, Dursun A.; Sahin, Onur; Oztas, Nursen A.
2018-04-01
Three boric acid mediated metal organic frameworks were synthesized by solution method with using succinic acid, fumaric acid and acetylene dicarboxylic acid as a ligand source and sodium as a metal source. The complexes were characterized by FT-IR, powder XRD, elemental analyses and single crystal measurements. The complexes with the formula, C4H18B2Na2O14, C4H16B2Na2O14 and C4H14B2Na2O14 were successfully obtained. BET surface area of complexes were calculated and found as 13.474 m2/g for catena-(tetrakis(μ2-hydroxo)-(μ2-trihydrogen borate)-(μ2-succinato)-di-sodium boric acid solvate), 1.692 m2/g for catena-(tetrakis(μ2-hydroxo)-(μ2-trihydrogen borate)-(μ2-fumarato)-di-sodium boric acid solvate) and 5.600 m2/g for catena-(tetrakis(μ2-hydroxo)-(μ2-trihydrogen borate)-(μ2-acetylenedicarboxylato)-di-sodium boric acid solvate). Hydrogen storage capacities of the complexes were also studied at 77 K 1 bar pressure and found as 0.108%, 0.033%, 0.021% by mass. When different ligands were used, the pore volume, pore width and surface area of the obtained complexes were changed. As a consequence, hydrogen storage capacities also changed.
Assembly and Properties of Heterobimetallic CoII/III/CaII Complexes with Aquo and Hydroxo Ligands
Lacy, David C.; Park, Young Jun; Ziller, Joseph W.; Yano, Junko; Borovik, A. S.
2012-01-01
The use of water as a reagent in redox-driven reactions is advantageous because it is abundant and environmentally compatible. The conversion of water to dioxygen in photosynthesis illustrates one example, in which a redox-inactive CaII ion and four manganese ions are required for function. In this report we describe the stepwise formation of two new heterobimetallic complexes containing CoII/III and CaII ions, and either hydroxo or aquo ligands. The preparation of a 4-coordinate CoII synthon was achieved with the tripodal ligand, N,N′,N″-[2,2′,2″-nitrilotris(ethane-2,1-diyl)]tris(2,4,6-trimethylbenzenesulfonamido, [MST]3−. Water binds to [CoIIMST]− to form the 5-coordinate [CoIIMST(OH2)]− complex that was used to prepare the CoII/CaII complex [CoIIMST(μ-OH2)CaII⊂15-crown-5(OH2)]+ ([CoII(μ-OH2)CaIIOH2]+). [CoII(μ-OH2)CaOH2]+ contained two aquo ligands, one bonded to the CaII ion and one bridging between the two metal ions and thus represents an unusual example of a heterobimetallic complex containing 2 aquo ligands spanning different metal ions. Both aquo ligands formed intramolecular hydrogen bonds with the [MST]3− ligand. [CoIIMST(OH2)]− was oxidized to form [CoIIIMST(OH2)] that was further converted to [CoIIIMST(μ-OH)CaII⊂15-crown-5]+ ([CoIII(μ-OH)CaII]+) in the presence of base and CaIIOTf2/15-crown-5. [CoIII(μ-OH)CaII]+ was also synthesized from the oxidation of [CoIIMST]− with PhIO in the presence of CaIIOTf2/15-crown-5. Allowing [CoIII(μ-OH)CaII]+ to react with diphenylhydrazine afforded [CoII(μ-OH2)CaIIOH2]+ and azobenzene. Additionally, the characterization of [CoIII(μ-OH)CaII]+ provides another formulation for the previously reported CoIV–oxo complex, [(TMG3tren)CoIV(μ-O)ScIII(OTf)3]2+ to one that instead could contain a CoIII–OH unit. PMID:22998407
NASA Astrophysics Data System (ADS)
Zhang, Weidong; Pan, Feng; Li, Jinjun; Wang, Zhen; Ding, Wei; Qin, Yi; Wu, Feng
2018-06-01
Silica-supported highly dispersed cobalt oxides prepared by adsorption are likely to be poorly reducible Co-phyllosilicates or CoO species. Here we report the synthesis of silica-supported monodispersed spinel nano-Co3O4 catalysts by inner-sphere complexation using CoIII ammine hydroxo complexes as precursors. The precursors were facilely prepared by stirring ammoniacal CoII solutions exposed to air. The cobalt loadings (up to 188 mg/g) and particle sizes (3-10 nm) were tailored by successive complexation-calcination cycles. Such catalysts showed significantly superior reducibility and catalytic activity in complete propane oxidation in comparison to supported Co-phyllosilicates and CoO. A further development of this synthesis process may provide a variety of cobalt-based catalysts for important catalytic applications.
Zhou, Ying-Hua; Chen, Li-Qing; Tao, Jun; Shen, Jun-Li; Gong, Dao-Yu; Yun, Rui-Rui; Cheng, Yong
2016-10-01
To construct the model of metallohydrolase, two inclusion complexes [MLCl 2 (β-CD)] (1, M=Zn(II); 2, M=Cu(II); L=N,N'-bis(2-pyridylmethyl)amantadine; β-CD=β-cyclodextrin) were synthesized by mixing β-CDs with the pre-synthesized complexes G1, [ZnLCl 2 ] and G2, [CuLCl 2 ]. Structures of G1, G2, 1 and 2 were characterized by X-ray crystallography, respectively. In solution, two chloride anions of G1 and G2 underwent ligand exchange with solvent molecules according to ESI-MS analysis. The chemical equilibrium constants were determined by potentiometric pH titration. The kinetics of bis(4-nitrophenyl) phosphate (BNPP) hydrolysis catalyzed by G1, G2, 1 and 2 were examined at pHs ranging from 7.50 to 10.50 at 308±0.1K. The pH profile of rate constant of BNPP hydrolysis catalyzed by 1 exhibited an exponential increase with the second-order rate constant of 2.68×10 -3 M -1 s -1 assigned to the di-hydroxo species, which was approximately an order of magnitude higher than those of reported mono-Zn(II)-hydroxo species. The high reactivity was presumably hydroxyl-rich microenvironment provided by β-CDs, which might effect in stabilizing either the labile zinc-hydroxo species or the catalytic transition state. Copyright © 2016 Elsevier Inc. All rights reserved.
DFT study of uranyl peroxo complexes with H2O, F-, OH-, CO3(2-), and NO3(-).
Odoh, Samuel O; Schreckenbach, Georg
2013-05-06
The structural and electronic properties of monoperoxo and diperoxo uranyl complexes with aquo, fluoride, hydroxo, carbonate, and nitrate ligands have been studied using scalar relativistic density functional theory (DFT). Only the complexes in which the peroxo ligands are coordinated to the uranyl moiety in a bidentate mode were considered. The calculated binding energies confirm that the affinity of the peroxo ligand for the uranyl group far exceeds that of the F(-), OH(-), CO3(2-), NO3(-), and H2O ligands. The formation of the monoperoxo complexes from UO2(H2O)5(2+) and HO2(-) were found to be exothermic in solution. In contrast, the formation of the monouranyl-diperoxo, UO2(O2)2X2(4-) or UO2(O2)2X(4-/3-) (where X is any of F(-), OH(-), CO3(2-), or NO3(-)), complexes were all found to be endothermic in aqueous solution. This suggests that the monoperoxo species are the terminal monouranyl peroxo complexes in solution, in agreement with recent experimental work. Overall, we find that the properties of the uranyl-peroxo complexes conform to well-known trends: the coordination of the peroxo ligand weakens the U-O(yl) bonds, stabilizes the σ(d) orbitals and causes a mixing between the uranyl π- and peroxo σ- and π-orbitals. The weakening of the U-O(yl) bonds upon peroxide coordination results in uranyl stretching vibrational frequencies that are much lower than those obtained after the coordination of carbonato or hydroxo ligands.
Chagas, Marcelo A; Pereira, Eufrásia S; Godinho, Marina P B; Da Silva, Júlio Cosme S; Rocha, Willian R
2018-05-21
In the present work, density functional theory (DFT) calculations at the B3LYP/6-31+G(d) and including dispersion effects were used to investigate the hydrolysis of paraoxon, using a cluster model of the active site of Cd 2+ /Cd 2+ -phosphotriesterase (PTE) from Pseudomonas diminuta. The mechanism proposed here consist of (i) Exchange of the coordinated water molecule and coordination of the substrate to the more solvent exposed Cd β center in monodentate fashion, (ii) protonation of the μ-hydroxo bridge by the uncoordinated water molecule and in situ formation of the nucleophile, (iii) formation of a pentacoordinate intermediate with significant bond breaking to the leaving group and bond formation to the nucleophile, and (iv) protonation of the Asp301 residue and restoration of the active site through the coordination of another water molecule of the medium. The water molecules initially coordinated to the active site play a crucial role in stabilizing the transition states and the pentacoordinate intermediate. The reaction takes place in a two-step (A N + D N ) mechanism, with energy barriers of 12.9 and 1.9 kcal/mol for the first and second steps, respectively, computed at the B3LYP-D3/6-311++G(2d,2p) level of theory, in excellent agreement with the experimental findings. Dispersion effects alone contribute to diminish the energy barriers as much as 26%. The base mechanism for the Cd 2+ /Cd 2+ -PTE proposed here, in conjunction with the agreement found with the experimental energetic value for the energy barrier, makes it a consistent and kinetically viable mechanistic proposal for the hydrolysis of phosphate triesters promoted by the Cd 2+ substituted PTE enzyme.
Sulfide mineralization: Its role in chemical weathering of Mars
NASA Technical Reports Server (NTRS)
Burns, Roger G.
1988-01-01
Pyrrhotite-pentlandite assemblages in mafic and ultramafic igneous rocks may have contributed significantly to the chemical weathering reactions that produced degradation products in the Martian regolith. By analogy with terrestrial processes, a model is proposed whereby supergene alteration of these primary Fe-Ni sulfides on Mars has generated secondary sulfides (e.g., pyrite) below the water table and produced acidic groundwater containing high concentrations of dissolved Fe, Ni and sulfate ions. The low pH solutions also initiated weathering reactions of igneous feldspars and ferromagnesian silicates to form clay silicate and ferric oxyhydroxide phases. Near-surface oxidation and hydrolysis of ferric sulfato- and hydroxo-complex ions and sols formed gossans above the water table consisting of poorly crystalline hydrated ferric sulfates (e.g., jarosite), oxides (ferrihydrite, goethite) and silica (opal). Underlying groundwater, now permafrost, contains hydroxo sulfato complexes of Fe, Al, Mg, Ni, etc., which may be stabilized in frozen acidic solutions beneath the surface of Mars. Sublimation of permafrost may replenish colloidal ferric oxides, sulfates and phyllosilicates during dust storms on Mars.
Weathering of sulfides on Mars
NASA Technical Reports Server (NTRS)
Burns, Roger G.; Fisher, Duncan S.
1987-01-01
Pyrrhotite-pentlandite assemblages in mafic and ultramafic igneous rocks may have contributed significantly to the chemical weathering reactions that produce degradation products in the Martian regolith. By analogy and terrestrial processes, a model is proposed whereby supergene alteration of these primary Fe-Ni sulfides on Mars has generated secondary sulfides (e.g., pyrite) below the water table and produced acidic groundwater containing high concentrations of dissolved Fe, Ni, and sulfate ions. The low pH solutions also initiated weathering reactions of igneous feldspars and ferromagnesian silicates to form clay silicate and ferric oxyhydroxide phases. Near-surface oxidation and hydrolysis of ferric sulfato-and hydroxo-complex ions and sols formed gossan above the water table consisting of poorly crystalline hydrated ferric sulfates (e.g., jarosite), oxides (ferrihydrite, goethite), and silica (opal). Underlying groundwater, now permafrost contains hydroxo sulfato complexes of Fe, Al, Mg, Ni, which may be stabilized in frozen acidic solutions beneath the surface of Mars. Sublimation of permafrost may replenish colloidal ferric oxides, sulfates, and phyllosilicates during dust storms on Mars.
Yi, Chae S.; Zeczycki, Tonya N.; Guzei, Ilia A.
2008-01-01
The tetrametallic ruthenium-oxo-hydroxo-hydride complex {[(PCy3)(CO)RuH]4(μ4-O)(μ3-OH)(μ2-OH)} (1) was synthesized in two steps from the monomeric complex (PCy3)(CO)RuHCl (2). The tetrameric complex 1 was found to be a highly effective catalyst for the transfer dehydrogenation of alcohols. Complex 1 showed a different catalytic activity pattern towards primary and secondary benzyl alcohols, as indicated by the Hammett correlation for the oxidation reaction of p-X-C6H4CH2OH (ρ = −0.45) and p-X-C6H4CH(OH)CH3 (ρ = +0.22) (X = OMe, CH3, H, Cl, CF3). Both a sigmoidal curve from the plot of initial rate vs [PhCH(OH)CH3] (K0.5 = 0.34 M; Hill coefficient, n = 4.2±0.1) and the phosphine inhibition kinetics revealed the highly cooperative nature of the complex for the oxidation of secondary alcohols. PMID:18726005
Santoro, Giuseppe; Zlateva, Theodora; Ruggi, Albert; Quaroni, Luca; Zobi, Fabio
2015-04-21
Constitutional isomers of cyanocobalamin adducts based on a fluorescent rhenium tris-carbonyl diimine complex were prepared, characterized and tested against PC-3 cancer cells. The adducts differ only in the relative binding position of the organometallic species which is either bound at the cyano or the 5'-hydroxo group of vitamin B12. When tested for their cytotoxic potency, the species showed IC50 values in the low μM rage. Upon conjugation to the vitamin an energy transfer process causes an extremely low quantum yield of fluorescence emission, making the conjugates unsuitable for fluorescence imaging. However, by exploiting the vibrational signature of the fac-[Re(CO)3](+) core, their cellular distribution was evaluated via FTIR spectromicroscopy.
Guesmi, Hazar; Berthomieu, Dorothee; Bromley, Bryan; Coq, Bernard; Kiwi-Minsker, Lioubov
2010-03-28
The characterization of Fe/ZSM5 zeolite materials, the nature of Fe-sites active in N(2)O direct decomposition, as well as the rate limiting step are still a matter of debate. The mechanism of N(2)O decomposition on the binuclear oxo-hydroxo bridged extraframework iron core site [Fe(II)(mu-O)(mu-OH)Fe(II)](+) inside the ZSM-5 zeolite has been studied by combining theoretical and experimental approaches. The overall calculated path of N(2)O decomposition involves the oxidation of binuclear Fe(II) core sites by N(2)O (atomic alpha-oxygen formation) and the recombination of two surface alpha-oxygen atoms leading to the formation of molecular oxygen. Rate parameters computed using standard statistical mechanics and transition state theory reveal that elementary catalytic steps involved into N(2)O decomposition are strongly dependent on the temperature. This theoretical result was compared to the experimentally observed steady state kinetics of the N(2)O decomposition and temperature-programmed desorption (TPD) experiments. A switch of the reaction order with respect to N(2)O pressure from zero to one occurs at around 800 K suggesting a change of the rate determining step from the alpha-oxygen recombination to alpha-oxygen formation. The TPD results on the molecular oxygen desorption confirmed the mechanism proposed.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Volkringer, Christophe; Loiseau, Thierry
2006-05-25
A new indium trimesate In{sub 12}O(OH){sub 12}({l_brace}OH{r_brace}{sub 4},{l_brace}H{sub 2}O{r_brace}{sub 5})[btc]{sub 6}.{approx}31H{sub 2}O, called MIL-96 (btc = 1,3,5-benzenetricarboxylate or trimesate species) was hydrothermally synthesized under mild condition (210 deg. C, 5 h) in the presence of trimethyl 1,3,5-benzenetricarboxylate in water and characterized by single-crystal X-ray diffraction technique. The MIL-96 (In) structure exhibits a three-dimensional metal-organic framework containing isolated trinuclear {mu} {sub 3}-oxo-bridged indium clusters and infinite chains of InO{sub 4}(OH){sub 2} and InO{sub 2}(OH){sub 3}(H{sub 2}O) octahedra generating a hexagonal network based on 18-membered ring. The two types of indium entities are connected to each other through the trimesate species whichmore » induce corrugated chains of indium octahedra, linked via {mu} {sub 2}-hydroxo bonds with the specific -cis-cis-trans- sequence. The 3D framework of MIL-96 reveals three kind of cavities (two of them have estimated {approx} 400 A{sup 3} volumes), in which are encapsulated free water molecules. The latter species are removed upon heating at 150 deg. C.« less
Kulik, Leonid V; Epel, Boris; Lubitz, Wolfgang; Messinger, Johannes
2007-11-07
The heart of the oxygen-evolving complex (OEC) of photosystem II is a Mn4OxCa cluster that cycles through five different oxidation states (S0 to S4) during the light-driven water-splitting reaction cycle. In this study we interpret the recently obtained 55Mn hyperfine coupling constants of the S0 and S2 states of the OEC [Kulik et al. J. Am. Chem. Soc. 2005, 127, 2392-2393] on the basis of Y-shaped spin-coupling schemes with up to four nonzero exchange coupling constants, J. This analysis rules out the presence of one or more Mn(II) ions in S0 in methanol (3%) containing samples and thereby establishes that the oxidation states of the manganese ions in S0 and S2 are, at 4 K, Mn4(III, III, III, IV) and Mn4(III, IV, IV, IV), respectively. By applying a "structure filter" that is based on the recently reported single-crystal EXAFS data on the Mn4OxCa cluster [Yano et al. Science 2006, 314, 821-825] we (i) show that this new structural model is fully consistent with EPR and 55Mn-ENDOR data, (ii) assign the Mn oxidation states to the individual Mn ions, and (iii) propose that the known shortening of one 2.85 A Mn-Mn distance in S0 to 2.75 A in S1 [Robblee et al. J. Am. Chem. Soc. 2002, 124, 7459-7471] corresponds to a deprotonation of a mu-hydroxo bridge between MnA and MnB, i.e., between the outer Mn and its neighboring Mn of the mu3-oxo bridged moiety of the cluster. We summarize our results in a molecular model for the S0 --> S1 and S1 --> S2 transitions.
Zhao, Hong-Bo; Zheng, Ming; Schreckenbach, Georg; Pan, Qing-Jiang
2017-03-06
To understand interfacial behavior of actinides adsorbed onto mineral surfaces and unravel their structure-property relationship, the structures, electronic properties, and energetics of various ligated uranyl species adsorbed onto TiO 2 surface nanoparticle clusters (SNCs) were examined using relativistic density functional theory. Rutile (110) and anatase (101) titania surfaces, experimentally known to be stable, were fully optimized. For the former, models studied include clean and water-free Ti 27 O 64 H 20 (dry), partially hydrated (Ti 27 O 64 H 20 )(H 2 O) 8 (sol) and proton-saturated [(Ti 27 O 64 H 20 )(H 2 O) 8 (H) 2 ] 2+ (sat), while defect-free and defected anatase SNCs involving more than 38 TiO 2 units were considered. The aquouranyl sorption onto rutile SNCs is energetically preferred, with interaction energies of -8.54, -10.36, and -2.39 eV, respectively. Energy decomposition demonstrates that the sorption is dominated by orbital attractive interactions and modified by steric effects. Greater hydrogen-bonding involvement leads to increased orbital interactions (i.e., more negative energy) from dry to sol/sat complexes, while much larger steric interaction in the sat complex significantly reduces the sorption interaction (i.e., more positive energy). For dry SNC, adsorbates were varied from aquo to aquo-carbonato, to carbonato, to hydroxo uranyl species. Longer U-O surf /U-Ti distances and more positive sorption energies were calculated upon introducing carbonato and hydroxo ligands, indicative of weaker uranyl sorption onto the substrate. This is consistent with experimental observations that the uranyl sorption rate decreases upon raising solution pH value or adding carbon dioxide. Anatase SNCs adsorbing aquouranyl are even more exothermic, because more bonds are formed than in the case of rutile. Moreover, the anatase sorption can be tuned by surface defects as well as its Ti and O stoichiometry. All the aquouranyl-SNC complexes show similar character of molecular orbitals and energetic order although differing in highest occupied molecular orbital (HOMO)-lowest unoccupied molecular orbital (LUMO) gaps and orbital energy levels, but changes can be accomplished by adding carbonato and hydroxo ligands.
The effects of prone bridge exercise on trunk muscle thickness in chronic low back pain patients.
Kong, Yong-Soo; Lee, Woo-Jin; Park, Seol; Jang, Gwon-Uk
2015-07-01
[Purpose] This study aimed to investigate the effects of prone bridge exercise on trunk muscle thickness. [Subjects and Methods] Thirty-seven chronic low back pain patients participated in this study. Each participant was randomly assigned to one of three exercise groups, namely, a prone bridge exercise group, supine bridge exercise on a Swiss ball group, and supine bridge exercise group. The thicknesses of the transverse abdominis (TrA), internal oblique (IO), and external oblique (EO) were measured using ultrasound. [Results] After eight weeks of training, the three groups showed significant increases in the thicknesses of the TrA, IO, and EO. Among the groups, TrA and IO showed significantly different muscle thicknesses. [Conclusion] The prone bridge exercise significantly affected the thicknesses of the TrA, IO, and EO unlike the supine bridge exercises. Based on the results of this study, the prone bridge exercise is a more effective method to improve trunk stability than conventional supine bridge exercises.
The effect of modified bridge exercise on balance ability of stroke patients.
Song, Gui-Bin; Heo, Ju-Young
2015-12-01
[Purpose] The purpose of this study was to verify the effects of a modified bridging exercise on stroke patients with improvement in weight bearing on the affected side in standing and static balancing ability. [Subjects] Thirty patients who had a stroke were randomly allocated into a supine bridge exercise group (SBG, n=10), a supine bridge exercise on a TOGU balance pad group (SBTG, n=10), and a unilateral bridge exercise group (UBG, n=10). [Methods] The SBG patients underwent supine bridge exercise, the SBTG patients underwent supine bridge exercise with a TOGU balance pad, and the UBG patients underwent unilateral bridge exercise. All groups received 20 minutes of training per day, five times per week, for four weeks. [Results] All groups showed significant changes in weight bearing in a standing position after the intervention. The SBTG and UBG groups showed significant changes in balance ability. [Conclusion] According to the results of this study, bridge exercise was effective in improving weight bearing in a standing position and improving balance on stroke patients. The bridge exercise with a TOGU balance pad and the unilateral bridge exercise were especially more effective in anterior, posterior length in limit of stability following on standing.
NASA Astrophysics Data System (ADS)
Guo, Lei; Zaera, Francisco
2014-12-01
A simple procedure has been developed for the processing of silicon wafers in order to facilitate the spatially resolved growth of thin solid films on their surfaces. Specifically, a combination of silylation and UV/ozonolysis was tested as a way to control the concentration of the surface hydroxo groups required for subsequent atomic layer deposition (ALD) of metals or oxides. Water contact angle measurements were used to evaluate the hydrophilicity/hydrophobicity of the surface, a proxy for OH surface coverage, and to optimize the UV/ozonolysis treatment. Silylation with hexamethyldisilazane, trichloro(octadecyl)silane, or trimethylchlorosilane was found to be an efficient way to block the hydroxo sites and to passivate the underlying surface, and UV/O3 treatments were shown to effectively remove the silylation layer and to regain the surface reactivity. Both O3 and 185 nm UV radiation were determined necessary for the removal of the silylation layer, and additional 254 nm radiation was found to enhance the process. Attenuated total reflection-infrared absorption spectroscopy was employed to assess the success of the silylation and UV/O3 removal steps, and atomic force microscopy data provided evidence for the retention of the original smoothness of the surface. Selective growth of HfO2 films via TDMAHf + H2O ALD was seen only on the UV/O3 treated surfaces; total inhibition of the deposition was observed on the untreated silylated surfaces (as determined by x-ray photoelectron spectroscopy and ellipsometry). Residual film growth was still detected on the latter if the ALD was carried out at high temperatures (250 °C), because the silylation layer deteriorates under such harsh conditions and forms surface defects that act as nucleation sites for the growth of oxide grains (as identified by electron microscopy and scanning electron microscopy). We believe that the silylation-UV/O3 procedure advanced here could be easily implemented for the patterning of surfaces in many microelectronic applications.
Ternary complex formation of Eu(III) with o-phthalate in aqueous solutions.
Park, K K; Jung, E C; Cho, H-R; Kim, W H
2009-08-15
Ternary hydroxo complex formation of Eu(III) with o-phthalate was investigated by potentiometry and fluorescence spectrophotometry. Curves of the equilibrium pH versus the amount of NaOH added showed that the pH value starting to form a Eu(III) precipitate was decreased due to the formation of a ternary hydroxo complex, EuOHL(s) (L = phthalate). The formation of EuOHL(s) was qualitatively confirmed by the enhancement of the fluorescence intensity of Eu(III) in the precipitate with the light absorbed by phthalate, and was quantitatively confirmed by the measurement of the amounts of Eu(III), OH(-) and phthalate included in the precipitate. The solubility product of EuOHL(s) was determined as pK(sp)(0) = 15.6+/-0.4. Characteristic features in the fluorescence spectra and the solubility product of the Eu(III)-phthalate complex were compared with those of the Eu(III)-PDA (PDA = pyridine-2,6-dicarboxylate) complex. The fluorescence intensity of the EuL(+) complex of L = PDA was about 11 times stronger than that of L = phthalate. The origin of the difference in the fluorescence intensity is discussed based on the intramolecular energy transfer effect from the lowest triplet energy level of the ligand to the resonance energy level of Eu(III).
Synthesis and characterization of thorium(IV) sulfates.
Knope, Karah E; Wilson, Richard E; Skanthakumar, S; Soderholm, L
2011-09-05
Three Th(IV) sulfates, two new and one previously reported, have been synthesized from aqueous solution. In all of the compounds, the sulfate anions coordinate the Th(4+) metal center(s) in a monodentate manner with Th-S distances of 3.7-3.8 Å. Th(SO(4))(2)(H(2)O)(7)·2(H(2)O) (1; P2(1)/m, a = 7.224(1) Å, b = 12.151(1) Å, c = 7.989(1) Å, ss =98.289(2)°) and Th(4)(SO(4))(7)(H(2)O)(7)(OH)(2)·H(2)O (2; Pnma, a = 18.139(2) Å, b = 11.173(1) Å, c = 14.391(2) Å) each contain 9-coordinate monomeric (1,2) and dimeric (2) Th(IV) cations in monocapped square antiprism geometry. Alternatively, Th(OH)(2)SO(4) (3; Pnma, a = 11.684(1) Å, b = 6.047(1) Å, c = 7.047(1) Å) is built from chains of hydroxo-bridged, 8-coordinate Th(4+) centers. Whereas 1 adopts a molecular structure, 2 and 3 both exhibit 3D architectures. Differences in the dimensionality and the topology of 1-3 are manifested in the local coordination environment about the Th(IV) centers, the formation of oligomeric Th(4+) species, and the extended connectivity of the sulfate ligands. Herein, we report the syntheses and characterization of 1-3 as well as the atomic correlations of 1 in solution, as determined by high-energy X-ray scattering (HEXS).
Structure-activity correlations in a nickel-borate oxygen evolution catalyst.
Bediako, D Kwabena; Lassalle-Kaiser, Benedikt; Surendranath, Yogesh; Yano, Junko; Yachandra, Vittal K; Nocera, Daniel G
2012-04-18
An oxygen evolution catalyst that forms as a thin film from Ni(aq)(2+) solutions containing borate electrolyte (Ni-B(i)) has been studied by in situ X-ray absorption spectroscopy. A dramatic increase in catalytic rate, induced by anodic activation of the electrodeposited films, is accompanied by structure and oxidation state changes. Coulometric measurements correlated with X-ray absorption near-edge structure spectra of the active catalyst show that the nickel centers in activated films possess an average oxidation state of +3.6, indicating that a substantial proportion of nickel centers exist in a formal oxidation state of Ni(IV). In contrast, nickel centers in nonactivated films exist predominantly as Ni(III). Extended X-ray absorption fine structure reveals that activated catalyst films comprise bis-oxo/hydroxo-bridged nickel centers organized into sheets of edge-sharing NiO(6) octahedra. Diminished long-range ordering in catalyst films is due to their ostensibly amorphous nature. Nonactivated films display a similar oxidic nature but exhibit a distortion in the local coordination geometry about nickel centers, characteristic of Jahn-Teller distorted Ni(III) centers. Our findings indicate that the increase in catalytic activity of films is accompanied by changes in oxidation state and structure that are reminiscent of those observed for conversion of β-NiOOH to γ-NiOOH and consequently challenge the long-held notion that the β-NiOOH phase is a more efficient oxygen-evolving catalyst. © 2012 American Chemical Society
DOE Office of Scientific and Technical Information (OSTI.GOV)
Bottomley, F.; Keizer, P.N.; White, P.S.
Hydrolysis of Cp{prime}NbCl{sub 4} (Cp{prime} = {eta}{sup 5}-C{sub 5}H{sub 5} (Cp), {eta}-C{sub 5}H{sub 4}Me (Cp{sup 1})) in tetrahydrofuran (THF) gave a mixture of products of general formula (Cp{prime}NbL{sub 4}){sub 2}({mu}-O), where L{sub 4} is a combination of H{sub 2}O and terminal or bridging Cl that gives eight-coordinate, pentavalent, niobium. For Cp{prime} = Cp, a major constituent of the mixture is (CpNb(H{sub 2}O)Cl{sub 3}){sub 2}({mu}-O) {times} 2THF {times} 0.05Et{sub 2}O (1), the structure of which was determined by X-ray diffraction. Reduction of (Cp{prime}NbL{sub 4}){sub 2}({mu}-O) with aluminum powder gave the cluster (Cp{prime}NbCl({mu}-Cl)){sub 3}({mu}{sub 3}-OH)({mu}{sub 3}-O) (2). The structure of 2 (Cp{prime}more » = Cp) as the THF adduct was determined by X-ray diffraction. Crystal data: monoclinic; P2{sub 1}/c; a = 9.966 (1) {angstrom}, b = 12.471 (2) {angstrom}, c = 20.321 (2) {angstrom}, {beta} = 93.86 (1){degree}.« less
Skin bridge versus rod colostomy in children - comparison between complications.
Askarpour, Shahnam; Peyvasteh, Mehran; Changai, Bahram; Javaherizadeh, Hazhir
2012-10-01
Due to economic problems, sigmoid loop colostomy using glass rod may cause problems for our patients for finding glass rod and several visits. The aim of the study was to compare rod versus skin bridge colostomy. In this study, 42 cases who are candidate for colostomy were included. Cases were randomly placed in skin bridge and rod colostomy group. Independent sample t-test and Chi-square were used for comparison. SPSS version 16.0 (SPSS Inc, Chicago, IL, USA) was used for analysis. Of 42 cases, 20 were male and 22 were female. Hirschsprung's disease was the indication of colostomy in 33 cases. In nine cases, imperforate anus was the indication of colostomy. Mean time of surgery was 79.4 and 82.5 minute for the rod and skin bridge group respectively (P>0.05). Retraction was seen in 2 case of rod group, and no case of skin bridge group. Prolapse was seen in 2 (9.5%) case of rod group and 1(4.7%) case in skin bridge. There were no reports of necrosis, stenosis, and hernia in both groups. In the skin bridge group the rates of complications were lower but the groups are too small for statistical analysis. Colostomy with a skin bridge method may decrease number of revision and expenses and may be appropriate option. Sigmoid loop colostomy using skin bridge flap may be appropriate choice in developing country. Another study with more samples is recommended to better comparison of Skin Bridge versus rod colostomy.
Kato, Merii; Tanase, Tomoaki; Mikuriya, Masahiro
2006-04-03
Reactions of CuX2.nH2O with the biscarboxylate ligand XDK (H2XDK = m-xylenediamine bis(Kemp's triacid imide)) in the presence of N-donor auxiliary ligands yielded a series of dicopper(II) complexes, [Cu2(mu-OH)(XDK)(L)2]X (L = N,N,N',N'-tetramethylethylenediamine (tetmen), X = NO3 (1a), Cl (1b); L = N,N,N'-trimethylethylenediamine (tmen), X = NO3 (2a), Cl (2b); L =2,2'-bipyridine (bpy), X = NO3 (3); L = 1,10-phenanthroline (phen), X = NO3 (4); L = 4,4'-dimethyl-2,2'-bipyridine (Me2bpy), X = NO3 (5); L = 4-methyl-1,10-phenanthroline (Mephen), X = NO3 (6)). Complexes 1-6 were characterized by X-ray crystallography (Cu...Cu = 3.1624(6)-3.2910(4) A), and the electrochemical and magnetic properties were also examined. Complexes 3 and 4 readily reacted with diphenyl phosphoric acid (HDPP) or bis(4-nitrophenyl) phosphoric acid (HBNPP) to give [Cu2(mu-phosphate)(XDK)(L)2]NO3 (L = bpy, phosphate = DPP (11); L = phen, phosphate = DPP (12), BNPP (13)), where the phsophate diester bridges the two copper ions in a mu-1,3-O,O' bidentate fashion (Cu...Cu = 4.268(3)-4.315(1) A). Complexes 4 and 6 with phen and Mephen have proven to be good precursors to accommodate a series of sugar monophosphate esters (Sugar-P) onto the biscarboxylate-bridged dicopper centers, yielding [Cu2(mu-Sugar-P)(XDK)(L)2] (Sugar-P = alpha-D-Glc-1-P (23a and b), D-Glc-6-P (24a and b), D-Man-6-P (25a), D-Fru-6-P (26a and b); L = phen (a), Mephen (b)) and [Cu2(mu-Gly-n-P)(XDK)(Mephen)2] (Gly-n-P = glycerol n-phosphate; n = 2 (21), 3 (22)), where Glc, Man, and Fru are glucose, mannose, and fructose, respectively. The structure of [Cu2(mu-MNPP)(XDK)(phen)2(CH3OH)] (20) was characterized as a reference compound (H2MNPP = 4-nitrophenyl phosphoric acid). Complexes 4 and 6 also reacted with d-fructose 1,6-bisphosphate (D-Fru-1,6-P2) to afford the tetranuclear copper(II) complexes formulated as [Cu4(mu-D-Fru-1,6-P2)(XDK)2(L)4] (L = phen (27a), Mephen (27b)). The detailed structure of 27a was determined by X-ray crystallography to involve two different tetranuclear complexes with alpha- and beta-anomers of D-Fru-1,6-P2, [Cu4(mu-alpha-D-Fru-1,6-P2)(XDK)2(phen)4] and [Cu4(mu-beta-D-Fru-1,6-P2)(XDK)2(phen)4], in which the D-Fru-1,6-P2 tetravalent anion bridges the two [Cu2(XDK)(phen)2]2+ units through the C1 and C6 phosphate groups in a mu-1,3-O,O' bidentate fashion (Cu...Cu = 4.042(2)-4.100(2) A). Notably, the structure with alpha-D-Fru-1,6-P2 demonstrated the presence of a strong hydrogen bond between the C2 hydroxyl group and the C1 phosphate oxygen atom, which may support the previously proposed catalytic mechanism in the active site of fructose-1,6-bisphosphatase.
Arroyo-Hernández, M; Mellado-Romero, M A; Páramo-Díaz, P; Martín-López, C M; Cano-Egea, J M; Vilá Y Rico, J
2015-01-01
The purpose of this study is to analyze if there is any difference between the arthroscopic reparation of full-thickness supraspinatus tears with simple row technique versus suture bridge technique. We accomplished a retrospective study of 123 patients with full-thickness supraspinatus tears between January 2009 and January 2013 in our hospital. There were 60 simple row reparations, and 63 suture bridge ones. The mean age in the simple row group was 62.9, and in the suture bridge group was 63.3 years old. There were more women than men in both groups (67%). All patients were studied using the Constant test. The mean Constant test in the suture bridge group was 76.7, and in the simple row group was 72.4. We have also accomplished a statistical analysis of each Constant item. Strength was higher in the suture bridge group, with a significant statistical difference (p 0.04). The range of movement was also greater in the suture bridge group, but was not statistically significant. Suture bridge technique has better clinical results than single row reparations, but the difference is not statistically significant (p = 0.298).
Kang, Taewook; Lee, Jaeseok; Seo, Junghoon; Han, Dongwook
2017-04-01
[Purpose] The purpose of this research is to investigate the effect of the method of bridge exercise on the change of rectus abdominis muscle and the muscle activity of paraspinal muscles while doing treadmill walking with high heels. [Subjects and Methods] The subjects of this research are healthy female students consisting of 10 persons performing bridge exercises in a supine group, 10 persons performing bridge exercises in a prone group, and 10 persons in a control group while in S university in Busan. Bridge exercise in supine position is performed in hook lying position. Bridge exercise in prone position is plank exercise in prostrate position. To measure the strength of rectus abdominis muscle, maintaining times of the posture was used. To measure the muscle activity of paraspinal muscles, EMG (4D-MT & EMD-11, Relive, Korea) was used. [Results] The strength of rectus abdominis muscle of both bridge exercises in the supine group and bridge exercises in the prone group increases significantly after exercise. The muscle activity of paraspinal muscle such as thoracic parts and lumbar parts in bridge exercises in the prone group decreases statistically while walking on a treadmill with high heels. Muscle activity of thoracic parts paraspinal muscle and bridge exercises in the supine group decreased significantly. [Conclusion] According to this study, we noticed that bridge exercise in a prone position is desirable for women who prefer wearing high heels as a back pain prevention exercise method.
Rice, Derek B; Wijeratne, Gayan B; Burr, Andrew D; Parham, Joshua D; Day, Victor W; Jackson, Timothy A
2016-08-15
A mononuclear hydroxomanganese(III) complex was synthesized utilizing the N5 amide-containing ligand 2-[bis(pyridin-2-ylmethyl)]amino-N-2-methyl-quinolin-8-yl-acetamidate (dpaq(2Me) ). This complex is similar to previously reported [Mn(III)(OH)(dpaq(H))](+) [Inorg. Chem. 2014, 53, 7622-7634] but contains a methyl group adjacent to the hydroxo moiety. This α-methylquinoline group in [Mn(III)(OH)(dpaq(2Me))](+) gives rise to a 0.1 Å elongation in the Mn-N(quinoline) distance relative to [Mn(III)(OH)(dpaq(H))](+). Similar bond elongation is observed in the corresponding Mn(II) complex. In MeCN, [Mn(III)(OH)(dpaq(2Me))](+) reacts rapidly with 2,2',6,6'-tetramethylpiperidine-1-ol (TEMPOH) at -35 °C by a concerted proton-electron transfer (CPET) mechanism (second-order rate constant k2 of 3.9(3) M(-1) s(-1)). Using enthalpies and entropies of activation from variable-temperature studies of TEMPOH oxidation by [Mn(III)(OH)(dpaq(2Me))](+) (ΔH(‡) = 5.7(3) kcal(-1) M(-1); ΔS(‡) = -41(1) cal M(-1) K(-1)), it was determined that [Mn(III)(OH)(dpaq(2Me))](+) oxidizes TEMPOH ∼240 times faster than [Mn(III)(OH)(dpaq(H))](+). The [Mn(III)(OH)(dpaq(2Me))](+) complex is also capable of oxidizing the stronger O-H and C-H bonds of 2,4,6-tri-tert-butylphenol and xanthene, respectively. However, for these reactions [Mn(III)(OH)(dpaq(2Me))](+) displays, at best, modest rate enhancement relative to [Mn(III)(OH)(dpaq(H))](+). A combination of density function theory (DFT) and cyclic voltammetry studies establish an increase in the Mn(III)/Mn(II) reduction potential of [Mn(III)(OH)(dpaq(2Me))](+) relative to [Mn(III)(OH)(dpaq(H))](+), which gives rise to a larger driving force for CPET for the former complex. Thus, more favorable thermodynamics for [Mn(III)(OH)(dpaq(2Me))](+) can account for the dramatic increase in rate with TEMPOH. For the more sterically encumbered substrates, DFT computations suggest that this effect is mitigated by unfavorable steric interactions between the substrate and the α-methylquinoline group of the dpaq(2Me) ligand. The DFT calculations, which reproduce the experimental activation free energies quite well, provide the first examination of the transition-state structure of mononuclear Mn(III)(OH) species during a CPET reaction.
Gong, Wontae
2015-01-01
[Purpose] The present study sought to investigate the influence on static and dynamic lumbar stability of bridge exercise accompanied by an abdominal drawing-in maneuver (ADIM) performed on an uneven support surface. [Subjects] A total of 30 participants were divided into an experimental group (15 participants) and a control group (15 participants). [Methods] The experimental group performed bridge exercise on an unstable surface, whereas the control group performed bridge exercise on a stable surface. The respective bridge exercises were performed for 30 minutes, 3 times per week, for 6 weeks. The static lumbar stability (SLS) and dynamic lumbar stability (DLS) of both the experimental group and the control group were measured using a pressure biofeedback unit. [Results] In the comparison of the initial and final results of the experimental and control groups, only the SLS and DLS of the experimental group were found to be statistically significant. [Conclusion] The results of the present study show that when using bridge exercise to improve SLS and DLS, performing the bridge exercise accompanied by ADIM on an uneven surface is more effective than performing the exercise on a stable surface.
Kheradmandan, S; Koutayas, S O; Bernhard, M; Strub, J R
2001-04-01
The purpose of this study was to evaluate the fracture strength of four different types of anterior 3-unit bridges after thermo-mechanical fatigue in a dual-axis chewing simulator. Sixty-four human maxillary incisors were prepared and 32 bridges fabricated. The four groups of eight bridges each were - (GC): AGC(R) galvano-ceramic bridges (CA): Celay(R) In-Ceram(R) Alumina bridges (E2): heat-pressed lithium disilicate glass-ceramic bridges and (CM) ceramo-metal (control). Fracture loads were recorded after a dual-axis chewing simulator and in a universal testing machine. The survival rate after 5 years for the CM and the GC groups was 100%, for the E2 group 75% and for the CA group 37.5% (Kaplan-Mayer analysis). The mean fracture strengths (N) were 681.52 +/- 151.90 (CM); 397.71 +/- 59.02 (GC); 292.92 +/- 46.45 (E2) and 239.95 +/- 33.39 (CA), respectively. The log-rank test showed a significant difference between the CA and the GC or the CA and the CM groups. No significant differences between the E2 and the CA or the E2 and the GC groups were found. The study indicates that heat-pressed lithium disilicate glass-ceramic and AGC(R) galvano-ceramic bridges are alternatives to ceramo-metal 3-unit anterior bridges.
Oh, Heung-Kwon; Han, Eon Chul; Song, Yoon Suk; Seo, Mi Sun; Ryoo, Seung-Bum; Jeong, Seung-Yong; Park, Kyu Joo
2015-01-01
A temporary defunctioning loop ileostomy is frequently created during low colorectal or coloanal anastomosis to prevent peritoneal sepsis associated with anastomotic leakage. We investigated whether routine support bridge placement prevents stoma retraction after the formation of a loop ileostomy. Prospective, nonrandomized trial. The study sample comprised 32 consecutive patients who underwent defunctioning loop ileostomy at an academic tertiary care center in Seoul Korea from February to September 2010. Patients were nonrandomly allocated to "no bridge," "short-term bridge" (1 week), and "long-term bridge" (3 weeks) groups based on the surgeon's clinical judgment. Group differences in stoma height changes over time were analyzed. Subjects' mean age was 59.5 (range: 43-82) years, and the male-to-female ratio was 2.2:1.0. The mean heights of the stoma on postoperative day 2 and postoperative month 3, respectively, were 1.07 ± 0.16 cm (mean ± SD) and 0.81 ± 0.17 cm in the no-bridge group, 1.70 ± 0.29 cm and 1.21 ± 0.18 cm in the short-term bridge group, and 1.18 ± 0.16 cm and 1.01 ± 0.20 cm in the long-term bridge group. The changes in the stoma height 3 months after the surgery showed no statistically significant differences among the groups (P = .430). Stoma Quality of Life scores at 3 weeks (47.4 vs 46.1; P = .730) were similar for patients with and without bridges. However, a significantly greater number of patients with bridges reported difficulty with pouch changes compared to those without bridges (72.7% vs 14.3%; P = .002). Routine use of support bridges during loop ileostomy is unnecessary and inconvenient to patients. If a support bridge must be used, it can be removed early.
Bridged graphite oxide materials
NASA Technical Reports Server (NTRS)
Herrera-Alonso, Margarita (Inventor); McAllister, Michael J. (Inventor); Aksay, Ilhan A. (Inventor); Prud'homme, Robert K. (Inventor)
2010-01-01
Bridged graphite oxide material comprising graphite sheets bridged by at least one diamine bridging group. The bridged graphite oxide material may be incorporated in polymer composites or used in adsorption media.
Todd, Emily M; Biswas Roy, Sreeja; Hashimi, A Samad; Serrone, Rosemarie; Panchanathan, Roshan; Kang, Paul; Varsch, Katherine E; Steinbock, Barry E; Huang, Jasmine; Omar, Ashraf; Patel, Vipul; Walia, Rajat; Smith, Michael A; Bremner, Ross M
2017-11-01
Extracorporeal membrane oxygenation has been used as a bridge to lung transplantation in patients with rapid pulmonary function deterioration. The reported success of this modality and perioperative and functional outcomes are varied. We retrospectively reviewed all patients who underwent lung transplantation at our institution over 1 year (January 1, 2015, to December 31, 2015). Patients were divided into 2 groups depending on whether they required extracorporeal membrane oxygenation support as a bridge to transplant; preoperative characteristics, lung transplantation outcomes, and survival were compared between groups. Of the 93 patients, 12 (13%) received bridge to transplant, and 81 (87%) did not. Patients receiving bridge to transplant were younger, had higher lung allocation scores, had lower functional status, and were more often on mechanical ventilation at listing. Most patients who received bridge to transplant (n = 10, 83.3%) had pulmonary fibrosis. Mean pretransplant extracorporeal membrane oxygenation support was 103.6 hours in duration (range, 16-395 hours). All patients who received bridge to transplant were decannulated immediately after lung transplantation but were more likely to return to the operating room for secondary chest closure or rethoracotomy. Grade 3 primary graft dysfunction within 72 hours was similar between groups. Lung transplantation success and hospital discharge were 100% in the bridge to transplant group; however, these patients experienced longer hospital stays and higher rates of discharge to acute rehabilitation. The 1-year survival was 100% in the bridge to transplant group and 91% in the non-bridge to transplant group (log-rank, P = .24). The 1-year functional status was excellent in both groups. Extracorporeal membrane oxygenation can be used to safely bridge high-acuity patients with end-stage lung disease to lung transplantation with good 30-day, 90-day, and 1-year survival and excellent 1-year functional status. Long-term outcomes are being studied. Copyright © 2017. Published by Elsevier Inc.
Hepatic artery bridging lessens temporary ischemic injury to bile canaliculi
Wang, Jia-Zhong; Liu, Yang; Wang, Jin-Long; Lu, Le; Zhang, Ya-Fei; Lu, Hong-Wei; Li, Yi-Ming
2015-01-01
AIM: To study whether transfer of blood between the right gastroepiploic artery and gastroduodenal artery could lessens the damage to bile canaliculi. METHODS: Forty male Bama miniature pigs were divided into four groups as follows: a control group, two hepatic artery ischemia groups (1 h and 2 h), and a hepatic artery bridging group. The hemodynamics of the hepatic artery in the hepatic artery bridging group was measured using color Doppler ultrasound. Morphological changes in the bile canaliculus were observed by transmission electron microscopy. Cofilin, heat shock protein 27 and F-actin expression was detected by immunohistochemistry, Western blot, and real-time polymerase chain reaction. Terminal deoxynucleotidyl transferase-mediated nick end-labeling method was used to evaluate liver injury. RESULTS: The hemodynamics was not changed in the hepatic artery bridging group. The microvilli in the bile canaliculus were impaired in the two hepatic artery ischemia groups. The down-regulation of cofilin and F-actin and up-regulation of heat shock protein 27 were observed in the two hepatic artery ischemia groups, while there were no significant differences between the control group and hepatic artery bridging group. CONCLUSION: Hepatic artery ischemia aggravates damage to bile canaliculi, and this damage can be diminished by a hepatic artery bridging duct. PMID:26401076
Wijeratne, Gayan B; Corzine, Briana; Day, Victor W; Jackson, Timothy A
2014-07-21
The mononuclear hydroxomanganese(III) complex, [Mn(III)(OH)(dpaq)](+), which is supported by the amide-containing N5 ligand dpaq (dpaq = 2-[bis(pyridin-2-ylmethyl)]amino-N-quinolin-8-yl-acetamidate) was generated by treatment of the manganese(II) species, [Mn(II)(dpaq)](OTf), with dioxygen in acetonitrile solution at 25 °C. This oxygenation reaction proceeds with essentially quantitative yield (greater than 98% isolated yield) and represents a rare example of an O2-mediated oxidation of a manganese(II) complex to generate a single product. The X-ray diffraction structure of [Mn(III)(OH)(dpaq)](+) reveals a short Mn-OH distance of 1.806(13) Å, with the hydroxo moiety trans to the amide function of the dpaq ligand. No shielding of the hydroxo group is observed in the solid-state structure. Nonetheless, [Mn(III)(OH)(dpaq)](+) is remarkably stable, decreasing in concentration by only 10% when stored in MeCN at 25 °C for 1 week. The [Mn(III)(OH)(dpaq)](+) complex participates in proton-coupled electron transfer reactions with substrates with relatively weak O-H and C-H bonds. For example, [Mn(III)(OH)(dpaq)](+) oxidizes TEMPOH (TEMPOH = 2,2'-6,6'-tetramethylpiperidine-1-ol), which has a bond dissociation free energy (BDFE) of 66.5 kcal/mol, in MeCN at 25 °C. The hydrogen/deuterium kinetic isotope effect of 1.8 observed for this reaction implies a concerted proton-electron transfer pathway. The [Mn(III)(OH)(dpaq)](+) complex also oxidizes xanthene (C-H BDFE of 73.3 kcal/mol in dimethylsulfoxide) and phenols, such as 2,4,6-tri-t-butylphenol, with BDFEs of less than 79 kcal/mol. Saturation kinetics were observed for phenol oxidation, implying an initial equilibrium prior to the rate-determining step. On the basis of a collective body of evidence, the equilibrium step is attributed to the formation of a hydrogen-bonding complex between [Mn(III)(OH)(dpaq)](+) and the phenol substrates.
De Servi, Stefano; Morici, Nuccia; Boschetti, Enrico; Rossini, Roberta; Martina, Paola; Musumeci, Giuseppe; D'Urbano, Maurizio; Lazzari, Ludovico; La Vecchia, Carlo; Senni, Michele; Klugmann, Silvio; Savonitto, Stefano
2016-05-01
Intravenous administration of a short acting glycoprotein IIb/IIIa inhibitor has been proposed as a bridge to surgery in patients on dual antiplatelet treatment, but data in comparison with other treatment options are not available. We conducted a retrospective analysis of consecutive patients who underwent un-deferrable, non-emergency surgery after coronary stenting. The bridge therapy was performed after discontinuation of the oral P2Y12 inhibitor by using i.v. tirofiban infusion. Net Adverse Clinical Events (NACE) was the primary outcome. We analyzed 314 consecutive patients: the bridge strategy was performed in 87 patients, whereas 227 were treated with other treatment options and represent the control group. Thirty-day NACE occurred in 8% of patients in the bridge group and in 22.5% in the control group (p < 0.01). Bridge therapy was associated with decreased 30-day NACE rate [Odds ratio (OR) 0.30; 95% confidence interval (CI) 0.13-0.39; p < 0.01], particularly when the time interval between stenting and surgery was ≤ 60 days (OR 0.09, 95% CI 0.01-0.72; p = 0.02). There were no cases of stent thrombosis in the bridge group and 3 (1.3%) in the control group. Bridge therapy was associated with decreased events rates as compared to both patients with and without P2Y12 inhibitors discontinuation in the control group. After adjustment for the most relevant covariates, the favorable effect of the bridge therapy was not materially modified. In conclusion, perioperative bridge therapy using tirofiban was associated with reduced 30-day NACE rate, particularly when surgery was performed within 60 days after stent implantation.
Cho, Misuk; Jeon, Hyewon
2013-06-01
[Purpose] We examined the effects of an abdominal drawing-in bridge exercise using a pressure biofeedback unit on different bases on the thickness of trunk and abdominal muscles, and lumbar stability. [Subjects] Thirty healthy young adults (2 males, 28 females) took part in this study. The subjects were randomly and equally assigned to a stable bridge exercise group and an unstable bridge exercise group. [Methods] The subjects performed bridge exercises using an abdominal drawing-in method on a stable base and on an unstable base, and changes in their abdominal muscle thickness and on the stable and on unstable bases lumbar stability were evaluated. [Results] After the intervention, the stable bridge exercise group showed a statistically significantly increased muscle thickness in the transversus abdominis, and the unstable bridge exercise group showed significantly increased muscle thicknesses of the transversus abdominis and internal obliques in static and dynamic lumbar stability. The unstable bridge exercise group showed significant increase after performing the exercise. [Conclusion] Lumbar stability exercise, with the compensation of the lumbar spine minimized, using an abdominal drawing-in method on an unstable support of base is effective and efforts to prevent the compensation may induce a greater exercise effect.
Integrating Gender and Group Differences into Bridging Strategy
ERIC Educational Resources Information Center
Yilmaz, Serkan; Eryilmaz, Ali
2010-01-01
The main goal of this study was to integrate gender and group effect into bridging strategy in order to assess the effect of bridging analogy-based instruction on sophomore students' misconceptions in Newton's Third Law. Specifically, the authors developed and benefited from anchoring analogy diagnostic test to merge the effect of group and gender…
Chitmongkolsuk, Somsak; Heydecke, Guido; Stappert, Christian; Strub, Joerg R
2002-03-01
The replacement of missing posterior teeth using all-ceramic bridges remains a challenge. This study compares the fracture resistance of all-ceramic 3-unit bridges for the replacement of first molars to conventional porcelain-fused-to-metal bridges. Human premolars and molars were used to create two test groups and one control group of 16 specimens each. To simulate clinical parameters, the specimens were exposed to cyclic fatigue loading in an artificial mouth with simultaneous thermocycling. All samples were thereafter exposed to fracture strength testing. Porcelain-fused-to-metal bridges showed significantly higher fracture strengths than all-ceramic bridges. However, the fracture strength of the all-ceramic bridges was higher than peak physiological chewing forces.
Zhang, Peng; Chen, TianWu; Chen, ShiYi
2016-01-01
Purpose. To compare the biomechanical properties of 3 suture-bridge techniques for rotator cuff repair. Methods. Twelve pair-matched fresh-frozen shoulder specimens were randomized to 3 groups of different repair types: the medially Knotted Suture Bridge (KSB), the medially Untied Suture Bridge (USB), and the Modified Suture Bridge (MSB). Cyclic loading and load-to-failure test were performed. Parameters of elongation, stiffness, load at failure, and mode of failure were recorded. Results. The MSB technique had the significantly greatest load to failure (515.6 ± 78.0 N, P = 0.04 for KSB group; P < 0.001 for USB group), stiffness (58.0 ± 10.7 N/mm, P = 0.005 for KSB group; P < 0.001 for USB group), and lowest elongation (1.49 ± 0.39 mm, P = 0.009 for KSB group; P = 0.001 for USB group) among 3 groups. The KSB repair had significantly higher ultimate load (443.5 ± 65.0 N) than USB repair (363.5 ± 52.3 N, P = 0.024). However, there was no statistical difference in stiffness and elongation between KSB and USB technique (P = 0.396 for stiffness and P = 0.242 for elongation, resp.). The failure mode for all specimens was suture pulling through the cuff tendon. Conclusions. Our modified suture bridge technique (MSB) may provide enhanced biomechanical properties when compared with medially knotted or knotless repair. Clinical Relevance. Our modified technique may represent a promising alternative in arthroscopic rotator cuff repair. PMID:27975065
NASA Astrophysics Data System (ADS)
Sun, Qijun; Lee, Seong Jun; Kang, Hyungseok; Gim, Yuseong; Park, Ho Seok; Cho, Jeong Ho
2015-04-01
An ultrathin conductive adhesion promoter using positively charged reduced graphene oxide (rGO-NH3+) has been demonstrated for preparing highly stable silver nanowire transparent conductive electrodes (AgNW TCEs). The adhesion promoter rGO-NH3+, spray coated between the substrate and AgNWs, significantly enhances the chemical and mechanical stabilities of the AgNW TCEs. Besides, the ultrathin thickness of the rGO-NH3+ ensures excellent optical transparency and mechanical flexibility for TCEs. The AgNW films prepared using the adhesion promoter are extremely stable under harsh conditions, including ultrasonication in a variety of solvents, 3M Scotch tape detachment test, mechanical bending up to 0.3% strain, or fatigue over 1000 cycles. The greatly enhanced adhesion force is attributed to the ionic interactions between the positively charged protonated amine groups in rGO-NH3+ and the negatively charged hydroxo- and oxo-groups on the AgNWs. The positively charged GO-NH3+ and commercial polycationic polymer (poly allylamine hydrochloride) are also prepared as adhesion promoters for comparison with rGO-NH3+. Notably, the closely packed hexagonal atomic structure of rGO offers better barrier properties to water permeation and demonstrates promising utility in durable waterproof electronics. This work offers a simple method to prepare high-quality TCEs and is believed to have great potential application in flexible waterproof electronics.An ultrathin conductive adhesion promoter using positively charged reduced graphene oxide (rGO-NH3+) has been demonstrated for preparing highly stable silver nanowire transparent conductive electrodes (AgNW TCEs). The adhesion promoter rGO-NH3+, spray coated between the substrate and AgNWs, significantly enhances the chemical and mechanical stabilities of the AgNW TCEs. Besides, the ultrathin thickness of the rGO-NH3+ ensures excellent optical transparency and mechanical flexibility for TCEs. The AgNW films prepared using the adhesion promoter are extremely stable under harsh conditions, including ultrasonication in a variety of solvents, 3M Scotch tape detachment test, mechanical bending up to 0.3% strain, or fatigue over 1000 cycles. The greatly enhanced adhesion force is attributed to the ionic interactions between the positively charged protonated amine groups in rGO-NH3+ and the negatively charged hydroxo- and oxo-groups on the AgNWs. The positively charged GO-NH3+ and commercial polycationic polymer (poly allylamine hydrochloride) are also prepared as adhesion promoters for comparison with rGO-NH3+. Notably, the closely packed hexagonal atomic structure of rGO offers better barrier properties to water permeation and demonstrates promising utility in durable waterproof electronics. This work offers a simple method to prepare high-quality TCEs and is believed to have great potential application in flexible waterproof electronics. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr00777a
Ryu, Keun Jung; Kim, Bang Hyun; Lee, Yohan; Lee, Yoon Seok; Kim, Jae Hwa
2015-03-01
The arthroscopic suture-bridge technique has proved to provide biomechanically firm fixation of the torn rotator cuff to the tuberosity by increasing the footprint contact area and pressure. However, a marginal dog-ear deformity is encountered not infrequently when this technique is used, impeding full restoration of the torn cuff. To evaluate the structural and functional outcomes of the use of a modified suture-bridge technique to prevent a marginal dog-ear deformity compared with a conventional suture-bridge method in rotator cuff repair. Cohort study; Level of evidence 2. A consecutive series of 71 patients aged 50 to 65 years who underwent arthroscopic rotator cuff repair for full-thickness medium-sized to massive tears was evaluated. Patients were divided into 2 groups according to repair technique: a conventional suture-bridge technique (34 patients; group A) versus a modified suture-bridge technique to prevent a marginal dog-ear deformity (37 patients; group B). Radiographic evaluations included postoperative cuff integrity using MRI. Functional evaluations included pre- and postoperative range of motion (ROM), pain visual analog scale (VAS), the University of California, Los Angeles (UCLA) shoulder rating scale, the Constant score, and the American Shoulder and Elbow Surgeons (ASES) score. All patients were followed up clinically at a minimum of 1 year. When the 2 surgical techniques were compared, postoperative structural integrity by Sugaya classification showed the distribution of types I:II:III:IV:V to be 4:20:2:4:4 in group A and 20:12:4:0:1 in group B. More subjects in group B had a favorable Sugaya type compared with group A (P < .001). The postoperative healed:retear rate was 26:8 in group A and 36:1 in group B, with a significantly lower retear rate in group B (P = .011). However, there were no significant differences in ROM and all functional outcome scores between the 2 groups postoperatively. When surgical techniques were compared across healed (n = 62) and retear (n = 9) groups, significantly fewer modified suture-bridge technique repairs were found in the retear group (P = .03). There were significant differences between healed and retear groups in functional outcome scores, with worse results in the retear group. A modified suture-bridge technique to prevent a marginal dog-ear deformity provided better structural outcomes than a conventional suture-bridge technique for medium-sized to massive rotator cuff tears. This technique may ultimately provide better functional outcomes by decreasing the retear rate. © 2014 The Author(s).
Lee, Sung Hyun; Kim, Jeong Woo; Kim, Tae Kyun; Kweon, Seok Hyun; Kang, Hong Je; Kim, Se Jin; Park, Jin Sung
2017-07-01
The purpose of this study was to compare functional outcomes and tendon integrity between the suture bridge and modified tension band techniques for arthroscopic rotator cuff repair. A consecutive series of 128 patients who underwent the modified tension band (MTB group; 69 patients) and suture bridge (SB group; 59 patients) techniques were enrolled. The pain visual analogue scale (VAS), Constant, and American Shoulder and Elbow Surgeons (ASES) scores were determined preoperatively and at the final follow-up. Rotator cuff hypotrophy was quantified by calculating the occupation ratio (OR). Rotator cuff integrity and the global fatty degeneration index were determined by using magnetic resonance imaging at 6 months postoperatively. The average VAS, Constant, and ASES scores improved significantly at the final follow-up in both groups (p < 0.05 for all scores). The retear rate of small-to-medium tears was similar in the modified tension band and suture bridge groups (7.0 vs. 6.8%, respectively; p = n.s.). The retear rate of large-to-massive tears was significantly lower in the suture bridge group than in the modified tension band group (33.3 vs. 70%; p = 0.035). Fatty infiltration (postoperative global fatty degeneration index, p = 0.022) and muscle hypotrophy (postoperative OR, p = 0.038) outcomes were significantly better with the suture bridge technique. The retear rate was lower with the suture bridge technique in the case of large-to-massive rotator cuff tears. Additionally, significant improvements in hypotrophy and fatty infiltration of the rotator cuff were obtained with the suture bridge technique, possibly resulting in better anatomical outcomes. The suture bridge technique was a more effective method for the repair of rotator cuff tears of all sizes as compared to the modified tension band technique. Retrospective Cohort Design, Treatment Study, level III.
Krewald, Vera; Neese, Frank; Pantazis, Dimitrios A
2016-04-28
The redox potential of synthetic oligonuclear transition metal complexes has been shown to correlate with the Lewis acidity of a redox-inactive cation connected to the redox-active transition metals of the cluster via oxo or hydroxo bridges. Such heterometallic clusters are important cofactors in many metalloenzymes, where it is speculated that the redox-inactive constituent ion of the cluster serves to optimize its redox potential for electron transfer or catalysis. A principal example is the oxygen-evolving complex in photosystem II of natural photosynthesis, a Mn4CaO5 cofactor that oxidizes water into dioxygen, protons and electrons. Calcium is critical for catalytic function, but its precise role is not yet established. In analogy to synthetic complexes it has been suggested that Ca(2+) fine-tunes the redox potential of the manganese cluster. Here we evaluate this hypothesis by computing the relative redox potentials of substituted derivatives of the oxygen-evolving complex with the cations Sr(2+), Gd(3+), Cd(2+), Zn(2+), Mg(2+), Sc(3+), Na(+) and Y(3+) for two sequential transitions of its catalytic cycle. The theoretical approach is validated with a series of experimentally well-characterized Mn3AO4 cubane complexes that are structural mimics of the enzymatic cluster. Our results reproduce perfectly the experimentally observed correlation between the redox potential and the Lewis acidities of redox-inactive cations for the synthetic complexes. However, it is conclusively demonstrated that this correlation does not hold for the oxygen evolving complex. In the enzyme the redox potential of the cluster only responds to the charge of the redox-inactive cations and remains otherwise insensitive to their precise identity, precluding redox-tuning of the metal cluster as a primary role for Ca(2+) in biological water oxidation.
Contact area and pressure in suture bridge rotator cuff repair using knotless lateral anchors.
Tompkins, Marc; Monchik, Keith O; Plante, Matthew J; Fleming, Braden C; Fadale, Paul D
2011-10-01
To evaluate whether the use of knotless lateral anchors in a suture bridge construct produces better contact area and pressure parameters than a suture bridge construct with standard lateral anchors that require knots or a double-row repair. The hypothesis was that knotless lateral anchors would produce better contact area and pressure parameters than the other two constructs. A total of fifteen matched pairs of cadaveric shoulders were divided into three groups. In Group 1, a suture bridge using knotless anchors for the lateral row was performed on five shoulders. A suture bridge using standard lateral row anchors that require knots was performed on the contralateral shoulders. In Group 2, suture bridge with knotless lateral row anchors was compared with double-row repair. In Group 3, suture bridge using standard lateral row anchors was compared with double-row repair. The contact conditions of the rotator cuff footprint were measured using pressure-sensitive film. There were no statistically significant differences between any of the techniques regarding contact area F(2, 15.7) = 3.09, P = 0.07 or mean contact pressure F(2, 15.1) = 2.35, P = 0.12. A post hoc power analysis suggests differences between techniques are likely less than 91-113 mm(2) for area and 0.071-0.089 N for pressure. The use of knotless anchors in the lateral row of a suture bridge repair did not increase the footprint contact area or contact pressure when compared to a suture bridge repair requiring knots laterally or to a double-row repair.
Won, Ki-Bum; Lee, Seung-Hyun; Chang, Hyuk-Jae; Shim, Chi-Young; Hong, Gue-Ru; Ha, Jong-Won; Chung, Namsik
2014-07-01
Bridge anticoagulation therapy is mostly utilized in patients with mechanical heart valves (MHV) receiving warfarin therapy during invasive dental procedures because of the risk of excessive bleeding related to highly vascular supporting dental structures. Bridge therapy using low molecular weight heparin may be an attractive option for invasive dental procedures; however, its safety and cost-effectiveness compared with unfractionated heparin (UFH) is uncertain. This study investigated the safety and cost-effectiveness of enoxaparin in comparison to UFH for bridge therapy in 165 consecutive patients (57±11 years, 35% men) with MHV who underwent invasive dental procedures. This study included 75 patients treated with UFH-based bridge therapy (45%) and 90 patients treated with enoxaparin-based bridge therapy (55%). The bleeding risk of dental procedures and the incidence of clinical adverse outcomes were not significantly different between the UFH group and the enoxaparin group. However, total medical costs were significantly lower in the enoxaparin group than in the UFH group (p<0.001). After multivariate adjustment, old age (≥65 years) was significantly associated with an increased risk of total bleeding independent of bridging methods (odds ratio, 2.51; 95% confidence interval, 1.15-5.48; p=0.022). Enoxaparin-based bridge therapy (β=-0.694, p<0.001) and major bleeding (β=0.296, p=0.045) were significantly associated with the medical costs within 30 days after dental procedures. Considering the benefit of enoxaparin in cost-effectiveness, enoxaparin may be more efficient than UFH for bridge therapy in patients with MHV who required invasive dental procedures.
Kumar, Annamalai Senthil; Tanase, Tomoaki; Iida, Masayasu
2007-01-16
Nanostructured molecular film containing the (micro-hydroxo)bis(micro-carboxylato) diruthenium(III) units, [RuIII2(micro-OH)(micro-CH3COO)2(HBpz3)2]+ ({RuIII2(micro-OH)}), was prepared by an in situ conversion of its micro-oxo precursor, [RuIII2(micro-O)(micro-CH3COO)2(HBpz3)2] ({RuIII2(micro-O)}), in a Nafion membrane matrix, where HBpz3 is hydrotris(1-pyrazolyl)borate. The conversion procedure results in fine nanoparticle aggregates of the {RuIII2(micro-OH)} units in the Nafion membrane (Nf-{RuIII2(micro-OH)}), where an average particle size (4.1 +/- 2.3 nm) is close to the Nafion's cluster dimension of approximately 4 nm. Chemically modified electrodes by using the Nafion molecular membrane films (Nf-{RuIII2(micro-OH)}-MMFEs) were further developed on ITO/glass and glassy carbon electrode (GCE) surfaces, and a selective reduction of nitrosonium ion (NO+), presumably through reaction of a {RuIIRuIII(micro-OH)} mixed-valence state with HNO2, was demonstrated without interference by molecular oxygen in an acidic aqueous solution. The Nf-{RuIII2(micro-OH)}-MMFEs are stable even in a physiological condition (pH 7), where the naked {RuIII2(-OH)} complex is readily transformed into its deprotonated {RuIII2(micro-O)} form, demonstrating an unusual stabilizing effects for the {RuIII2(micro-OH)} unit by the Nafion cluster environment.
Ruiz, José; Martínez, M Teresa; Florenciano, Félix; Rodríguez, Venancio; López, Gregorio; Pérez, José; Chaloner, Penny A; Hitchcock, Peter B
2003-06-02
Mononuclear palladium hydroxo complexes of the type [Pd(N[bond]N)(C(6)F(5))(OH)] [(N[bond]N = 2,2'-bipyridine (bipy), 4,4'-dimethyl-2,2'-bipyridine (Me(2)bipy), 1,10-phenanthroline (phen), or N,N,N',N'-tetramethylethylenediamine (tmeda)] have been prepared by reaction of [Pd(N[bond]N)(C(6)F(5))(acetone)]ClO(4) with KOH in methanol. These hydroxo complexes react, in methanol, with CO (1 atm, room temperature) to yield the corresponding methoxycarbonyl complexes [Pd(N[bond]N)(C(6)F(5))(CO(2)Me)]. Similar alkoxycarbonyl complexes [Pd(N[bond]N)(C(6)F(5))(CO(2)R)] (N[bond]N = bis(3,5-dimethylpyrazol-1-yl)methane); R = Me, Et, or (i)Pr) are obtained when [Pd(N[bond]N)(C(6)F(5))Cl] is treated with KOH in the corresponding alcohol ROH and CO is bubbled through the solution. The reactions of [Pd(N[bond]N)(C(6)F(5))(OH)] (N[bond]N = bipy or Me(2)bipy) with CO(2), in tetrahydrofuran, lead to the formation of the binuclear carbonate complexes [(N[bond]N)(C(6)F(5))Pd(mu-eta(2)-CO(3))Pd(C(6)F(5))(N[bond]N)]. Complexes [Pd(N[bond]N)(C(6)F(5))(OH)] react in alcohol with PhNCS to yield the corresponding N-phenyl-O-alkylthiocarbamate complexes [Pd(N[bond]N)(C(6)F(5))[SC(OR)NPh
Structural Modification of Sol-Gel Materials through Retro Diels-Alder Reaction
DOE Office of Scientific and Technical Information (OSTI.GOV)
SHALTOUT,RAAFAT M.; LOY,DOUGLAS A.; MCCLAIN,MARK D.
1999-12-08
Hydrolysis and condensation of organically bridged bis-triethoxysilanes, (EtO){sub 3}Si-R-Si(OEt){sub 3}, results in the formation of three dimensional organic/inorganic hybrid networks (Equation 1). Properties of these materials, including porosity, are dependent on the nature of the bridging group, R. Flexible groups (akylene-spacers longer than five carbons in length) polymerize under acidic conditions to give non-porous materials. Rigid groups (such as arylene-, alkynylene-, or alkenylene) form non-porous, microporous, and macroporous gels. In many cases the pore size distributions are quite narrow. One of the motivations for preparing hybrid organic-inorganic materials is to extend the range of properties available with sol-gel systems bymore » incorporating organic groups into the inorganic network. For example, organically modified silica gels arc either prepared by co-polymerizing an organoalkoxysilane with a silica precursor or surface silylating the inorganic gel. This can serve to increase hydrophobicity or to introduce some reactive organic functionality. However, the type and orientation of these organic functionalities is difficult to control. Furthermore, many organoalkoxysilanes can act to inhibitor even prevent gelation, limiting the final density of organic functionalities. We have devised a new route for preparing highly functionalized pores in hybrid materials using bridging groups that are thermally converted into the desired functionalities after the gel has been obtained. In this paper, we present the preparation and characterization of bridged polysilsesquioxanes with Diels-Alder adducts as the bridging groups from the sol-gel polymerization of monomers 2 and 4. The bridging groups are constructed such that the retro Diela-Alder reaction releases the dienes and leaves the dienophiles as integral parts of the network polymers. In the rigid architecture of a xerogel, this loss of organic functionality should liberate sufficient space to modify the overall porosity. Furthermore, the new porosity will be functionalized with the dienophilic olefin bridging group. We also demonstrate that by changing the type of Diels-Alder adduct used as the bridging group, we can change the temperature at which the retro-Diels-Alder reaction will occur.« less
Esteves, Lucas F; Rey, Nicolás A; Dos Santos, Hélio F; Costa, Luiz Antônio S
2016-03-21
The catalytic mechanism that involves the cleavage of the phosphate diester model BDNPP (bis(2,4-dinitrophenyl) phosphate) catalyzed through a dinuclear copper complex is investigated in the current study. The metal complex was originally designed to catalyze catechol oxidation, and it showed an interesting catalytic promiscuity case in biomimetic systems. The current study investigates two different reaction mechanisms through quantum mechanics calculations in the gas phase, and it also includes the solvent effect through PCM (polarizable continuum model) single-point calculations using water as solvent. Two mechanisms are presented in order to fully describe the phosphate diester hydrolysis. Mechanism 1 is of the S(N)2 type, which involves the direct attack of the μ-OH bridge between the two copper(II) ions toward the phosphorus center, whereas mechanism 2 is the process in which hydrolysis takes place through proton transfer between the oxygen atom in the bridging hydroxo ligand and the other oxygen atom in the phosphate model. Actually, the present theoretical study shows two possible reaction paths in mechanism 1. Its first reaction path (p1) involves a proton transfer that occurs immediately after the hydrolytic cleavage, so that the proton transfer is the rate-determining step, which is followed by the entry of two water molecules. Its second reaction path (p2) consists of the entry of two water molecules right after the hydrolytic cleavage, but with no proton transfer; thus, hydrolytic cleavage is the rate-limiting step. The most likely catalytic path occurs in mechanism 1, following the second reaction path (p2), since it involves the lowest free energy activation barrier (ΔG(⧧) = 23.7 kcal mol(-1), in aqueous solution). A kinetic analysis showed that the experimental k(obs) value of 1.7 × 10(-5) s(-1) agrees with the calculated value k1 = 2.6 × 10(-5) s(-1); the concerted mechanism is kinetically favorable. The KIE (kinetic isotope effect) analysis applied to the second reaction path (p2) in mechanism 1 was also taken into account to assess the changes that take place in TS1-i (transition state of mechanism 1) and to perfectly characterize the mechanism described herein.
Using expert opinion to quantify accuracy and reliability of nondestructive evaluation on bridges.
DOT National Transportation Integrated Search
2015-08-01
Bridge inspection is an important phase in bridge management. In 2009, a joint American Society of Civil : Engineers Structural Engineering Institute and AASHTO Ad-Hoc group was created to identify the issues : in bridge safety and to study current b...
Didia, E E; Akon, A B; Thiam, A; Djeredou, K B
2010-03-01
One of the concerns of the dental surgeon in the realization of any operational act is the durability of this one. The mechanical resistance of the provisional prostheses contributes in a large part to the durability of those. The resins in general, have weak mechanical properties. The purpose of this study is to evaluate the resistance in inflection of temporary bridges reinforced with glass fibre. To remedy the weak mechanical properties of resins, we thought in this study, to reinforce them with glass fibres. For this purpose, we realized with two different resins, four groups of temporary bridges of 3 elements, including two groups reinforced fibreglass and the others not. Tests of inflection 3 points have been made on these bridges and resistance to fracture was analysed. The statistical tests showed a significant difference in four groups with better resistance for the reinforced bridges.
Relationship between ion pair geometries and electrostatic strengths in proteins.
Kumar, Sandeep; Nussinov, Ruth
2002-01-01
The electrostatic free energy contribution of an ion pair in a protein depends on two factors, geometrical orientation of the side-chain charged groups with respect to each other and the structural context of the ion pair in the protein. Conformers in NMR ensembles enable studies of the relationship between geometry and electrostatic strengths of ion pairs, because the protein structural contexts are highly similar across different conformers. We have studied this relationship using a dataset of 22 unique ion pairs in 14 NMR conformer ensembles for 11 nonhomologous proteins. In different NMR conformers, the ion pairs are classified as salt bridges, nitrogen-oxygen (N-O) bridges and longer-range ion pairs on the basis of geometrical criteria. In salt bridges, centroids of the side-chain charged groups and at least a pair of side-chain nitrogen and oxygen atoms of the ion-pairing residues are within a 4 A distance. In N-O bridges, at least a pair of the side-chain nitrogen and oxygen atoms of the ion-pairing residues are within 4 A distance, but the distance between the side-chain charged group centroids is greater than 4 A. In the longer-range ion pairs, the side-chain charged group centroids as well as the side-chain nitrogen and oxygen atoms are more than 4 A apart. Continuum electrostatic calculations indicate that most of the ion pairs have stabilizing electrostatic contributions when their side-chain charged group centroids are within 5 A distance. Hence, most (approximately 92%) of the salt bridges and a majority (68%) of the N-O bridges are stabilizing. Most (approximately 89%) of the destabilizing ion pairs are the longer-range ion pairs. In the NMR conformer ensembles, the electrostatic interaction between side-chain charged groups of the ion-pairing residues is the strongest for salt bridges, considerably weaker for N-O bridges, and the weakest for longer-range ion pairs. These results suggest empirical rules for stabilizing electrostatic interactions in proteins. PMID:12202384
NASA Astrophysics Data System (ADS)
Maskaeva, L. N.; Fedorova, E. A.; Yusupov, R. A.; Markov, V. F.
2018-05-01
The potentiometric titration of tin chloride SnCl2 is performed in the concentration range of 0.00009-1.1 mol/L with a solution of sodium hydroxide NaOH. According to potentiometric titration data based on modeling equilibria in the SnCl2-H2O-NaOH system, basic equations are generated for the main processes, and instability constants are calculated for the resulting hydroxo complexes and equilibrium constants of low-soluble tin(II) compounds. The data will be of interest for specialists in the field of theory of solutions.
Simplified bridge load rating methodology using the national bridge inventory file : user manual
DOT National Transportation Integrated Search
1988-08-01
The purpose of this research was to develop a computerized system to determine the adequacy of a bridge or group of bridges to carry specified overload vehicles. The system utilizes two levels of analysis. The Level 1 analysis is the basic rating sys...
Simplified bridge load rating methodology using the national bridge inventory file : program listing
DOT National Transportation Integrated Search
1987-08-01
The purpose of this research was to develop a computerized system to determine the adequacy of a bridge or group of bridges to carry specified overload vehicles. The system utilizes two levels of analysis. The Level 1 analysis is the basic rating sys...
Yoshitake, Shuichi; Kinoshita, Osamu; Nawata, Kan; Hoshino, Yasuhiro; Itoda, Yoshifumi; Kimura, Mitsutoshi; Yamauchi, Haruo; Ono, Minoru
2018-06-25
Currently, we use the Nipro paracorporeal VAD (p-VAD) for initial short-term ventricular support, as a bridge to decision (BTD) or a bridge to candidacy (BTC) treatment, in Interagency Registry for Mechanically Assisted Circulatory Support (INTERMACS) levels 1 and 2 patients. However, it is possible that compared to patients with primary implantable-VADs (P-iVAD), the bridge-to-bridge (BTB) patients are more likely to develop complications. This retrospective study used data from 24 consecutive BTB patients who were initially implanted with Nipro p-VAD as BTD or BTC treatments between April 2011 and March 2016, and subsequently underwent conversion to an i-VAD. The data from 72 patients who underwent a primary i-VAD (P-iVAD) procedure were used for comparison. Between the two groups, there was no significant difference in the incidence of infectious events (p = 0.72) or stroke (p = 0.44). Orthotropic heart transplantation was performed in 6 of the 24 patients in the BTB group and in 21 of the 72 patients in the P-iVAD group. The 1- and 2-year survival rates were 95.8% and 95.8% in the BTB group and 91% and 85.8% in the P-iVAD group; these values were not significantly different between groups (p = 0.91). Based on these results we conclude that BTB using Nipro p-VAD is a reasonable strategy for treating patients with severe decompensated end-stage heart failure.
Modal Identification of Tsing MA Bridge by Using Improved Eigensystem Realization Algorithm
NASA Astrophysics Data System (ADS)
QIN, Q.; LI, H. B.; QIAN, L. Z.; LAU, C.-K.
2001-10-01
This paper presents the results of research work on modal identification of Tsing Ma bridge ambient testing data by using an improved eigensystem realization algorithm. The testing was carried out before the bridge was open to traffic and after the completion of surfacing. Without traffic load, ambient excitations were much less intensive, and the bridge responses to such ambient excitation were also less intensive. Consequently, the bridge responses were significantly influenced by the random movement of heavy construction vehicles on the deck. To cut off noises in the testing data and make the ambient signals more stationary, the Chebyshev digital filter was used instead of the digital filter with a Hanning window. Random decrement (RD) functions were built to convert the ambient responses to free vibrations. An improved eigensystem realization algorithm was employed to improve the accuracy and the efficiency of modal identification. It uses cross-correlation functions ofRD functions to form the Hankel matrix instead of RD functions themselves and uses eigenvalue decomposition instead of singular value decomposition. The data for response accelerations were acquired group by group because of limited number of high-quality accelerometers and channels of data loggers available. The modes were identified group by group and then assembled by using response accelerations acquired at reference points to form modes of the complete bridge. Seventy-nine modes of the Tsing Ma bridge were identified, including five complex modes formed in accordance with unevenly distributed damping in the bridge. The identified modes in time domain were then compared with those identified in frequency domain and finite element analytical results.
Bridge inspector's manual for movable bridges.
DOT National Transportation Integrated Search
1977-01-01
Importance of Inspection-Movable bridges are built to the rigid specifications : of such groups as the American Association of State Highway and : Transportation Officials (AASHTO), the American Road Builders Association : (ARBA) and Underwriters Lab...
Ren, Jiangtao; Xu, Cong; Liu, Xianglin; Wang, Jiansong; Li, Zhihuai; Lü, Yongming
2017-10-01
To explore the effectiveness of the arthroscopic separate double-layer suture bridge technique in treatment of the delaminated rotator cuff tear. Between May 2013 and May 2015, 54 patients with the delaminated rotator cuff tears were recruited in the study. They were randomly allocated into 2 groups to receive repair either using arthroscopic separate double-layer suture bridge technique (trial group, n =28) or using arthroscopic whole-layer suture bridge technique (control group, n =26). There was no significant difference in gender, age, injured side, tear type, and preoperative visual analogue scale (VAS) score, Constants score, American Shoulder and Elbow Surgeons (ASES) score, University of California Los Angeles (UCLA) score, and the range of motion of shoulder joint between 2 groups ( P >0.05). Postoperative functional scores, range of motion, and recurrence rate of tear in 2 groups were observed and compared. The operation time was significant longer in trial group than in control group ( t =8.383, P =0.000). All incisions healed at stage Ⅰ without postoperative complication. All the patients were followed up 12 months. At 12 months postoperatively, the UCLA score, ASES score, VAS score, Constant score, and the range of motion were significantly improved when compared with the preoperative values in 2 groups ( P <0.05). However there was no significant difference in above indexes between 2 groups ( P >0.05). Four cases (14.3%) of rotator cuff tear recurred in trial group while 5 cases (19.2%) in control group, showing no significant difference ( χ 2 =0.237, P =0.626). Compared with the arthroscopic whole-layer suture bridge technique, arthroscopic separate double-layer suture bridge technique presents no significant difference in the shoulder function score, the range of motion, and recurrence of rotator cuff tear, while having a longer operation time.
Bridging Studies: An Alternative Pathway to University for Rural Australians.
ERIC Educational Resources Information Center
Ellis, Bronwyn; Cooper, Nancy; Sawyer, Janet
Bridging courses are courses that prepare adult and other nontraditional students for undergraduate study. Focus groups examined the strengths, limitations, and impacts of bridging courses offered at a rural university campus in South Australia. A survey based on their responses was returned by 12 current students in bridging courses and 2 who had…
Tseng, Hsi-Ching; Chen, Hsing-Yin; Huang, Yen-Tzu; Lu, Wei-Yi; Chang, Yu-Lun; Chiang, Michael Y; Lai, Yi-Chun; Chen, Hsuan-Ying
2016-02-15
A series of titanium (Ti) complexes bearing hydrazine-bridging Schiff base ligands were synthesized and investigated as catalysts for the ring-opening polymerization (ROP) of L-lactide (LA). Complexes with electron withdrawing or steric bulky groups reduced the catalytic activity. In addition, the steric bulky substituent on the imine groups reduced the space around the Ti atom and then reduced LA coordination with Ti atom, thereby reducing catalytic activity. All the dinuclear Ti complexes exhibited higher catalytic activity (approximately 10-60-fold) than mononuclear L(Cl-H)-TiOPr2 did. The strategy of bridging dinuclear Ti complexes with isopropoxide groups in the ROP of LA was successful, and adjusting the crowded heptacoordinated transition state by the bridging isopropoxide groups may be the key to our successful strategy.
BUILDING "BRIDGES" WITH QUALITY ASSURANCE
The papr describes how, rather than building "bridges" across centuries, quality assurance (QA) personnel have the opportunity to build bridges across technical disciplines, between public and private organizations, and between different QA groups. As reviewers and auditors of a...
Werthel, Jean-David; Pelissier, Alexandre; Massin, Philippe; Boyer, Patrick; Valenti, Philippe
2014-10-01
The double row cuff repair with suture bridging is commonly used for arthroscopic rotator cuff repair (RCR). Despite its biomechanical qualities, the rate of iterative tears with this technique is important. The aim of our study was to evaluate the effect of autologous conditioned plasma (ACP) on functional results and on the rate of iterative tears after RCR by suture bridging. A consecutive series of 65 patients who underwent arthroscopic double-row suture bridge (Speed-Bridge, Arthrex) primary cuff repair of symptomatic full-thickness supraspinatus tear (retraction <3 in the Patte classification) were evaluated. Mean patient age was 60 (+/-8). The supraspinatus was repaired by knot-less bridging (SwiveLock, Arthrex) with suture tape material. 2 homogenous groups were created (A: 33 patients, B: 32 patients). In group A, all patients received, besides the cuff repair, an intra-tendinous ACP injection. Constant scores and Simple Shoulder Tests (SST) were measured pre-operatively and after a minimum follow-up period of 12 months post-operatively. Structural integrity of the repairs was evaluated by MRI according to the Sugaya classification. Sugaya >4 were considered as iterative tears. Mean follow-up was 19 months (+/-42) in the 2 groups. The mean quantity of ACP injected was 6ml. (+/-1.5) and no specific complication of the injection was found. Mean preoperative Constant-Murley scores were 41,2 (±7,7) and 38 (±11)in group B. Mean normalized Constant-Murley score increased from 41 points (±7) pre-operatively to 70 points (±8) post-operatively in group A and from 38 points (±11) to 73 points (±11) in group B. There were no significative differences between the two groups (P > 0.05). In group A, 31 repairs were Sugaya 1-3 (94%), vs. 30 in group B (93%), and 1 was type 4 in group A (5%) vs. 2 in group B (8%). In both groups, RCR with suture bridging gave successful functional outcomes, with a low rate of iterative tear. In this preliminary study, the adjuvant effect of ACP injections could not be showed on both functional and structural results. Longer follow-up is needed to evaluate potential differences.
Full-Scale Testing of Thermoplastic Composite I-Beams for Bridges
2017-06-01
ER D C/ CE RL T R- 17 -1 8 ACSIM Technology Standards Group Full-Scale Testing of Thermoplastic Composite I-Beams for Bridges Co ns tr...default. ACSIM Technology Standards Group ERDC/CERL TR-17-18 June 2017 Full-Scale Testing of Thermoplastic Composite I-Beams for Bridges Ghassan... tests were con- ducted on commercially available, thermoplastic polymer composite I- beams at U.S. Army Corps of Engineers, Engineer Research and
The evolution of massive stars: bridging the gap in the Local Group
NASA Astrophysics Data System (ADS)
Massey, Philip; Neugent, Kathryn F.; Levesque, Emily M.
2017-09-01
The nearby galaxies of the Local Group can act as our laboratories in helping to bridge the gap between theory and observations. In this review, we will describe the complications of identifying samples of OB stars, yellow and red supergiants, and Wolf-Rayet stars, and what we have so far learned from these studies. This article is part of the themed issue 'Bridging the gap: from massive stars to supernovae'.
The Great American Biotic Interchange in birds
Weir, Jason T.; Bermingham, Eldredge; Schluter, Dolph
2009-01-01
The sudden exchange of mammals over the land bridge between the previously isolated continents of North and South America is among the most celebrated events in the faunal history of the New World. This exchange resulted in the rapid merging of continental mammalian faunas that had evolved in almost complete isolation from each other for tens of millions of years. Yet, the wider importance of land bridge-mediated interchange to faunal mixing in other groups is poorly known because of the incompleteness of the fossil record. In particular, the ability of birds to fly may have rendered a land bridge unnecessary for faunal merging. Using molecular dating of the unique bird faunas of the two continents, we show that rates of interchange increased dramatically after land bridge completion in tropical forest-specializing groups, which rarely colonize oceanic islands and have poor dispersal abilities across water barriers, but not in groups comprised of habitat generalists. These results support the role of the land bridge in the merging of the tropical forest faunas of North and South America. In contrast to mammals, the direction of traffic across the land bridge in birds was primarily south to north. The event transformed the tropical avifauna of the New World. PMID:19996168
Instrumentation, monitoring, and modeling of the I-35W bridge.
DOT National Transportation Integrated Search
2012-08-01
The new I-35W Bridge was instrumented incorporating "smart bridge technology" by Figg Engineering Group in : conjunction with Flatiron-Manson. The purpose of the instrumentation was to monitor the structure during service, : and to use this informati...
The evolution of massive stars: bridging the gap in the Local Group.
Massey, Philip; Neugent, Kathryn F; Levesque, Emily M
2017-10-28
The nearby galaxies of the Local Group can act as our laboratories in helping to bridge the gap between theory and observations. In this review, we will describe the complications of identifying samples of OB stars, yellow and red supergiants, and Wolf-Rayet stars, and what we have so far learned from these studies.This article is part of the themed issue 'Bridging the gap: from massive stars to supernovae'. © 2017 The Author(s).
Increase in mean platelet volume in patients with myocardial bridge.
Bilen, Emine; Tanboga, Ibrahim Halil; Kurt, Mustafa; Kocak, Umran; Ayhan, Huseyin; Keles, Telat; Bozkurt, Engin
2013-01-01
Myocardial bridge is associated with atherosclerosis altered in shear stress and endothelial dysfunction. Mean platelet volume (MPV), a determinant of platelet activation, is shown to be related with atherosclerosis and endothelial dysfunction. In this study, we aimed to evaluate platelet function assessed by MPV in patients with myocardial bridge. Forty-two patients with myocardial bridge in the left anterior descending artery (LAD) and 43 age- and gender-matched healthy participants were included in the study. Myocardial bridging was defined as an intramyocardial systolic compression or milking of a segment of an epicardial coronary artery on angiography. For the entire study population, MPV was measured using an automatic blood counter. The study population consisted of 42 patients with myocardial bridge (52.7 ± 10.2, 76.2% male) and 43 age- and sex-matched healthy control participants (52.1 ± 10.4, 74.4% male). Compared to the control group, MPV value was significantly higher in patients with myocardial bridge (8.9 ± 1.24 vs 8.3 ± 0.78; P = .01). Further, there were no significant differences between groups regarding hemoglobin level, platelet count, fasting blood glucose, and creatinine levels. Our study findings indicated that myocardial bridge is associated with elevated MPV values. Our results might partly explain the increased cardiovascular events in patients with myocardial bridge.
Cho, Misuk
2013-01-01
[Purpose] The purpose of this study was to compare the effects of bridge exercises applying the abdominal drawing-in method and modified wall squat exercises on deep abdominal muscle thickness and lumbar stability. [Subjects] A total of 30 subjects were equally divided into an experimental group and a control group. [Methods] The experimental group completed modified wall squat exercises, and the control group performed bridge exercises. Both did so for 30 minutes three times per week over a six-week period. Both groups’ transversus abdominis (Tra), internal oblique (IO), and multifidus muscle thickness were measured using ultrasonography, while their static lumbar stability and dynamic lumbar stability were measured using a pressure biofeedback unit. [Results] A comparison of the pre-intervention and post-intervention measures of the experimental group and the control group was made; the Tra and IO thicknesses were significantly different in both groups. [Conclusion] The modified wall squat exercise and bridge exercise affected the thicknesses of the Tra and the IO muscles. While the bridge exercise requirs space and a mattress to lie on, the modified wall squat exercise can be conveniently performed anytime. PMID:24259831
NASA Astrophysics Data System (ADS)
Braund, Martin; Hames, Vicky
2005-07-01
This article reports research from a project set up to implement ‘bridging work’ in science in England. Group interviews of 59 pupils in Year 6 (at the end of primary school) and 48 pupils in Year 7 (at beginning of secondary school) were carried out after pupils had completed bridging work. Twenty-six of this sample were the same pupils. Semi-structured interviews were carried out in groups to ascertain: their aspirations and fears concerning secondary science, their reactions to bridging work and their memories of investigations. Year 6 pupils were positive about studying science at secondary school and remained so after transfer. Pupils' reactions to bridging at both ages were very positive. Findings challenge recent critiques of bridging. The lack of progression in pupils' communication about the variables and findings from investigations suggest that the planned progression of work was not recognized by some teachers. Bridging work alone may not guarantee improved progression and continuity in science, but as part of a carefully planned and structured programme of collaboration it has merit.
Dorsal bridge plating or transarticular screws for Lisfranc fracture dislocations.
Kirzner, N; Zotov, P; Goldbloom, D; Curry, H; Bedi, H
2018-04-01
Aims The aim of this retrospective study was to compare the functional and radiological outcomes of bridge plating, screw fixation, and a combination of both methods for the treatment of Lisfranc fracture dislocations. Patients and Methods A total of 108 patients were treated for a Lisfranc fracture dislocation over a period of nine years. Of these, 38 underwent transarticular screw fixation, 45 dorsal bridge plating, and 25 a combination technique. Injuries were assessed preoperatively according to the Myerson classification system. The outcome measures included the American Orthopaedic Foot and Ankle Society (AOFAS) score, the validated Manchester Oxford Foot Questionnaire (MOXFQ) functional tool, and the radiological Wilppula classification of anatomical reduction. Results Significantly better functional outcomes were seen in the bridge plate group. These patients had a mean AOFAS score of 82.5 points, compared with 71.0 for the screw group and 63.3 for the combination group (p < 0.001). Similarly, the mean Manchester Oxford Foot Questionnaire score was 25.6 points in the bridge plate group, 38.1 in the screw group, and 45.5 in the combination group (p < 0.001). Functional outcome was dependent on the quality of reduction (p < 0.001). A trend was noted which indicated that plate fixation is associated with a better anatomical reduction (p = 0.06). Myerson types A and C2 significantly predicted a poorer functional outcome, suggesting that total incongruity in either a homolateral or divergent pattern leads to worse outcomes. The greater the number of columns fixed the worse the outcome (p < 0.001). Conclusion Patients treated with dorsal bridge plating have better functional and radiological outcomes than those treated with transarticular screws or a combination technique. Cite this article: Bone Joint J 2018;100-B:468-74.
Integrating Gender and Group Differences into Bridging Strategy
NASA Astrophysics Data System (ADS)
Yılmaz, Serkan; Eryılmaz, Ali
2010-08-01
The main goal of this study was to integrate gender and group effect into bridging strategy in order to assess the effect of bridging analogy-based instruction on sophomore students' misconceptions in Newton's Third Law. Specifically, the authors developed and benefited from anchoring analogy diagnostic test to merge the effect of group and gender into the strategy. Newton's third law misconception test, attitude scale toward Newton's third law, and classroom observation checklists were the other measuring tools utilized throughout this quasi-experimental study. The researchers also developed or used several teaching/learning materials such as gender and group splitted concept diagrams, lesson plans, gender splitted frequency tables, make sense scales, PowerPoint slides, flash cards, and demonstrations. The convenience sample of the study chosen from the accessible population involved 308 students from two public universities. The results of multivariate analysis of covariance indicated that the bridging strategy had a significant effect on students' misconceptions in Newton's third law whereas it had no significant effect on students' attitudes toward Newton's third law.
Company, Anna; Jee, Joo-Eun; Ribas, Xavi; Lopez-Valbuena, Josep Maria; Gómez, Laura; Corbella, Montserrat; Llobet, Antoni; Mahía, José; Benet-Buchholz, Jordi; Costas, Miquel; van Eldik, Rudi
2007-10-29
A study of the reversible CO2 fixation by a series of macrocyclic dicopper complexes is described. The dicopper macrocyclic complexes [Cu2(OH)2(Me2p)](CF3SO3)2, 1(CF3SO3)2, and [Cu2(mu-OH)2(Me2m)](CF3SO3)2, 2(CF3SO3)2, (Scheme 1) containing terminally bound and bridging hydroxide ligands, respectively, promote reversible inter- and intramolecular CO2 fixation that results in the formation of the carbonate complexes [{Cu2(Me2p)}2(mu-CO3)2](CF3SO3)4, 4(CF3SO3)4, and [Cu2(mu-CO3)(Me2m)](CF3SO3)2, 5(CF3SO3)2. Under a N2 atmosphere the complexes evolve CO2 and revert to the starting hydroxo complexes 1(CF3SO3)2 and 2(CF3SO3)2, a reaction the rate of which linearly depends on [H2O]. In the presence of water, attempts to crystallize 5(CF3SO3)2 afford [{Cu2(Me2m)(H2O)}2(mu-CO3)2](CF3SO3)4, 6(CF3SO3)4, which appears to rapidly convert to 5(CF3SO3)2 in acetonitrile solution. [Cu2(OH)2(H3m)]2+, 7, which contains a larger macrocyclic ligand, irreversibly reacts with atmospheric CO2 to generate cagelike [{Cu2(H3m)}2(mu-CO3)2](ClO4)4, 8(ClO4)4. However, addition of 1 equiv of HClO4 per Cu generates [Cu2(H3m)(CH3CN)4]4+ (3), and subsequent addition of Et3N under air reassembles 8. The carbonate complexes 4(CF3SO3)4, 5(CF3SO3)2, 6(CF3SO3)4, and 8(ClO4)4 have been characterized in the solid state by X-ray crystallography. This analysis reveals that 4(CF3SO3)4, 6(CF3SO3)4, and 8(ClO4)4 consist of self-assembled molecular boxes containing two macrocyclic dicopper complexes, bridged by CO32- ligands. The bridging mode of the carbonate ligand is anti-anti-mu-eta1:eta1 in 4(CF3SO3)4, anti-anti-mu-eta2:eta1 in 6(CF3SO3)4 and anti-anti-mu-eta2:eta2 in 5(CF3SO3)2 and 8(ClO4)4. Magnetic susceptibility measurements on 4(CF3SO3)4, 6(CF3SO3)4, and 8(ClO4)4 indicate that the carbonate ligands mediate antiferromagnetic coupling between each pair of bridged CuII ions (J = -23.1, -108.3, and -163.4 cm-1, respectively, H = -JS1S2). Detailed kinetic analyses of the reaction between carbon dioxide and the macrocyclic complexes 1(CF3SO3)2 and 2(CF3SO3)2 suggest that it is actually hydrogen carbonate formed in aqueous solution on dissolving CO2 that is responsible for the observed formation of the different carbonate complexes controlled by the binding mode of the hydroxy ligands. This study shows that CO2 fixation can be used as an on/off switch for the reversible self-assembly of supramolecular structures based on macrocyclic dicopper complexes.
Yun, Sung Su; Hwang, Dae Wook; Kim, Se Won; Park, Sang Hwan; Park, Sang Jin; Lee, Dong Shick; Kim, Hong Jin
2010-07-01
Laparoscopic cholecystectomy is the best treatment choice for acute cholecystitis. However, it still carries high conversion and mortality rates. The purpose of this study was to find out better treatment strategies for high surgical risk patients with acute cholecystitis. Between January 2002 and June 2008, we performed percutaneous cholecystostomy instead of emergency cholecystectomy in 44 patients with acute cholecystitis and American Society of Anesthesiologists (ASA) classification 3 or greater. This was performed in 31 patients as a bridge procedure before elective cholecystectomy (bridge group) and as a palliative procedure in 11 patients (palliation group). The mean age of patients was 71.6 years (range 52-86 years). The mean ASA classifications before and after percutaneous cholecystostomy were 3.3 +/- 0.5 and 2.5 +/- 0.6, respectively, in the bridge group, and 3.6 +/- 0.7 and 3.1 +/- 1.0, in the palliation group, respectively. Percutaneous cholecystostomy was technically successful in all patients. There were two deaths after percutaneous cholecystostomy in the palliation group due to underlying ischemic heart disease and multiple organ failure. Resumption of oral intake was possible 2.9 +/- 1.8 days in the bridge group and 3.9 +/- 3.5 days in the palliation group after percutaneous cholecystostomy. We attempted 17 laparoscopic cholecystectomies and experienced one failure due to bile duct injury (success rate: 94.1%). The postoperative course of all cholecystectomy patients was uneventful. Percutaneous cholecystostomy is an effective bridge procedure before cholecystectomy in patients with acute cholecystitis and ASA classification 3 or greater.
De Rita, Fabrizio; Hasan, Asif; Haynes, Simon; Peng, Edward; Gandolfo, Fabrizio; Ferguson, Lee; Kirk, Richard; Smith, Jon; Griselli, Massimo
2015-12-01
Mechanical cardiac support (MCS) can successfully be applied as a bridging strategy for heart transplantation (OHTx) in children with life-threatening heart failure. Emergent use of MCS is often required before establishing the likelihood of OHTx. This can require bridge-to-bridge strategies to increase survival on the waiting list. We compared the outcome of children with heart failure who underwent single MCS with those who required multiple MCS as a bridge to OHTx. A retrospective study of patients aged less than 16 years was conducted. From March 1998 to October 2005, we used either a veno-arterial extracorporeal membrane oxygenator (VA-ECMO), or the Medos® para-corporeal ventricular assist device (VAD). From November 2005 onwards, the Berlin Heart EXCOR® (BHE) device was implanted in the majority of cases. Several combinations of bridge-to-bridge strategies have been used: VA-ECMO and then conversion to BHE; BHE and then conversion to VA-ECMO; left VAD and then upgraded to biventricular support (BIVAD); conversion from pulsatile to continuous-flow pumps. A total of 92 patients received MCS with the intent to bridge to OHTx, including 21 (23%) supported with more than one modality. The mean age and weight at support was similar in both groups, but multimodality MCS was used more often in infancy (P = 0.008) and in children less than 10 kg in weight (P = 0.02). The mean duration of support was longer in the multiple MCS group: 40 ± 48 vs 84 ± 43 days (P = 0.0003). Usage of multimodality MCS in dilated cardiomyopathy (19%) and in other diagnoses (29%) was comparable. Incidence of major morbidity (haematological sequelae, cerebrovascular events and sepsis) was similar in both groups. Survival to OHTx/explantation of the device (recovery) and survival to discharge did not differ between single MCS and multiple MCS groups (78 vs 81% and 72 vs 76%, respectively). Bridge to OHTx with multiple MCS does not seem to influence the outcome in our population. Infancy and body weight less than 10 kg do not tend to produce higher mortality in the multiple MCS group. However, children receiving more than one modality are supported for longer durations. © The Author 2015. Published by Oxford University Press on behalf of the European Association for Cardio-Thoracic Surgery. All rights reserved.
Matsunaga, Fabio Teruo; Tamaoki, Marcel Jun Sugawara; Matsumoto, Marcelo Hide; Netto, Nicola Archetti; Faloppa, Flavio; Belloti, Joao Carlos
2017-04-05
Nonoperative treatment has historically been considered the standard for fractures of the shaft of the humerus. Minimally invasive bridge-plate osteosynthesis for isolated humeral shaft fractures has been proven to be a safe technique, with good and reproducible results. This study was designed to compare clinical and radiographic outcomes between patients who had been treated with bridge plate osteosynthesis and those who had been managed nonoperatively with a functional brace. A prospective randomized trial was designed and included 110 patients allocated to 1 of 2 groups: surgery with a bridge plate or nonoperative treatment with a functional brace. The primary outcome was the Disabilities of the Arm, Shoulder and Hand (DASH) score at 6 months. The score on the Short Form-36 (SF-36) life-quality questionnaire, complications of treatment, Constant-Murley score for the shoulder, pain level, and radiographic results were assessed as secondary outcomes. Participants were assessed at 2 weeks; 1, 2, and 6 months; and 1 year after the interventions. The mean DASH score of the bridge plate group was statistically superior to that of the functional brace group (mean scores, 10.9 and 16.9, respectively; p = 0.046) only at 6 months. The bridge plate group also had a significantly more favorable nonunion rate (0% versus 15%) and less mean residual angular displacement seen on the anteroposterior radiograph (2.0° versus 10.5°) (both p < 0.05). No difference between the groups was detected with regard to the SF-36 score, pain level, Constant-Murley score, or angular displacement seen on the lateral radiograph. This trial demonstrates that, compared with functional bracing, surgical treatment with a bridge plate has a statistically significant advantage, of uncertain clinical benefit, with respect to self-reported outcome (DASH score) at 6 months, nonunion rate, and residual deformity in the coronal plane as seen on radiographs. Therapeutic Level I. See Instructions for Authors for a complete description of levels of evidence.
Doan, Jon B; Copeland, Jennifer L; Brown, Lesley A; Newman, Jeff T; Hudson, D Shane
2014-01-01
Bridge employment (scheduled paid work after retirement age) may promote successful aging and continued health, as work can be an important component of daily physical activity. Appropriate work demands for older adults are neither well-established nor well-applied, however, and excessive loading or increased perceptions of discomfort may negate the health benefits of work activity. This study examined work status and musculoskeletal discomfort (MSD) amongst older Albertans. 1044 Albertans aged 55 years and older participating in an organized 'Games' received a research package. Enclosed in the package were an introductory letter, a return envelope, and modified versions of validated questionnaires examining leisure and work activities, activity frequency, and perceptions of musculoskeletal health. 228 respondents were classified into one of three employment trajectory groups: fully retired, fully employed, or bridge employed. Groups differed in age, and both employed groups more frequently reported MSDs in all body areas. Bridge employed reported increased 'occasional' frequency of musculoskeletal injury risk factors, while both groups reported similar overall ratings of work-related exertion. The increased MSDs reported by bridge employed adults may be the result of irregularity of work activity and soft tissue loading. Detailed examination of work demands and musculoskeletal injuries amongst bridge employed adults could help define safer levels for less regular work activity.
Laser-synthesized Y2O3:Eu3+ nanophosphors and their stabilization in water suspensions
NASA Astrophysics Data System (ADS)
Ivanov, M. G.; Krutikova, I. V.; Kynast, U.; Lezhnina, M.; Puzyrev, I. S.
2017-12-01
Europium doped yttrium oxide nanophosphors (Y2O3 doped with 5% Eu3+), which consists of spherical single-phase monoclinic particles with an average size of 17 nm, was prepared by laser synthesis. While the monoclinic material has a low efficiency of only 19% of a μm-sized commercial Y2O3:Eu product, the cubic phase after calcination at 900 °C achieves 68% despite the remaining hydroxo-groups at the surface and still small crystallite size (56 nm). An ethanolammonium salt of citric acid (Dolapix CE64) was used as a dispersant in water suspension. To estimate the stability of the dispersed phase, the electrokinetic potential and agglomerate sizes were measured as a function of pH. With this dispersant, a 30 wt% nanopowder water suspension, showing a Newtonian viscosity of about 6 mPa × s, was obtained. Maximum content of the nanopowder of about 60 wt% can be accomplished in the slurry, still fluid enough to be used to cast a highly uniform and dense ceramic green body to sinter nanostructured Y2O3:Eu3+ phosphors ceramics.
CAMPARE and Cal-Bridge: Two Institutional Networks Increasing Diversity in Astronomy
NASA Astrophysics Data System (ADS)
Rudolph, Alexander L.; Smecker-Hane, Tammy A.
2017-01-01
We describe two programs, CAMPARE and Cal-Bridge, with the common mission of increasing participation of groups traditionally underrepresented in astronomy, through summer research opportunities, in the case of CAMPARE, scholarships in the case of Cal-Bridge, and significant mentoring in both programs, creating a national impact on their numbers successfully pursuing a PhD in the field.In 7 years, the CAMPARE program has sent 80 students, >80% from underrepresented groups, to conduct summer research at one of 14 major research institutions throughout the country. The graduation rate among CAMPARE scholars is 98%, and of the CAMPARE scholars who have graduated with a Bachelor’s degree, more than 60% have completed or are pursuing graduate education in astronomy or a related field, at institutions including UCLA, UC Riverside, UC Irvine, UC Santa Barbara, USC, Stanford, Univ. of Arizona, Univ. of Washington, and the Fisk-Vanderbilt Master’s-to-PhD program.Now entering its third year, the Cal-Bridge program is a CSU-UC Bridge program comprised of over 75 physics and astronomy faculty from 5 University of California (UC), 9 California State University (CSU), and 14 California Community College (CCC) campuses in Southern California. In the first three years, 22 Cal-Bridge Scholars have been selected, including 11 Hispanic, 3 African-American and 8 female students, 5 of whom are from URM groups. Nineteen (19) of the 22 Cal-Bridge Scholars are first-generation college students. The entire first cohort of 4 Cal-Bridge scholars was accepted to one or more PhD programs in astronomy or physics, including UC Irvine, UC Santa Cruz, UC Davis, Michigan State, and Georgia State Universities. The second cohort of 8 Cal-Bridge scholars is applying to graduate schools this fall.Cal-Bridge provides much deeper mentoring and professional development experiences over the last two years of undergraduate and first year of graduate school to students from this diverse network of higher education institutions. Cal-Bridge Scholars benefit from substantial financial support, intensive, joint mentoring by CSU and UC faculty, professional development workshops, and exposure to research opportunities at the participating UC campuses.
2013-01-01
Background To date, only a small amount of research on bonding/bridging social capital has separately examined their effects on health though they have been thought to have differential effects on health outcomes. By using a large population-based sample of elderly Japanese people, we sought to investigate the association between bonding and bridging social capital and self-rated health for men and women separately. Methods In August 2010, questionnaires were sent to all residents aged ≥65 years in three municipalities in Okayama prefecture (n = 21232), and 13929 questionnaires were returned (response rate: 65.6%). Social capital was measured from survey responses to questions on participation in six different types of groups: a) the elderly club or sports/hobby/culture circle; b) alumni association; c) political campaign club; d) citizen’s group or environmental preservation activity; e) community association; and f) religious organization. Participant perception of group homogeneity (gender, age, and previous occupation) was used to divide social capital into bonding or bridging. Odds ratios (ORs) and 95% confidence intervals (CIs) for poor self-rated health were calculated. Results A total of 11146 subjects (4441 men and 6705 women) were available for the analysis. Among men, bonding and bridging social capital were inversely associated with poor self-rated health (high bonding social capital; OR: 0.55, 95% CI: 0.31–0.99; high bridging social capital; OR: 0.62, 95% CI: 0.48–0.81) after adjusting for age, educational attainment, smoking status, frequency of alcohol consumption, overweight, living arrangements, and type-D personality. The beneficial effect among women was more likely limited to bonding social capital (high bonding social capital; OR: 0.34, 95% CI: 0.12–1.00), and the association between bridging social capital and self-rated health was less clear (high bridging social capital; OR: 0.69, 95% CI: 0.44–1.07). Conclusions Bonding/bridging social capital could have differential associations with self-rated health among the Japanese elderly depending on the individual’s sex. Considering the lack of consensus on how to measure bonding and bridging social capital, however, we need to carefully assess the generalizability of our findings. Further research is warranted to identify health-relevant dimensions of social capital in different cultural or economic settings. PMID:24341568
Wasser, Ian M; Martens, Constantinus F; Verani, Claudio N; Rentschler, Eva; Huang, Hong-Wei; Moënne-Loccoz, Pierre; Zakharov, Lev N; Rheingold, Arnold L; Karlin, Kenneth D
2004-01-26
In this paper, we describe the synthesis and study of a series of heme/non-heme Fe-O-Fe' complexes supported by a porphyrin and the tripodal nitrogen ligand TMPA [TMPA = tris(2-pyridylmethyl)amine]. The complete synthesis of [((6)L)Fe-O-Fe(X)](+) (1) (X = OMe(-) or Cl(-), 69:31 ratio), where (6)L is the dianion of 5-(o-O-[(N,N-bis(2-pyridylmethyl)-2-(6-methoxyl)pyridinemethanamine)phenyl]-10,15,20-tris(2,6-difluorophenyl)porphine, is reported. The crystal structure for 1.PF(6) reveals an intramolecular heme/non-heme diferric complex bridged by an Fe-O-Fe' moiety; 90 degree angle (Fe-O-Fe') = 166.7(3) degrees, and d(Fe.Fe') = 3.556 A. Crystal data for C(70)H(57)ClF(12)Fe(2)N(8)O(3)P (1.PF(6)): triclinic, Ponemacr;, a = 13.185(3) A, b = 14.590 (3) A, c = 16.885(4) A, alpha = 104.219(4) degrees, beta = 91.572(4) degrees, gamma = 107.907(4) degrees, V = 2977.3(11) A(3), Z = 2, T = 150(2) K. Complex 1 (where X = Cl(-)) is further characterized by UV-vis (lambda(max) = 328, 416 (Soret), 569 nm), (1)H NMR (delta 27-24 [TMPA -CH(2)-], 16.1 [pyrrole-H], 15.2-10.5 [PY-3H, PY-5H], 7.9-7.2 [m- and p-phenyl-H], 6.9-5.8 [PY-4H] ppm), resonance Raman (nu(as)(Fe-O-Fe') 844 cm(-)(1)), and Mössbauer (delta(Fe) = 0.47, 0.41 mm/s; deltaE(A) = 1.59, 0.55 mm/s; 80 K) spectroscopies, MALDI-TOF mass spectrometry (m/z 1202), and SQUID susceptometry (J = - 114.82 cm(-)(1), S = 0). We have also synthesized a series of 3-, 4-, and 5-methyl-substituted as well as selectively deuterated TMPA(Fe') complexes and condensed these with the hydroxo complex (F(8))FeOH or (F(8)-d(8))FeOH to yield "untethered" Fe-O-Fe' analogues. Along with selective deuteration of the methylene hydrogens in TMPA, complete (1)H NMR spectroscopic assignments for 1 have been accomplished. The magnetic properties of several of the untethered complexes and a comparison to those of 1 are also presented. Complex 1 and related species represent good structural and spectroscopic models for the heme/non-heme diiron active site in the enzyme nitric oxide reductase.
Code of Federal Regulations, 2012 CFR
2012-04-01
... the bridge formula. (c) The maximum gross weight upon any one axle, including any one axle of a group... following formula, referred to as the Bridge Gross Weight Formula: EC14OC91.012 except that two consecutive... derived from the Bridge Formula, up to a maximum of 80,000 pounds, including all enforcement tolerances...
Code of Federal Regulations, 2011 CFR
2011-04-01
... the bridge formula. (c) The maximum gross weight upon any one axle, including any one axle of a group... following formula, referred to as the Bridge Gross Weight Formula: EC14OC91.012 except that two consecutive... derived from the Bridge Formula, up to a maximum of 80,000 pounds, including all enforcement tolerances...
Kim, Yu-Ri; Yoo, Won-Gyu
2016-01-01
[Purpose] The purpose of this study was to investigate activities of the hip extensors and erector spinae during bridging exercise by using instruments with a laser pointer on the pelvic belt. [Subjects] Twelve subjects (age, 23 to 33 years) with non-specific low back pain volunteered for this study. [Methods] Subjects performed bridging exercises with and without trajectory exercises by using a laser pointer fixed to a pelvic strap. The erector spinae, gluteus maximus and hamstring activities with and without trajectory exercises using a laser pointer were recorded on using electromyography. [Results] Compared to the without laser pointer group, the group that underwent bridging with trajectory exercises using a laser pointer had significantly higher gluteus maximus activity and significantly lower erector spinae activity. Significantly higher gluteus maximus/erector spinae activity ratios were observed when performing trajectory exercises using a laser pointer during bridging exercises. [Conclusion] This result suggests that trajectory exercises using a laser pointer during a bridging exercise would be effective for improving gluteus maximus activity.
Eijgenraam, Pieter; ten Cate, Hugo; Ten Cate-Hoek, Arina
2013-01-01
Surgical interventions in patients on long term vitamin K antagonist (VKA) treatment create a dilemma; periprocedural interruption of anticoagulation raises the risk of thrombosis, while continuation raises the risk of bleeding. The anticoagulation- free interval is minimized by "bridging" with parenteral anticoagulants. The efficacy and safety of bridging with low molecular weight heparins (LMWH) has however not been unequivocally established. We performed an EMBASE and MEDLINE search for studies that compared bridging anticoagulation with continuation or cessation of VKA without bridging; with thromboembolism (TE) and bleeding as outcomes. We identified 878 articles and finally selected 17. Results of individual studies were pooled. None of the included studies reported significant differences in incidence of TEs between the bridging group and the comparator group; 4 out of 13 studies reported zero TEs. Heparin was identified as a risk factor for bleeding in multivariable adjusted analyses in 3 studies on pacemaker/implantable cardioverter defibrillator (PM/ICD) surgery. In 5 studies (different types of surgery) with unadjusted analyses, bridging was compared to warfarin cessation: 3 studies reported null results for bleeding; 2 studies identified bridging as a risk factor. We pooled a subset of 6 studies regarding postoperative bleeding after PM/ICD surgery and found a relative risk (RR) of 3.03 (95% confidence interval (CI), 1.86-4.95) for bridging compared to continuation of VKA. While the antithrombotic efficacy of bridging with LMWH has not been demonstrated, increased bleeding risk is observed in different types of surgery. PM/ICD surgery can be safely performed on continued VKA.
Extracorporeal Life Support Bridge to Ventricular Assist Device: The Double Bridge Strategy.
Marasco, Silvana F; Lo, Casey; Murphy, Deirdre; Summerhayes, Robyn; Quayle, Margaret; Zimmet, Adam; Bailey, Michael
2016-01-01
In patients requiring left ventricular assist device (LVAD) support, it can be difficult to ascertain suitability for long-term mechanical support with LVAD and eventual transplantation. LVAD implantation in a shocked patient is associated with increased morbidity and mortality. Interest is growing in the utilization of extracorporeal life support (ECLS) as a bridge-to-bridge support for these critically unwell patients. Here, we reviewed our experience with ECLS double bridging. We hypothesized that ECLS double bridging would stabilize end-organ dysfunction and reduce ventricular assist device (VAD) implant perioperative mortality. We conducted a retrospective review of prospectively collected data for 58 consecutive patients implanted with a continuous-flow LVAD between January 2010 and December 2013 at The Alfred Hospital, Melbourne, Victoria, Australia. Twenty-three patients required ECLS support pre-LVAD while 35 patients underwent LVAD implantation without an ECLS bridge. Preoperative morbidity in the ECLS bridge group was reflected by increased postoperative intensive care duration, blood loss, blood product use, and postoperative renal failure, but without negative impact upon survival when compared with the no ECLS group. ECLS stabilization improved end-organ function pre-VAD implant with significant improvements in hepatic and renal dysfunction. This series demonstrates that the use of ECLS bridge to VAD stabilizes end-organ dysfunction and reduces VAD implant perioperative mortality from that traditionally reported in these "crash and burn" patients. Copyright © 2015 International Center for Artificial Organs and Transplantation and Wiley Periodicals, Inc.
Biomechanical comparison of supraacetabular external fixation and anterior pelvic bridge plating.
Çavuşoğlu, Ali Turgay; Erbay, Fatma Kübra; Özsoy, Mehmet Hakan; Demir, Teyfik
2017-10-01
Unstable pelvic ring injuries are complex and risky injuries due to high morbidity and mortality. Although anterior pelvic external fixator is a suitable method for rapid stabilization of an injured pelvic ring, due to some disadvantages such as high complication rate, nerve damage, and difficulties of patient's mobility and comfort, there has recently been increased searching for alternative methods for stabilization of the pelvic ring. Pubic symphysis zone freely moves in pelvic models. This study aims to evaluate the biomechanical stability of anterior pelvic bridge plating and compare it with supraacetabular external fixators in an untreated unstable pelvic fracture model. Samples were loaded statically with 2-mm/min loading rate in single leg standing position. Maximum load was 2.3 kN. When loading the samples, photographs were taken continuously. Stiffness values were calculated from the load displacement curves. Some reference parameters were described and were measured from unloaded and 2.3-kN-loaded photographs of the test. The mean stiffness values were 491.14 ± 52.22, 478.55 ± 41.44, and 470.25 ± 44.51 N/mm for anterior pelvic bridge plating group, supraacetabular external fixator group, and Control group, respectively. According to the measured parameters from photographs, the mean displacement at the pubic symphysis was 4.7 ± 0.32, 15.8 ± 2.01, and 18.2 ± 0.47 mm for anterior pelvic bridge plating, supraacetabular external fixator, and Control group, respectively. The highest displacement in the pubic symphysis was found in Control group, and minimum displacement was observed in anterior pelvic bridge plating group. When the perpendicular distance between the right and left lower end of ischium was examined, it was observed that displacement was minimum in anterior pelvic bridge plating group compared to other two groups, regarding to the high stability of pubic symphysis. In conclusion, this study revealed superiority of anterior subcutaneous plate fixation with biomechanical results.
Wang, Shousen; Ying, Jianbin; Wei, Liangfeng; Li, Shiqing; Jing, Junjie
2015-01-01
This study is to investigate the compensatory intracranial venous pathways in parasagittal meningiomas (PSM) patients by virtual reality technology. A total of 48 PSM patients (tumor group) and 20 patients with trigeminal neuralgia and hemifacial spasm but without intracranial venous diseases (control group) were enrolled. All patients underwent 3D CE-MRV examination. The 3D reconstructed images by virtual reality technology were used for assessment of diameter and number of intracranial veins, tumor location, venous sinus invasion degree and collateral circulation formation. Diameter of bridging veins in posterior 1/3 superior sagittal sinus (SSS) in tumor group was significantly smaller than that of the control group (P < 0.05). For tumors located in mid 1/3 SSS, diameter of bridging veins and vein of Labbé (VL) in posterior 1/3 SSS decreased significantly (P < 0.05). For tumors located in posterior 1/3 SSS, bridging vein number and transverse sinus (TS) diameter significantly decreased while superficial Sylvian vein (SSV) diameter increased significantly (P < 0.05). Compared with tumor in posterior 1/3 SSS subgroup, number of bridging veins in the tumor in mid 1/3 SSS subgroup increased significantly (P < 0.05). Compared with control group, only the bridging vein number in anterior 1/3 SSS segment in invasion Type 3-4 tumor subgroup decreased significantly (P < 0.05). Diameter of TS and bridging veins in posterior 1/3 SSS segment in sinus invasion Type 5-6 tumor subgroup decreased significantly (P < 0.05). Compared with control group, only the diameter of VL and TS of collateral circulation Grade 1 tumor subgroup decreased significantly (P < 0.05) while in Grade 3 tumor subgroup, TS diameter decreased and SSV diameter increased significantly (P < 0.05). The intracranial blood flow is mainly drained through SSV drainage after SSS occlusion by PSM.
Wang, Shousen; Ying, Jianbin; Wei, Liangfeng; Li, Shiqing; Jing, Junjie
2015-01-01
Objective: This study is to investigate the compensatory intracranial venous pathways in parasagittal meningiomas (PSM) patients by virtual reality technology. Methods: A total of 48 PSM patients (tumor group) and 20 patients with trigeminal neuralgia and hemifacial spasm but without intracranial venous diseases (control group) were enrolled. All patients underwent 3D CE-MRV examination. The 3D reconstructed images by virtual reality technology were used for assessment of diameter and number of intracranial veins, tumor location, venous sinus invasion degree and collateral circulation formation. Results: Diameter of bridging veins in posterior 1/3 superior sagittal sinus (SSS) in tumor group was significantly smaller than that of the control group (P < 0.05). For tumors located in mid 1/3 SSS, diameter of bridging veins and vein of Labbé (VL) in posterior 1/3 SSS decreased significantly (P < 0.05). For tumors located in posterior 1/3 SSS, bridging vein number and transverse sinus (TS) diameter significantly decreased while superficial Sylvian vein (SSV) diameter increased significantly (P < 0.05). Compared with tumor in posterior 1/3 SSS subgroup, number of bridging veins in the tumor in mid 1/3 SSS subgroup increased significantly (P < 0.05). Compared with control group, only the bridging vein number in anterior 1/3 SSS segment in invasion Type 3-4 tumor subgroup decreased significantly (P < 0.05). Diameter of TS and bridging veins in posterior 1/3 SSS segment in sinus invasion Type 5-6 tumor subgroup decreased significantly (P < 0.05). Compared with control group, only the diameter of VL and TS of collateral circulation Grade 1 tumor subgroup decreased significantly (P < 0.05) while in Grade 3 tumor subgroup, TS diameter decreased and SSV diameter increased significantly (P < 0.05). Conclusions: The intracranial blood flow is mainly drained through SSV drainage after SSS occlusion by PSM. PMID:26550184
NASA Astrophysics Data System (ADS)
Krkošková, Katarína; Papán, Daniel; Papánová, Zuzana
2017-10-01
The technical seismicity negatively affects the environment, buildings and structures. Technical seismicity means seismic shakes caused by force impulse, random process and unnatural origin. The vibration influence on buildings is evaluated in the Eurocode 8 in Slovak Republic, however, the Slovak Technical Standard STN 73 0036 includes solution of the technical seismicity. This standard also classes bridges into the group of structures that are significant in light of the technical seismicity - the group “U”. Using the case studies analysis by FEM simulation and comparison is necessary because of brief norm evaluation of this issue. In this article, determinate dynamic parameters by experimental measuring and numerical method on two real bridges are compared. First bridge, (D201 - 00) is Scaffold Bridge on the road I/11 leading to the city of Čadca and is situated in the city of Žilina. It is eleven - span concrete road bridge. The railway is the obstacle, which this bridge spans. Second bridge (M5973 Brodno) is situated in the part of Žilina City on the road of I/11. It is concrete three - span road bridge built as box girder. The computing part includes 3D computational models of the bridges. First bridge (D201 - 00) was modelled in the software of IDA Nexis as the slab - wall model. The model outputs are natural frequencies and natural vibration modes. Second bridge (M5973 Brodno) was modelled in the software of VisualFEA. The technical seismicity corresponds with the force impulse, which was put into this model. The model outputs are vibration displacements, velocities and accelerations. The aim of the experiments was measuring of the vibration acceleration time record of bridges, and there was need to systematic placement of accelerometers. The vibration acceleration time record is important during the under - bridge train crossing, about the first bridge (D201 - 00) and the vibration acceleration time domain is important during deducing the force impulse under the bridge, about second bridge (M5973 Brodno). The analysis was done in the software of Sigview. About the first bridge (D201 - 00), the analysis output were values of power spectral density adherent to the frequencies values. These frequencies were compared with the natural frequencies values from the computational model whereby the technical seismicity influence on bridge natural frequencies was found out. About the second bridge (M5973 Brodno), the Sigview display of recorded vibration velocity time history was compared with the final vibration velocity time history from the computational model, whereby the results were incidental.
The Case for Summer Bridge: Building Social and Cultural Capital for Talented Black STEM Students
ERIC Educational Resources Information Center
Stolle-McAllister, Kathleen
2011-01-01
This study uses focus groups to examine the importance of a pre-college summer bridge program for highly talented black students in science, technology, engineering, and mathematics (STEM). Longitudinal data were collected from 134 participants who identified three aspects of Summer Bridge that were particularly helpful: academic, social, and…
Two-photon or higher-order absorbing optical materials for generation of reactive species
NASA Technical Reports Server (NTRS)
Marder, Seth R. (Inventor); Cumpston, Brian (Inventor); Lipson, Matthew (Inventor); Perry, Joseph W. (Inventor)
2003-01-01
Disclosed are highly efficient multiphoton absorbing compounds and methods of their use. The compounds generally include a bridge of pi-conjugated bonds connecting electron donating groups or electron accepting groups. The bridge may be substituted with a variety of substituents as well. Solubility, lipophilicity, absorption maxima and other characteristics of the compounds may be tailored by changing the electron donating groups or electron accepting groups, the substituents attached to or the length of the pi-conjugated bridge. Numerous photophysical and photochemical methods are enabled by converting these compounds to electronically excited states upon simultaneous absorption of at least two photons of radiation. The compounds have large two-photon or higher-order absorptivities such that upon absorption, one or more Lewis acidic species, Lewis basic species, radical species or ionic species are formed.
Two-photon or higher-order absorbing optical materials for generation of reactive species
NASA Technical Reports Server (NTRS)
Perry, Joseph W (Inventor); Cumpston, Brian (Inventor); Lipson, Matthew (Inventor); Marder, Seth R (Inventor)
2007-01-01
Disclosed are highly efficient multiphoton absorbing compounds and methods of their use. The compounds generally include a bridge of pi-conjugated bonds connecting electron donating groups or electron accepting groups. The bridge may be substituted with a variety of substituents as well. Solubility, lipophilicity, absorption maxima and other characteristics of the compounds may be tailored by changing the electron donating groups or electron accepting groups, the substituents attached to or the length of the pi-conjugated bridge. Numerous photophysical and photochemical methods are enabled by converting these compounds to electronically excited states upon simultaneous absorption of at least two photons of radiation. The compounds have large two-photon or higher-order absorptivities such that upon absorption, one or more Lewis acidic species, Lewis basic species, radical species or ionic species are formed.
Two-Photon or Higher-Order Absorbing Optical Materials for Generation of Reactive Species
NASA Technical Reports Server (NTRS)
Perry, Joseph W. (Inventor); Cumpston, Brian (Inventor); Lipson, Matthew (Inventor); Marder, Seth R. (Inventor)
2013-01-01
Disclosed are highly efficient multiphoton absorbing compounds and methods of their use. The compounds generally include a bridge of pi-conjugated bonds connecting electron donating groups or electron accepting groups. The bridge may be substituted with a variety of substituents as well. Solubility, lipophilicity, absorption maxima and other characteristics of the compounds may be tailored by changing the electron donating groups or electron accepting groups, the substituents attached to or the length of the pi-conjugated bridge. Numerous photophysical and photochemical methods are enabled by converting these compounds to electronically excited states upon simultaneous absorption of at least two photons of radiation. The compounds have large two-photon or higher-order absorptivities such that upon absorption, one or more Lewis acidic species, Lewis basic species, radical species or ionic species are formed.
Cal-Bridge and CAMPARE: Engaging Underrepresented Students in Physics and Astronomy
NASA Astrophysics Data System (ADS)
Rudolph, Alexander L.; Cal-Bridge and CAMPARE Teams
2018-01-01
We describe two programs, Cal-Bridge and CAMPARE, with the common mission of increasing participation of groups traditionally underrepresented in astronomy, through summer research opportunities, in the case of CAMPARE, scholarships in the case of Cal-Bridge, and significant mentoring in both programs, creating a national impact on their numbers successfully pursuing a PhD in the field.In 8 years, the CAMPARE program has sent 112 students, >80% from underrepresented groups, to conduct summer research at one of 14 major research institutions throughout the country. Of the CAMPARE scholars who have graduated with a Bachelor’s degree, almost two-thirds (65%) have completed or are pursuing graduate education in physics, astronomy, or a related field, at institutions including UCLA, UC Riverside, UC Irvine, UC Santa Barbara, USC, Stanford, Univ. of Arizona, Univ. of Washington, Univ. of Rochester, Michigan State Univ., Georgia Tech, Georgia State Univ., Kent State, Indiana Univ., Univ. of Oregon, Syracuse Univ., Montana State Univ., and the Fisk-Vanderbilt Master’s-to-PhD program.Now entering its fourth year, the Cal-Bridge program is a CSU-UC Bridge program comprised of >140 physics and astronomy faculty from 9 University of California (UC), 15 California State University (CSU), and 30 California Community College (CCC) campuses throughout California. In the first four years, 34 Cal-Bridge Scholars have been selected, including 22 Hispanic, 3 African-American and 13 women students, 10 of whom are from URM groups. Thirty (30) of the 34 Cal-Bridge Scholars are first generation college students. In the last two years, 11 of 13 Cal-Bridge Scholars have begun PhD programs in physics or astronomy at top PhD programs nationally. Three (3) of these 11 scholars have won NSF Graduate Research Fellowships; one more received an Honorable Mention. The next cohort applies this fall.Cal-Bridge provides much deeper mentoring and professional development experiences over the last two years of undergraduate and first year of graduate school to students from this diverse network of higher education institutions. Cal-Bridge Scholars benefit from substantial financial support, intensive, joint mentoring by CSU and UC faculty, professional development workshops, and exposure to research opportunities at the participating UC campuses.
Results of celiac trunk stenting during fenestrated or branched aortic endografting.
Wattez, Hélène; Martin-Gonzalez, Teresa; Lopez, Benjamin; Spear, Rafaëlle; Clough, Rachel E; Hertault, Adrien; Sobocinski, Jonathan; Haulon, Stéphan
2016-12-01
Endovascular repair of aortic aneurysms involving the visceral segment of the aorta often requires placement of a covered bridging stent in the celiac axis (CA). The median arcuate ligament (MAL) is a fibrous arch that unites the diaphragmatic crura on either side of the aortic hiatus. The ligament may compress and distort the celiac artery and result in difficult cannulation, or stenosis and occlusion of the vessel. This study evaluated the influence of the MAL compression on the technical success and the patency of the celiac artery after branched and fenestrated endovascular aortic repair. We retrospectively analyzed a cohort of consecutive patients treated electively for complex aneurysms with branched and fenestrated endovascular aortic repair between January 2007 and April 2014. All data were collected prospectively. Analysis of preoperative computed tomography angiography on a three-dimensional workstation determined the presence of MAL compression. Patency of the CA bridging stent was assessed during follow-up by computed tomography angiography and duplex ultrasound evaluation. Statistical analysis was performed to compare the outcomes of patients with MAL (MAL+) and without MAL (MAL-) compression. Of 315 patients treated for aortic disease involving the visceral segment during the study period, 113 had endografts designed with a branch (n = 57) or fenestration (n = 56) for the CA. In 45 patients (39.8%), asymptomatic compression of the CA by the MAL was depicted (MAL+). Complex endovascular techniques were required in this group to access the CA in 16 (14.2%) patients (vs none in the MAL- group; P = .003), which lead to a failed bridging stent implantation in seven patients (6.2%). Increased operative time and dose area product were observed in the MAL+ group, but this did not reach statistical significance. In the MAL+ group, no thrombosis of the CA bridging stents were observed during follow-up; an external compression of the CA bridging stent was depicted in six patients but without hemodynamic effect on duplex ultrasound imaging. In the MAL- group, one CA bridging stent occlusion occurred owing to an embolus from a cardiac source. MAL compression is associated with good celiac trunk bridging stent patency during follow-up, but with a higher rate of technical difficulties and failed bridging stent implantation during the procedure. Copyright © 2016 Society for Vascular Surgery. Published by Elsevier Inc. All rights reserved.
Structure and dynamics of a salt-bridge model system in water and DMSO
NASA Astrophysics Data System (ADS)
Lotze, S.; Bakker, H. J.
2015-06-01
We study the interaction between the ions methylguanidinium and trifluoroacetate dissolved in D2O and dimethylsulfoxide with linear infrared spectroscopy and femtosecond two-dimensional infrared spectroscopy. These ions constitute model systems for the side chains of arginine and glutamic and aspartic acid that are known to form salt bridges in proteins. We find that the salt-bridge formation of methylguanidinium and trifluoroacetate leads to a significant acceleration of the vibrational relaxation dynamics of the antisymmetric COO stretching vibration of the carboxyl moiety of trifluoroacetate. Salt-bridge formation has little effect on the rate of the spectral fluctuations of the CN stretching vibrations of methylguanidinium. The anisotropy of the cross peaks between the antisymmetric COO stretching vibration of trifluoroacetate and the CN stretching vibrations of methylguanidinium reveals that the salt-bridge is preferentially formed in a bidentate end-on configuration in which the two C=O groups of the carboxylate moiety form strong hydrogen bonds with the two -NH2 groups of methylguanidinium.
Dynamic characterization and damage detection in the I-40 bridge over the Rio Grande
DOE Office of Scientific and Technical Information (OSTI.GOV)
Farrar, C.R.; Baker, W.E.; Bell, T.M.
In the 1960`s and 1970`s over 2500 bridges were built in the U.S. with a design similar to those on Interstate 40 over the Rio Grande in Albuquerque, New Mexico. These bridges were built without structural redundancy and typically have only two plate girders carrying the entire dead and live loads. Failure of either girder is assumed to produce catastrophic failure of the bridge, hence these bridges are referred to as fracture-critical bridges. The Federal Highway Administration (FHWA) and the National Science Foundation (NSF) have provided funds to New Mexico State University (NMSU) through the New Mexico State Highway andmore » Transportation Department (NMSH&TD) and The Alliance For Transportation Research (ATR) for evaluation and testing of the existing fracture critical bridges over the Rio Grande. Because the 1-40 bridges over the Rio Grande were to be razed during the summer of 1993, the investigators were able to introduce simulated fatigue cracks, similar to those observed in the field, into the structure in order to test various damage identification methods and to observe the changes in load paths through the structure caused by the cracking. To support this research effort, NMSU contracted Los Alamos National Laboratory (LANL) to perform experimental modal analyses, and to develop experimentally verified numerical models of the bridge. Scientists from the LANL`s Condensed Matter and Thermal Physics Group (P-10) applied state-of-the-art sensors and data acquisition software to the modal tests. Engineers from the LANL`s Advanced Engineering Technology Group (MEE-13) conducted ambient and forced vibration tests to verify detailed and simplified finite element models of the bridge. Forced vibration testing was done in conjunction with engineers from Sandia National Laboratory (SNL) who provided and operated a hydraulic shaker.« less
Evaluation of a Summer Bridge: Critical Component of the Leadership 2.0 Program.
Pritchard, Tracy J; Perazzo, Joseph D; Holt, Julie A; Fishback, Benjamin P; McLaughlin, Michaela; Bankston, Karen D; Glazer, Greer
2016-04-01
Summer bridges facilitate the transition from high school to college. Although many schools employ summer bridges, few have published outcomes. This article's purpose is to share preconceptions of college by underrepresented and disadvantaged nursing students and describe important elements and long-term impact of a summer bridge, a component of the Leadership 2.0 program. A longitudinal study design was used to collect baseline, short-term, and long-term post-summer bridge data. Methods included pre- and postsurveys, interviews, and focus groups. After bridge completion, students felt more prepared for the nursing program. Students ranked socialization components as most important. The summer bridge had lasting impact through the first year, where grade point average and retention of underrepresented and disadvantaged bridge students was comparable to the majority first-year students. The summer bridge was effective in preparing nursing students for the first year of college. Through holistic evaluation, unique aspects of socialization critical to student success were uncovered. Copyright 2016, SLACK Incorporated.
NASA Astrophysics Data System (ADS)
Mo, Zhao-Hua; Luo, Zheng; Huang, Qiang; Deng, Jian-Ping; Wu, Yi-Xian
2018-05-01
Grafting single end-tethered polymer chains on the surface of graphene is a conventional way to modify the surface properties of graphene oxide. However, grafting arc-like macromolecular bridges on graphene surfaces has been barely reported. Herein, a novel arc-like polydimethylsiloxane (PDMS) macromolecular bridges grafted graphene sheets (GO-g-Arc PDMS) was successfully synthesized via a confined interface reaction at 90 °C. Both the hydrophilic α- and ω-amino groups of linear hydrophobic NH2-PDMS-NH2 macromolecular chains rapidly reacted with epoxy and carboxyl groups on the surfaces of graphene oxide in water suspension to form arc-like PDMS macromolecular bridges on graphene sheets. The grafting density of arc-like PDMS bridges on graphene sheets can reach up to 0.80 mmol g-1 or 1.32 arc-like bridges per nm2 by this confined interface reaction. The water contact angle (WCA) of the hybrid membrane could be increased with increasing both the grafting density and content of covalent arc-like bridges architecture. The superhydrophobic hybrid membrane with a WCA of 153.4° was prepared by grinding of the above arc-like PDMS bridges grafted graphene hybrid, dispersing in ethanol and filtrating by organic filter membrane. This superhydrophobic hybrid membrane shows good self-cleaning and complete oil-water separation properties, which provides potential applications in anticontamination coating and oil-water separation. To the best of our knowledge, this is the first report on the synthesis of functional hybrid membranes by grafting arc-like PDMS macromolecular bridges on graphene sheets via a confined interface reaction.
Comparison of submuscular and open plating of pediatric femur fractures: a retrospective review.
Abbott, Matthew D; Loder, Randall T; Anglen, Jeffrey O
2013-01-01
Plate osteosynthesis is an accepted method of treatment of pediatric femur fractures. Historically, open plating has been used. Submuscular bridge plating has gained recent popularity due to the theoretical advantages of decreased operative time, decreased blood loss, and decreased risk for infection. The purpose of this study was to compare submuscular bridge plating to open plating of pediatric femur fractures. We retrospectively reviewed 79 patients (80 treated femur fractures) between 1999 and 2011 that underwent either open plating (58 femur fractures) or submuscular bridge plating (22 femur fractures). The outcome measures evaluated were operative time, estimated blood loss, malunion, leg length discrepancy, time to union, infection, unplanned return to the operating room, and length of hospital stay after surgery. Among our outcome measures, there was no difference between the 2 groups in terms of operative time, leg length discrepancy, time to union, infection, or length of hospital stay after surgery. There was greater estimated blood loss in the open plating group (P≤0.0001) and greater rotational asymmetry in the submuscular bridge plating group (P=0.005). There was a trend of increased unplanned return to the operating room in the open plating group (5/58 vs. 0/22) although not statistically significant (P=0.32). Submuscular bridge plating and open plating seem to be equally viable options for the management of pediatric diaphyseal femur fractures. In this study, open plating had an increase in estimated blood loss and a trend of more unplanned returns to the operating room, whereas submuscular bridge plating had an increase in asymptomatic rotational asymmetry. Further larger, prospective, randomized studies are necessary to further evaluate these operative techniques. Therapeutic Level III.
Guanidinium-Induced Denaturation by Breaking of Salt Bridges.
Meuzelaar, Heleen; Panman, Matthijs R; Woutersen, Sander
2015-12-07
Despite its wide use as a denaturant, the mechanism by which guanidinium (Gdm(+) ) induces protein unfolding remains largely unclear. Herein, we show evidence that Gdm(+) can induce denaturation by disrupting salt bridges that stabilize the folded conformation. We study the Gdm(+) -induced denaturation of a series of peptides containing Arg/Glu and Lys/Glu salt bridges that either stabilize or destabilize the folded conformation. The peptides containing stabilizing salt bridges are found to be denatured much more efficiently by Gdm(+) than the peptides containing destabilizing salt bridges. Complementary 2D-infrared measurements suggest a denaturation mechanism in which Gdm(+) binds to side-chain carboxylate groups involved in salt bridges. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Final Environmental Assessment, Horse Creek Bridge Replacement
2010-10-01
Final Environmental Assessment Horse Creek Bridge Replacement 78th Civil Engineer Group...Final Environmental Assessment Horse Creek Bridge Replacement 5a. CONTRACT NUMBER 5b. GRANT NUMBER 5c. PROGRAM ELEMENT NUMBER 6. AUTHOR(S) 5d...Form 298 (Rev. 8-98) Prescribed by ANSI Std Z39-18 FINDING OF NO SIGNIFICANT IMPACT (FONSI)/ FINDING OF NO PRACTICABLE ALTERNATIVE (FONP A) HORSE
DOE Office of Scientific and Technical Information (OSTI.GOV)
Li, Zhanyong; Peters, Aaron W.; Platero-Prats, Ana E.
Few-atom cobalt-oxide clusters, when dispersed on a Zr-based metal–organic framework (MOF) NU-1000, have previously been shown to be active for the oxidative dehydrogenation (ODH) of propane at low temperatures (< 230 °C), affording a selective and stable propene production catalyst. In our current work, a series of promoter ions with varying Lewis acidity, including Ni(II), Zn(II), Al(III), Ti(IV) and Mo(VI), are anchored as metal-oxide,hydroxide clusters to NU-1000 via SIM (solvothermal deposition within MOFs–specifically the nodes) followed by incorporation of Co(II) ions via vapor-phase AIM (atomic layer deposition (ALD) in MOFs). This process yields a series of NU-1000-supported bimetallic-oxo,hydroxo,aqua clusters. Usingmore » difference envelope density (DED) analyses, the spatial locations of the promoter ions and catalytic cobalt ions are determined. For all samples the SIM-anchored promoter ions are sited between pairs of Zr 6 nodes along the MOF c-axis (channel-aligned axis) whereas the location of the AIM-anchored cobalt ions varies depending on the identity of promoter metal ion. With Ni(II)-, Al(III)-, or Ti(IV)-containing clusters as promoters, the oxy-cobalt species are sited atop the promoter sites; with Mo(VI) they grow exclusively on the MOF nodes sites (hexa-Zr(IV)- oxo,hydroxo,aqua units); with Zn(II) they grow on both the node and promoter. The NU-1000- supported bimetallic-oxide clusters are active for propane ODH after thermal activation under O 2 to open a cobalt coordination site and to oxidize Co(II) to Co(III), as evidenced by operando Xray absorption spectroscopy at the Co K-edge. The cobalt component is exclusively responsible for the observed catalysis. In accord with the decreasing Lewis acidity of the promoter ion, catalytic activity increases in the order: Mo(VI)« less
Li, Zhanyong; Peters, Aaron W.; Platero-Prats, Ana E.; ...
2017-10-04
Few-atom cobalt-oxide clusters, when dispersed on a Zr-based metal–organic framework (MOF) NU-1000, have previously been shown to be active for the oxidative dehydrogenation (ODH) of propane at low temperatures (< 230 °C), affording a selective and stable propene production catalyst. In our current work, a series of promoter ions with varying Lewis acidity, including Ni(II), Zn(II), Al(III), Ti(IV) and Mo(VI), are anchored as metal-oxide,hydroxide clusters to NU-1000 via SIM (solvothermal deposition within MOFs–specifically the nodes) followed by incorporation of Co(II) ions via vapor-phase AIM (atomic layer deposition (ALD) in MOFs). This process yields a series of NU-1000-supported bimetallic-oxo,hydroxo,aqua clusters. Usingmore » difference envelope density (DED) analyses, the spatial locations of the promoter ions and catalytic cobalt ions are determined. For all samples the SIM-anchored promoter ions are sited between pairs of Zr 6 nodes along the MOF c-axis (channel-aligned axis) whereas the location of the AIM-anchored cobalt ions varies depending on the identity of promoter metal ion. With Ni(II)-, Al(III)-, or Ti(IV)-containing clusters as promoters, the oxy-cobalt species are sited atop the promoter sites; with Mo(VI) they grow exclusively on the MOF nodes sites (hexa-Zr(IV)- oxo,hydroxo,aqua units); with Zn(II) they grow on both the node and promoter. The NU-1000- supported bimetallic-oxide clusters are active for propane ODH after thermal activation under O 2 to open a cobalt coordination site and to oxidize Co(II) to Co(III), as evidenced by operando Xray absorption spectroscopy at the Co K-edge. The cobalt component is exclusively responsible for the observed catalysis. In accord with the decreasing Lewis acidity of the promoter ion, catalytic activity increases in the order: Mo(VI)« less
DOE Office of Scientific and Technical Information (OSTI.GOV)
Hammann, Blake A.; Marsh, David A.; Ma, Zayd L.
Solid-state {sup 71}Ga NMR was used to characterize a series of [Ga{sub 13}(μ{sub 3}-OH){sub 6}(μ{sub 2}-OH){sub 18}(H{sub 2}O)](NO{sub 3}){sub 15} “Ga{sub 13}” molecular clusters synthesized by multiple methods. These molecular clusters are precursors to thin film electronics and may be employed in energy applications. The synthetic routes provide varying levels of impurities in the solid phase, and these impurities often elude traditional characterization techniques such as powder X-ray diffraction and Raman spectroscopy. Solid-state NMR can provide a window into the gallium species even in amorphous phases. This information is vital in order to prevent the impurities from causing defect sitesmore » in the corresponding thin films upon gelation and condensation (polymerization) of the Ga{sub 13} clusters. This work demonstrates the resolving power of solid-state NMR to evaluate structure and synthetic quality in the solid state, and the application of high-field NMR to study quadrupolar species, such as {sup 71}Ga. - Graphical abstract: The various synthetic routes and {sup 71}Ga solid-state NMR spectra of the nanoscale inorganic cluster [Ga{sub 13}(μ{sub 3}-OH){sub 6}(μ{sub 2}-OH){sub 18}(H{sub 2}O)](NO{sub 3}){sub 15}. - Highlights: • Solid-state {sup 71}Ga NMR of hydroxo-aquo metal clusters and the impurities present. • High-field NMR capability allows for quadrupolar species, such as {sup 71}Ga, to be routinely studied. • Efficient and environmentally friendly synthetic routes have been developed to prepare hydroxo-aquo metal clusters.« less
DOT National Transportation Integrated Search
2013-09-01
Accelerated Bridge Construction techniques have resulted in innovative options that : save time and money during the construction of bridges. One such group of techniques : that has generated considerable interest is the usage of individual precast c...
Study of the influence of the bridge on the magnetic coupling in cobalt(II) complexes.
Fabelo, Oscar; Cañadillas-Delgado, Laura; Pasán, Jorge; Delgado, Fernando S; Lloret, Francesc; Cano, Joan; Julve, Miguel; Ruiz-Pérez, Catalina
2009-12-07
Two new cobalt(II) complexes of formula [Co(2)(bta)(H(2)O)(6)](n) x 2nH(2)O (1) and [Co(phda)(H(2)O)](n) x nH(2)O (2) [H(4)bta = 1,2,4,5-benzenetetracarboxylic acid, H(2)phda = 1,4-phenylenediacetic acid] have been characterized by single crystal X-ray diffraction. Compound 1 is a one-dimensional compound where the bta(4-) ligand acts as 2-fold connector between the cobalt(II) ions through two carboxylate groups in para-conformation. Triply bridged dicobalt(II) units occur within each chain, a water molecule, a carboxylate group in the syn-syn conformation, and an oxo-carboxylate with the mu(2)O(1);kappa(2)O(1),O(2) coordination mode acting as bridges. Compound 2 is a three-dimensional compound, where the phda(2-) group acts as a bridge through its two carboxylate groups, one of them adopting the mu-O,O' coordination mode in the syn-syn conformation and the other exhibiting the single mu(2)-O'' bridging mode. As in 1, chains of cobalt(II) ions occur in 2 with a water molecule, a syn-syn carboxylate group, and an oxo-carboxylate constitute the triply intrachain bridging skeleton. Each chain is linked to other four ones through the phda(2-) ligand, giving rise to the three-dimensional structure. The values of the intrachain cobalt-cobalt separation are 3.1691(4) (1) and 3.11499(2) A (2) whereas those across the phenyl ring of the extended bta(4-) (1) and phda(2-) (2) groups are 10.1120(6) and 11.4805(69 A, respectively. The magnetic properties of 1 and 2 have been investigated in the temperature range 1.9-300 K, and their analysis has revealed the occurrence of moderate intrachain ferromagnetic couplings [J = +5.4 (1) and +2.16 cm(-1) (2), J being the isotropic magnetic coupling parameter], the magnetic coupling through the extended bta(4-) and phda(2-) with cobalt-cobalt separations larger than 10 A being negligible. The nature and magnitude of the magnetic interactions between the high-spin cobalt(II) ions in 1 and 2 are compared to those of related systems and discussed as a function of the complementarity-countercomplementarity effects of the triple bridges.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Svetlichnyi, V. M., E-mail: valsvet@hq.macro.ru; Aleksandrova, E. L.; Myagkova, L. A.
2011-10-15
Photophysical and electrical properties of new synthesized 2,6-polyphenylquinolines (PPQs) containing an oxygen or phenylamine bridging group between quinoline cycles and, as an arylene radical, alkylated derivatives of carbazole or indolo[3,2-b]carbazole are studied. It is shown that the photosensitivity for new PPQs is 10{sup 4}-10{sup 5} cm{sup 2}/J and the photogeneration quantum yield of free carriers is as high as 0.15. Photophysical parameters increase with the phenylamine bridging group in place of the oxygen one and when using indolocarbazole instead of carbazole. It is found that a film of polyphenylquinoline containing an oxygen bridging group and an alkylcarbazole fragment in themore » polymer repeat unit exhibits 'white' luminescence. Both electron and hole transport with a mobility of {approx}10{sup -6} cm{sup 2}/(V s) are detected in films of all studied polymers. The conductivity value and type can be controlled by varying the chemical structure of the (oxygen or phenylamine) bridging group between PPQ cycles and by choosing carbazole or indolo[3,2-b]carbazole derivatives as an arylene radical.« less
Flor-Lorente, Blas; Báguena, Gloria; Frasson, Matteo; García-Granero, Alvaro; Cervantes, Andrés; Sanchiz, Vicente; Peña, Andres; Espí, Alejandro; Esclapez, Pedro; García-Granero, Eduardo
2017-03-01
The use of a self-expanding metallic stent as a bridge to surgery in acute malignant left colonic obstruction has been suggested as an alternative treatment to emergency surgery. The aim of the present study was to compare the morbi-mortality, cost-benefit and long-term oncological outcomes of both therapeutic options. This is a prospective, comparative, controlled, non-randomized study (2005-2010) performed in a specialized unit. The study included 82 patients with left colon cancer obstruction treated by stent as a bridge to surgery (n=27) or emergency surgery (n=55) operated with local curative intention. The main outcome measures (postoperative morbi-mortaliy, cost-benefit, stoma rate and long-term oncological outcomes) were compared based on an "intention-to-treat" analysis. There were no significant statistical differences between the two groups in terms of preoperative data and tumor characteristics. The technically successful stenting rate was 88.9% (11.1% perforation during stent placement) and clinical success was 81.4%. No difference was observed in postoperative morbi-mortality rates. The primary anastomosis rate was higher in the bridge to surgery group compared to the emergency surgery group (77.8% vs. 56.4%; P=.05). The mean costs in the emergency surgery group resulted to be €1,391.9 more expensive per patient than in the bridge to surgery group. There was no significant statistical difference in oncological long-term outcomes. The use of self-expanding metalllic stents as a bridge to surgery is a safe option in the urgent treatment of obstructive left colon cancer, with similar short and long-term results compared to direct surgery, inferior mean costs and a higher rate of primary anastomosis. Copyright © 2017 AEC. Publicado por Elsevier España, S.L.U. All rights reserved.
Cal-Bridge and CAMPARE: Engaging Underrepresented Students in Physics and Astronomy
NASA Astrophysics Data System (ADS)
Rudolph, Alexander L.; Smecker-Hane, Tammy A.; Cal-Bridge Team; CAMPARE Team
2018-06-01
We describe two programs, Cal-Bridge and CAMPARE, with the common mission of increasing participation of groups traditionally underrepresented in astronomy, through summer research opportunities, in the case of CAMPARE, scholarships in the case of Cal-Bridge, and significant mentoring in both programs, creating a national impact on their numbers successfully pursuing a PhD in the field. In 9 years, the CAMPARE program has sent 150 students, >80% from underrepresented groups, to conduct summer research at one of 14 major research institutions throughout the country. Of the CAMPARE scholars who have graduated with a Bachelor’s degree, almost two-thirds (65%) have completed or are pursuing graduate education in physics, astronomy, or a related field, at institutions including UCLA, UC Riverside, UC Irvine, UC Santa Barbara, USC, Stanford, Univ. of Arizona, Univ. of Washington, Univ. of Rochester, Michigan State Univ., Georgia Tech, Georgia State Univ., Kent State, Indiana Univ., Univ. of Oregon, Syracuse Univ., Montana State Univ., and the Fisk- Vanderbilt Master’s-to-PhD program. Now in its fourth year, the Cal-Bridge program is a CSU-UC Bridge program comprised of physics and astronomy faculty from 9 University of California (UC), 15 California State University (CSU), and more than 30 California Community College (CCC) campuses throughout California. In the first four years, 34 Cal-Bridge Scholars have been selected, including 22 Hispanic, 3 African-American and 13 women students, 10 of whom are from URM groups. Thirty (30) of the 34 Cal-Bridge Scholars are first generation college students. In the last three years, 17 of 21 Cal-Bridge Scholars have begun or been accepted PhD programs in physics or astronomy at top PhD programs nationally. Three (3) of these scholars have won NSF Graduate Research Fellowships; one more received an Honorable Mention. Once selected, Cal-Bridge Scholars benefit from substantial financial support, intensive, joint mentoring by CSU and UC faculty, professional development workshops, and exposure to research opportunities at the participating UC campuses. Funding for this program is provided by NSF-DUE SSTEM Grant #1356133.
The prone bridge test: Performance, validity, and reliability among older and younger adults.
Bohannon, Richard W; Steffl, Michal; Glenney, Susan S; Green, Michelle; Cashwell, Leah; Prajerova, Kveta; Bunn, Jennifer
2018-04-01
The prone bridge maneuver, or plank, has been viewed as a potential alternative to curl-ups for assessing trunk muscle performance. The purpose of this study was to assess prone bridge test performance, validity, and reliability among younger and older adults. Sixty younger (20-35 years old) and 60 older (60-79 years old) participants completed this study. Groups were evenly divided by sex. Participants completed surveys regarding physical activity and abdominal exercise participation. Height, weight, body mass index (BMI), and waist circumference were measured. On two occasions, 5-9 days apart, participants held a prone bridge until volitional exhaustion or until repeated technique failure. Validity was examined using data from the first session: convergent validity by calculating correlations between survey responses, anthropometrics, and prone bridge time, known groups validity by using an ANOVA comparing bridge times of younger and older adults and of men and women. Test-retest reliability was examined by using a paired t-test to compare prone bridge times for Session1 and Session 2. Furthermore, an intraclass correlation coefficient (ICC) was used to characterize relative reliability and minimal detectable change (MDC 95% ) was used to describe absolute reliability. The mean prone bridge time was 145.3 ± 71.5 s, and was positively correlated with physical activity participation (p ≤ 0.001) and negatively correlated with BMI and waist circumference (p ≤ 0.003). Younger participants had significantly longer plank times than older participants (p = 0.003). The ICC between testing sessions was 0.915. The prone bridge test is a valid and reliable measure for evaluating abdominal performance in both younger and older adults. Copyright © 2017 Elsevier Ltd. All rights reserved.
Yamamoto, Tatsuo; Kondo, Katsunori; Aida, Jun; Suzuki, Kayo; Misawa, Jimpei; Nakade, Miyo; Fuchida, Shinya; Hirata, Yukio
2014-06-03
Studies suggest that using a denture/bridge may prevent disability in older people. However, not all older people with few remaining teeth use a denture/bridge. This cross-sectional study aimed to examine the social determinants which promote denture/bridge use among older Japanese. A total of 54,388 (25,630 males and 28,758 females) community-dwelling individuals aged 65 or over, living independently, able to perform daily activities, and with 19 or fewer teeth. The dependent variable was denture/bridge use. Socio-demographics, number of teeth, present illness, social participation, social support, and social networks were used as individual-level independent variables. Data for social capital were aggregated and used as local district (n = 561 for males, n = 562 for females) -level independent variables. Number of dentists working in hospitals/clinics per population and population density were used as municipality (n = 28) -level independent variables. Three-level multilevel Poisson regression analysis was performed for each sex. High equivalent income, low number of teeth, present illness, and living in a municipality with high population density were significantly associated with denture/bridge use in both sexes in the fully adjusted models (p < 0.05). Denture/bridge use was significantly associated with high educational attainment in males and participating in social groups in females in the fully adjusted model (p < 0.05). No significant associations were observed between denture/bridge use and social capital. Denture/bridge use was significantly associated with high economic status and present illness in both sexes, high educational attainment in males, and participation in social groups in females among community-dwelling older Japanese after adjusting for possible confounders.
The association of sacroiliac joint bridging with other enthesopathies in the human body.
Dar, Gali; Peleg, Smadar; Masharawi, Youssef; Steinberg, Nili; Rothschild, Bruce M; Hershkovitz, Israel
2007-05-01
A descriptive study of the association between sacroiliac joint (extra-articular) bridging and other enthesopathies. To examine the relationship between sacroiliac joint bridging with other entheseal reaction sites in the skeleton, and its prognostic value in spinal diseases. Sacroiliac joint bridging is considered a hallmark of spinal diseases (e.g., ankylosing spondylitis). Nevertheless, its association with other enthesopathies has never been quantified and analyzed. A total of 289 human male skeletons with sacroiliac joint bridging and 127 without (of similar demographic structure) were evaluated for the presence of entheseal ossification, cartilaginous calcification, and other axial skeleton joint fusion (a total of 18 anatomic sites). The presence of diffuse idiopathic skeletal hyperostosis and spondyloarthropathy was also recorded. Sacroiliac joint bridging was strongly associated with entheseal reactions in other parts of the body. Of the sacroiliac joint bridging group, 24.91% had diffuse idiopathic skeletal hyperostosis, and 8.05% had spondyloarthropathy. The presence of sacroiliac joint bridging indicates an intensive general entheseal process in the skeleton.
Yen, Ngo Thi Hai; Bogdanović, Xenia; Palm, Gottfried J; Kühl, Olaf; Hinrichs, Winfried
2010-02-01
Crystal structures of polypeptide deformylase (PDF) of Escherichia coli with nickel(II) replacing the native iron(II) have been solved with chloride and formate as metal ligands. The chloro complex is a model for the correct protonation state of the hydrolytic hydroxo ligand and the protonated status of the Glu133 side chain as part of the hydrolytic mechanism. The ambiguity that recently some PDFs have been identified with Zn(2+) ion as the active-site centre whereas others are only active with Fe(2+) (or Co(2+), Ni(2+) is discussed with respect to Lewis acid criteria of the metal ion and substrate activation by the CD loop.
The role of halide ions on the electrochemical behaviour of iron in alkali solutions
NASA Astrophysics Data System (ADS)
Begum, S. Nathira; Muralidharan, V. S.; Basha, C. Ahmed
2008-02-01
Active dissolution and passivation of transition metals in alkali solutions is of technological importance in batteries. The performance of alkaline batteries is decided by the presence of halides as they influence passivation. Cyclic voltammetric studies were carried out on iron in different sodium hydroxide solutions in presence of halides. In alkali solutions iron formed hydroxo complexes and their polymers in the interfacial diffusion layer. With progress of time they formed a cation selective layer. The diffusion layer turned into bipolar ion selective layer consisted of halides, a selective inner sublayer to the metal side and cation selective outer layer to the solution side. At very high anodic potentials, dehydration and deprotonation led to the conversion of salt layer into an oxide.
Grzybowski, Marek; Taki, Masayasu; Yamaguchi, Shigehiro
2017-09-21
The substitution of an oxygen atom in rhodols with a phosphine oxide (P=O) moiety affords P=O-bridged rhodols as a new type of near-infrared (NIR) fluorophore. This compound class can be readily accessed upon exposure of the corresponding rhodamines to aqueous basic conditions. The electron-withdrawing effect of the P=O group facilitates the hydrolytic deamination, and, moreover, prolonged exposure to aqueous basic conditions generates P=O-bridged fluoresceins, that is, a series of three P=O-bridged xanthene dyes is available in one simple operation. The P=O-bridged rhodols show significant bathochromic shifts of the longest-wavelength absorption maximum (Δλ=125 nm; >3600 cm -1 ) upon changing the solvent from toluene to water, whereas the emission is shifted less drastically (Δλ=70 nm; 1600 cm -1 ). The hydrogen bonding between the P=O and C=O groups with protic solvents results in substantial stabilization of the LUMO level, which is responsible for the solvatochromism. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
Pacemaker or defibrillator surgery without interruption of anticoagulation.
Birnie, David H; Healey, Jeff S; Wells, George A; Verma, Atul; Tang, Anthony S; Krahn, Andrew D; Simpson, Christopher S; Ayala-Paredes, Felix; Coutu, Benoit; Leiria, Tiago L L; Essebag, Vidal
2013-05-30
Many patients requiring pacemaker or implantable cardioverter-defibrillator (ICD) surgery are taking warfarin. For patients at high risk for thromboembolic events, guidelines recommend bridging therapy with heparin; however, case series suggest that it may be safe to perform surgery without interrupting warfarin treatment. There have been few results from clinical trials to support the safety and efficacy of this approach. We randomly assigned patients with an annual risk of thromboembolic events of 5% or more to continued warfarin treatment or to bridging therapy with heparin. The primary outcome was clinically significant device-pocket hematoma, which was defined as device-pocket hematoma that necessitated prolonged hospitalization, interruption of anticoagulation therapy, or further surgery (e.g., hematoma evacuation). The data and safety monitoring board recommended termination of the trial after the second prespecified interim analysis. Clinically significant device-pocket hematoma occurred in 12 of 343 patients (3.5%) in the continued-warfarin group, as compared with 54 of 338 (16.0%) in the heparin-bridging group (relative risk, 0.19; 95% confidence interval, 0.10 to 0.36; P<0.001). Major surgical and thromboembolic complications were rare and did not differ significantly between the study groups. They included one episode of cardiac tamponade and one myocardial infarction in the heparin-bridging group and one stroke and one transient ischemic attack in the continued-warfarin group. As compared with bridging therapy with heparin, a strategy of continued warfarin treatment at the time of pacemaker or ICD surgery markedly reduced the incidence of clinically significant device-pocket hematoma. (Funded by the Canadian Institutes of Health Research and the Ministry of Health and Long-Term Care of Ontario; BRUISE CONTROL ClinicalTrials.gov number, NCT00800137.).
Wang, Zhen; Wang, Dong; Qian, Zhenchao; Guo, Jing; Dong, Haixia; Zhao, Ning; Xu, Jian
2015-01-28
Aerogels are a family of highly porous materials whose applications are commonly restricted by poor mechanical properties. Herein, thiol-ene chemistry is employed to synthesize a series of novel bridged silsesquioxane (BSQ) precursors with various alkoxy groups. On the basis of the different hydrolyzing rates of the methoxy and ethoxy groups, robust superhydrophobic BSQ aerogels with tailorable morphology and mechanical performances have been prepared. The flexible thioether bridge contributes to the robustness of the as-formed aerogels, and the property can be tuned on the basis of the distinct combinations of alkoxy groups with the density of the aerogels almost unchanged. To the best of our knowledge, the lowest density among the ambient pressure dried aerogels is obtained. Further, potential application of the aerogels for oil/water separation and acoustic materials has also been presented.
Qiu, Jie; Dong, Sining; Szymanowski, Jennifer E S; Dobrowolska, Malgorzata; Burns, Peter C
2017-04-03
A hybrid uranium-iron cage nanocluster, [(UO 2 ) 24 (FeOH) 24 (O 2 ) 24 (PO 4 ) 8 (CH(COO)(PO 3 ) 2 ) 24 ] 96- (U 24 Fe 24 ), was synthesized using bridging ligands containing bisphosphonate and carboxylate groups. U 24 Fe 24 contains six tetramers of uranyl hexagonal bipyramids and eight iron trimers, each of which consists of three corner-sharing Fe 3+ octahedra and is stabilized by in situ formed phosphate and 2,2-bis(phosphonato)acetate (C 2 P 2 ) groups. Tetramers and trimers are bridged by 24 C 2 P 2 groups into a cage cluster. Crystals of U 24 Fe 24 present a paramagnetic-like behavior. X-ray scattering showed that U 24 Fe 24 forms in the reactant solution prior to crystallization and is stable upon dissolution in water.
Kim, Chang-O; Cho, Byong-Hee
2016-10-01
The growing number of people living in deprived urban neighborhoods, which often have unhealthy environments, is of growing concern to inequality researchers. Social capital could be a resource to help such communities get ahead. In this study, we examined the differential effects of bonding and bridging social capital on self-rated health using two operational definitions, which we call personal and geographic social capital. Bonding and bridging social capital were operationally distinguished as respondents' perceived similarity to other members of a group with respect to personal characteristics (personal social capital) or as structural similarity with respect to geographical location (geographic social capital). The results showed that although both bonding and bridging social capital as defined by person-based criteria were associated with increased odds of self-rated health compared to those who reported zero participation, when defined by place-based criteria, only bridging social capital was associated with increased odds of self-rated health; no clear association was found between health and belonging to groups within the neighborhood, so-called geographic bonding social capital. The present study suggests that geographic bridging social capital can function as linking social capital that enables an upward approach depending on the political and economic contexts of urbanization. © The Author(s) 2015.
Cox, Joseph T; Shorten, Peter L; Gould, Gregory C; Markert, Ronald J; Barnett, Michael D; Laughlin, Richard T
2014-11-01
Surgical treatment of insertional Achilles tendinopathy often involves detachment and debridement of the Achilles tendon insertion. A recent study has shown that knotted suture bridge fixation of the Achilles to the calcaneus is biomechanically superior to single-row fixation, but there is an absence of literature on the use of different suture bridge constructs to repair the Achilles tendon. There will be no significant difference in the load to failure, mode of failure, tendon strain, tendon stiffness, repair site gapping, or footprint size when comparing knotted suture bridge repair to knotless suture bridge repair of the Achilles tendon after detachment for insertional Achilles tendinopathy. Controlled laboratory study. A single specimen from each pair of 10 cadaveric Achilles tendons was randomized to 1 of 2 Achilles insertion repair groups: knotted (n = 10) or knotless (n = 10) suture bridge repair. Repaired footprint size was measured, and then cyclic testing from 10 to 100 N for 2000 cycles was performed. This was followed by measurement of tendon strain, repair site displacement, load to failure, and tendon stiffness. The knotted suture bridge repair had a significantly higher load to failure compared with the knotless suture bridge (mean ± SD, 317.8 ± 93.6 N vs 196.1 ± 12.1 N, respectively; P = .001). All constructs failed at the tendon-suture interface. Tendon strain after cyclic testing was significantly greater in the knotless (1.20 ± 1.05) compared with the knotted (0.39 ± 0.4) suture repair groups (P = .011). There was no significant difference in footprint size between the knotted (230.3 ± 63.3 mm(2)) and knotless (248.5 ± 48.8 mm(2)) groups (P = .40). There was also no significant difference in stiffness (knotted = 76.4 ± 8.0 N/mm; knotless = 69.6 ± 10.9 N/mm; P = .17) and repair site displacement after cyclic testing (knotted = 2.8 ± 1.2 mm; knotless = 3.6 ± 1.1 mm; P = .17). During suture bridge repair of the Achilles tendon after detachment, knots at the proximal suture anchors significantly improve the biomechanical strength of the repair. This study demonstrated that the knotless suture bridge repair had a significantly lower load to failure than the knotted suture bridge. Surgeons should be aware of these biomechanical differences, as they influence the postoperative rehabilitation protocol and may lead to higher surgical complication rates. © 2014 The Author(s).
Water vapor adsorption on goethite.
Song, Xiaowei; Boily, Jean-François
2013-07-02
Goethite (α-FeOOH) is an important mineral contributing to processes of atmospheric and terrestrial importance. Their interactions with water vapor are particularly relevant in these contexts. In this work, molecular details of water vapor (0.0-19.0 Torr; 0-96% relative humidity at 25 °C) adsorption at surfaces of synthetic goethite nanoparticles reacted with and without HCl and NaCl were resolved using vibrational spectroscopy. This technique probed interactions between surface (hydr)oxo groups and liquid water-like films. Molecular dynamics showed that structures and orientations adopted by these waters are comparable to those adopted at the interface with liquid water. Particle surfaces reacted with HCl accumulated less water than acid-free surfaces due to disruptions in hydrogen bond networks by chemisorbed waters and chloride. Particles reacted with NaCl had lower loadings below ∼10 Torr water vapor but greater loadings above this value than salt-free surfaces. Water adsorption reactions were here affected by competitive hydration of coexisting salt-free surface regions, adsorbed chloride and sodium, as well as precipitated NaCl. Collectively, the findings presented in this study add further insight into the initial mechanisms of thin water film formation at goethite surfaces subjected to variations in water vapor pressure that are relevant to natural systems.
ERIC Educational Resources Information Center
Stassun, Keivan Guadalupe; Burger, Arnold; Lange, Sheila Edwards
2010-01-01
We describe the Fisk-Vanderbilt Masters-to-PhD Bridge program as a successful model for effective partnerships with minority-serving institutions toward significantly broadening the participation of underrepresented groups in the physical sciences. The program couples targeted recruitment with active retention strategies, and is built upon a…
De Rita, Fabrizio; Hasan, Asif; Haynes, Simon; Crossland, David; Kirk, Richard; Ferguson, Lee; Peng, Edward; Griselli, Massimo
2014-10-01
A significant number of children affected by congenital heart disease (CHD) develop heart failure early or late after surgery, and heart transplantation (OHTx) remains the last treatment option. Due to shortage of donor organs in paediatric group, mechanical circulatory support (MCS) is now routinely applied as bridging strategy to increase survival on the waiting list for OTHx. We sought to assess the impact of MCS as intention to bridge to OHTx in patients with CHD less than 16 years of age. From 1998 to 2013, 106 patients received 113 episodes of MCS with paracorporeal devices as intention to bridge to OHTx. Twenty-nine had CHD, 15 (52%) with two-ventricle (Group A) and 14 (48%) with single-ventricle physiology (Group B). In Group A, 5 children had venoarterial extracorporeal membrane oxygenation (VA ECMO), 6 left ventricular assist device (LVAD), 2 biventricular assist device (BIVAD), 1 VA ECMO followed by BIVAD and 1 BIVAD followed by VA ECMO. In Group B, VA ECMO was used in 7 children, univentricular assist device (UVAD) changed to VA ECMO in 4, UVAD in 2 and surgical conversion to two-ventricles physiology with BIVAD support changed to VA ECMO in 1. Twenty-one of 29 (72%) children survived to recovery/OHTx. Seven of 29 (59%) survived to discharge. In Group A, 11/15 (73%) survived to recovery/OHTx and 9/15 (60%) survived to discharge. Four of 15 (27%) died awaiting OHTx. One child had graft failure requiring VA ECMO and was bridged successfully to retransplantation. One child dying after OHTx had acute rejection, was supported with VA ECMO and then BIVAD but did not recover. One patient had an unsuccessful second run on BIVAD 1 year after recovery from VA ECMO. In Group B, 10/14 (71%) survived to recovery/OHTx and 8/14 (57%) survived to discharge. Four of 14 (29%) died awaiting OHTx. Of deaths after OHTx, 1 occurred intraoperatively and 1 was consequent to graft failure and had an unsuccessful second run with VA ECMO. Children with CHD can be successfully bridged with MCS to heart transplantation. Single-ventricle circulation compared with biventricular physiology does not increase the risk of death before transplant or before hospital discharge. © The Author 2014. Published by Oxford University Press on behalf of the European Association for Cardio-Thoracic Surgery. All rights reserved.
Free energy landscape of a minimalist salt bridge model.
Li, Xubin; Lv, Chao; Corbett, Karen M; Zheng, Lianqing; Wu, Dongsheng; Yang, Wei
2016-01-01
Salt bridges are essential to protein stability and dynamics. Despite the importance, there has been scarce of detailed discussion on how salt bridge partners interact with each other in distinct solvent exposed environments. In this study, employing a recent generalized orthogonal space tempering (gOST) method, we enabled efficient molecular dynamics simulation of repetitive breaking and reforming of salt bridge structures within a minimalist salt-bridge model, the Asp-Arg dipeptide and thereby were able to map its detailed free energy landscape in aqueous solution. Free energy surface analysis shows that although individually-solvated states are more favorable, salt-bridge states still occupy a noticeable portion of the overall population. Notably, the competing forces, e.g. intercharge attractions that drive the formation of salt bridges and solvation forces that pull the charged groups away from each other, are energetically comparable. As the result, the salt bridge stability is highly tunable by local environments; for instance when local water molecules are perturbed to interact more strongly with each other, the population of the salt-bridge states is likely to increase. Our results reveal the critical role of local solvent structures in modulating salt-bridge partner interactions and imply the importance of water fluctuations on conformational dynamics that involves solvent accessible salt bridge formations. © 2015 The Protein Society.
Xu, Qinqin; Yang, Guang; Ren, Yu; Lu, Futai; Zhang, Nuonuo; Qamar, Muhammad; Yang, Manlin; Zhang, Bao; Feng, Yaqing
2017-11-01
Three donor-π conjugated unit-acceptor (D-π-A) type zinc porphyrin sensitizers LX1, LX2 and LX3 bearing meso acrylic acid, α-cyanoacrylic acid, and α-cyanopentadienoic acid, respectively, as the π-bridged acceptors were designed and synthesized for use in dye-sensitized solar cells (DSCs). The interesting role of the cyano group attached to the α position of the acrylic and pentadienoic acid acceptor was investigated. It was shown that even though the introduction of the cyano group and the elongation of the π-bridge can both increase the light-harvesting as indicated by the UV-vis absorption spectra, the relevant cell performance dropped significantly. The photo to power conversion efficiencies (PCEs) of the devices increase in the order of LX1 > LX2 > LX3, with the highest PCE of 6.04% achieved for the LX1-based cell, which bears acrylic acid as the π-bridged acceptor. To further explore the effect of -CN and -CH[double bond, length as m-dash]CH- on the interaction between the absorbed dye and TiO 2 substrates, their density of states (DOS) and partial density of states (PDOS), as well as electronic properties were investigated in detail using theoretical calculations. The results suggest that introducing the -CN group into the acceptor and extending the conjugation of the π-bridge have decreased the LUMO levels of the dyes, leading to weak interfacial coupling, low electron injection driving force, low J sc , and thus poor cell performance.
Rotator Cuff Repair with a Tendon-Fibrocartilage-Bone Composite Bridging Patch
Ji, Xiaoxi; Chen, Qingshan; Thoreson, Andrew R.; Qu, Jin; An, Kai-Nan; Amadio, Peter C.; Steinmann, Scott P.; Zhao, Chunfeng
2015-01-01
Background To compare the mechanical performance of a rotator cuff repaired with a novel tendon-fibrocartilage-bone composite bridging patch vs the traditional Mason-Allen repair in an in vitro canine model. Methods Twenty shoulders and 10 bridging patches from patellar tendon were harvested. The patches were trimmed and sliced into 2 layers. An infraspinatus tendon tear was created in each shoulder. Modified Mason-Allen sutures were used to repair the infraspinatus tendon to the greater tuberosity, with or without the bridging patch (bridging patch group and controls, respectively). Shoulders were loaded to failure under displacement control at a rate of 0.5mm/sec. Findings The ultimate tensile load was significantly higher in the bridging patch group than control (mean [SD], 365.46 [36.45] vs 272.79 [48.88] N; P<.001). Stiffness at the greater tuberosity repair site and the patch-infraspinatus tendon repair site was significantly higher than the control repair site (93.96 [27.72] vs 42.62 [17.48] N/mm P<.001; 65.94 [24.51] vs 42.62 [17.48] N/mm P=.02, respectively). Interpretation The tendon-fibrocartilage-bone composite bridging patch achieved higher ultimate tensile load and stiffness at the patch–greater tuberosity repair site compared with traditional repair in a canine model. This composite tissue transforms the traditional tendon-to-bone healing interface (with dissimilar tissues) into a pair of bone-to-bone and tendon-to-tendon interfaces, which may improve healing quality and reduce retear rate. PMID:26190097
Rotator cuff repair with a tendon-fibrocartilage-bone composite bridging patch.
Ji, Xiaoxi; Chen, Qingshan; Thoreson, Andrew R; Qu, Jin; An, Kai-Nan; Amadio, Peter C; Steinmann, Scott P; Zhao, Chunfeng
2015-11-01
To compare the mechanical performance of a rotator cuff repaired with a novel tendon-fibrocartilage-bone composite bridging patch vs the traditional Mason-Allen repair in an in vitro canine model. Twenty shoulders and 10 bridging patches from patellar tendon were harvested. The patches were trimmed and sliced into 2 layers. An infraspinatus tendon tear was created in each shoulder. Modified Mason-Allen sutures were used to repair the infraspinatus tendon to the greater tuberosity, with or without the bridging patch (bridging patch group and controls, respectively). Shoulders were loaded to failure under displacement control at a rate of 0.5mm/s. The ultimate tensile load was significantly higher in the bridging patch group than control (mean [SD], 365.46 [36.45] vs 272.79 [48.88] N; P<.001). Stiffness at the greater tuberosity repair site and the patch-infraspinatus tendon repair site was significantly higher than the control repair site (93.96 [27.72] vs 42.62 [17.48] N/mm P<.001; 65.94 [24.51] vs 42.62 [17.48] N/mm P=.02, respectively). The tendon-fibrocartilage-bone composite bridging patch achieved higher ultimate tensile load and stiffness at the patch-greater tuberosity repair site compared with traditional repair in a canine model. This composite tissue transforms the traditional tendon-to-bone healing interface (with dissimilar tissues) into a pair of bone-to-bone and tendon-to-tendon interfaces, which may improve healing quality and reduce retear rate. Copyright © 2015 Elsevier Ltd. All rights reserved.
CAMPARE and Cal-Bridge: Two Institutional Networks Increasing Diversity in Astronomy
NASA Astrophysics Data System (ADS)
Rudolph, Alexander L.; Impey, Chris David; Smecker-Hane, Tammy A.
2016-01-01
We describe two programs, CAMPARE and Cal-Bridge, with the common mission of increasing participation of groups traditionally underrepresented in astronomy, through summer research opportunities, in the case of CAMPARE, scholarships in the case of Cal-Bridge, and significant mentoring in both programs, leading to an increase in their numbers successfully pursuing a PhD in the field.In 6 years, the CAMPARE program has sent 62 students, >85% from underrepresented groups, to conduct summer research at one of twelve major research institutions in California, Arizona, and Wyoming. The graduation rate among CAMPARE scholars is 97%, and of the 37 CAMPARE scholars who have graduated with a Bachelor's degree, almost 60% (21) have completed or are pursuing graduate education in astronomy or a related field, at institutions including UCLA, USC, UC Riverside, Stanford, Univ. of Rochester, Georgia Tech, Kent State, Indiana Univ., Univ. of Oregon, Syracuse, and the Fisk-Vanderbilt Master's-to-PhD program. The Cal-Bridge program is a CSU-UC Bridge program comprised of faculty form 5 University of California (UC), 8 California State University (CSU), and 8 California Community College (CCC) campuses in Southern California. Cal-Bridge provides much deeper mentoring and professional development experiences over the last two years of undergraduate and first year of graduate school to students from this diverse network of higher education institutions. Cal-Bridge Scholars benefit from financial support, intensive, joint mentoring by CSU and UC faculty, professional development workshops, and exposure to research opportunities at the participating UC campuses.
Chok, Kenneth S H; Cheung, Tan To; Lo, Regina C L; Chu, Ferdinand S K; Tsang, Simon H Y; Chan, Albert C Y; Sharr, William W; Fung, James Y Y; Dai, Wing Chiu; Chan, See Ching; Fan, Sheung Tat; Lo, Chung Mau
2014-08-01
The objective of this study was to investigate the outcomes of high-intensity focused ultrasound (HIFU) ablation as a bridging therapy for patients with hepatocellular carcinoma (HCC) who had been wait-listed for deceased donor liver transplantation (DDLT). Adult patients with unresectable and unablatable HCCs within the University of California San Francisco criteria who had been wait-listed for DDLT were screened for their suitability for HIFU ablation as a bridging therapy if they were not suitable for transarterial chemoembolization (TACE). Treatment outcomes for patients receiving HIFU ablation, TACE, and best medical treatment (BMT) were compared. Fifty-one patients were included in the analysis. Before the introduction of HIFU ablation, only 39.2% of the patients had received bridging therapy (TACE only, n = 20). With HIFU ablation in use, the rate increased dramatically to 80.4% (TACE + HIFU, n = 41). The overall dropout rate was 51% (n = 26). Patients in the BMT group had a significantly higher dropout rate (P = 0.03) and significantly poorer liver function as reflected by higher Model for End-Stage Liver Disease scores and higher Child-Pugh grading. Clinically relevant ascites was found in 5 patients in the HIFU group and 2 patients in the BMT group, but none was found in the TACE group (P = 0.01 and P = 0.03, respectively). The TACE and HIFU groups had comparable percentages of tumor necrosis in excised livers (P = 0.35), and both were significantly higher than that in the BMT group (P = 0.01 and P = 0.02, respectively). In conclusion, HIFU ablation was safe even for HCC patients with Child-Pugh C disease. Its adoption increased the percentage of patients receiving bridging therapy from 39.2% to 80.4%. A randomized controlled trial for further validation of its efficacy is warranted. © 2014 American Association for the Study of Liver Diseases.
Merkle, Frank; Boettcher, Wolfgang; Stiller, Brigitte; Hetzer, Roland
2003-06-01
Mechanical cardiac assistance for neonates, infants, children and adolescents may be accomplished with pulsatile ventricular assist devices (VAD) instead of extracorporeal membrane oxygenation or centrifugal pumps. The Berlin Heart VAD consists of extracorporeal, pneumatically driven blood pumps for pulsatile univentricular or biventricular assistance for patients of all age groups. The blood pumps are heparin-coated. The stationary driving unit (IKUS) has the required enhanced compressor performance for pediatric pump sizes. The Berlin Heart VAD was used in a total number of 424 patients from 1987 to November 2001 at our institution. In 45 pediatric patients aged 2 days-17 years the Berlin Heart VAD was applied for long-term support (1-111 days, mean 20 days). There were three patient groups: Group I: "Bridge to transplantation" with various forms of cardiomyopathy (N = 21) or chronic stages of congenital heart disease (N = 9); Group II: "Rescue" in intractable heart failure after corrective surgery for congenital disease (N = 7) or in early graft failure after heart transplantation (N = 1); and Group III: "Acute myocarditis" (N = 7) as either bridge to transplantation or bridge to recovery. Seventeen patients were transplanted after support periods of between 4 and 111 days with 12 long-term survivors, having now survived for up to 10 years. Five patients (Groups I and III) were weaned from the system with four long-term survivors. In Group II only one patient survived after successful transplantation. Prolonged circulatory support with the Berlin Heart VAD is an effective method for bridging until cardiac recovery or transplantation in the pediatric age group. Extubation, mobilization, and enteral nutrition are possible. For long-term use, the Berlin Heart VAD offers advantages over centrifugal pumps and ECMO in respect to patient mobility and safety.
Steib, A; Barre, J; Mertes, M; Morel, M H; Nathan, N; Ozier, Y; Treger, M; Samama, C M
2010-03-01
After a vitamin K antagonist (VKA) overdose, 1-2 mg of oral vitamin K can lower the International Normalized Ratio (INR) to the therapeutic range. To establish whether oral vitamin K can substitute for heparin bridging and decrease the INR to < or = 1.5 before elective surgery. Patients on long-term VKAs were randomized either to heparin bridging after the last VKA dose on day -5 before surgery (group H) or to VKA treatment until day -2, followed by 1 mg of oral vitamin K on the day before surgery (group K). Blood clotting variables were assessed on days -5/-2, 1 and 0, and postoperatively. If the target INR was not achieved 2 h before incision, surgery was deferred or performed after injection of prothrombin complex concentrate (PCC). In 30 of 94 included patients, baseline INR was outside the chosen range (18, INR < 2; 12, INR > 3.5), leaving 34 eligible patients in group H and 30 in group K. The groups were balanced in terms of body mass index, VKA treatment duration and indication, scheduled surgery, preoperative and postoperative hemoglobin, and blood loss. The INR was significantly higher in group K on days -1 and 0 than in group H. An INR < or = 1.5 was not achieved in 20 group K patients (66%). Surgery was postponed or performed after PCC injection in 12 of these 20 patients. Oral vitamin K (1 mg) cannot substitute for heparin bridging before surgery. In addition, one-third of patients on VKAs were exposed to a risk of bleeding (overdose) or thrombosis (underdose), thus highlighting the need for new oral anticoagulants.
Removal of failed crown and bridge
Rahul, G R.; Poduval, Soorya T.; Shetty, Karunakar
2012-01-01
Crown and bridge have life span of many years but they fail for a number of reasons. Over the years, many devices have been designed to remove crowns and bridges from abutment teeth. While the removal of temporary crowns and bridges is usually very straightforward, the removal of a definitive cast crown with unknown cement is more challenging. Removal is often by destructive means. There are a number of circumstances, however, in which conservative disassembly would aid the practitioner in completing restorative/endodontic procedures. There are different mechanisms available to remove a failed crown or bridge. But there is no information published about the classification of available systems for crown and bridge removal. So it is logical to classify these systems into different groups which can help a clinician in choosing a particular type of system depending upon the clinical situation. The aim of this article is to provide a classification for various crown and bridge removal systems; describe how a number of systems work; and when and why they might be used. A PubMed search of English literature was conducted up to January 2010 using the terms: Crown and bridge removal, Crown and bridge disassembly, Crown and bridge failure. Additionally, the bibliographies of 3 previous reviews, their cross references as well as articles published in various journals like International Endodontic Journal, Journal of Endodontics and were manually searched. Key words:Crown and bridge removal, Crown and bridge disassembly, Crown and bridge failure. PMID:24558549
Li, Huiyang; Fang, Manman; Hou, Yingqin; Tang, Runli; Yang, Yizhou; Zhong, Cheng; Li, Qianqian; Li, Zhen
2016-05-18
Four organic sensitizers (LI-68-LI-71) bearing various conjugated bridges were designed and synthesized, in which the only difference between LI-68 and LI-69 (or LI-70 and LI-71) was the absence/presence of the CN group as the auxiliary electron acceptor. Interestingly, compared to the reference dye of LI-68, LI-69 bearing the additional CN group exhibited the bad performance with the decreased Jsc and Voc values. However, once one thiophene moiety near the anchor group was replaced by pyrrole with the electron-rich property, the resultant LI-71 exhibited a photoelectric conversion efficiency increase by about 3 folds from 2.75% (LI-69) to 7.95% (LI-71), displaying the synergistic effect of the two moieties (CN and pyrrole). Computational analysis disclosed that pyrrole as the auxiliary electron donor (D') in the conjugated bridge can compensate for the lower negative charge in the electron acceptor, which was caused by the CN group as the electron trap, leading to the more efficient electron injection and better photovoltaic performance.
Wongcharoen, Wanwarang; Pinyosamosorn, Kittipong; Gunaparn, Siriluck; Boonnayhun, Suchada; Thonghong, Tasalak; Suwannasom, Pannipa; Phrommintikul, Arintaya
2017-08-01
Warfarin discontinuation with heparin bridging is a common practice in patients receiving warfarin prior to elective coronary angiography (CAG). The uninterrupted warfarin strategy has been suggested to be alternative option for patients with high thromboembolic risk. Therefore, we aimed to assess the safety of elective transfemoral CAG during uninterrupted warfarin therapy compared to heparin bridging. This study was a randomized open-label design with blinded event evaluation. The 110 consecutive patients (age ≥ 18 years) receiving warfarin before the planned transfemoral CAG were randomly assigned to either heparin bridging or uninterrupted warfarin with targeted INR (2.0-3.0). The primary outcome was the incidence of major vascular access site complications. The baseline characteristics were comparable between two groups (mean age was 60.1 ± 7.8 years, 49 males). The mean INR on the day of CAG of heparin bridging and uninterrupted warfarin groups was 1.2 ± 0.3 and 2.2 ± 0.5 (P < 0.001). The major vascular access site complications occurred in 3 of 55 (5.5%) heparin-bridging patients and in none of 55 uninterrupted warfarin patients (P = 0.243). The total vascular access site complications occurred in 6 (10.9%) heparin-bridging and one (1.8%) uninterrupted warfarin patients (P = 0.113). No patient developed either other bleeding or thromboembolic events during 7 days after CAG. We demonstrated that an uninterrupted warfarin strategy did not increase vascular access site complications in patients undergoing transfemoral CAG compared to heparin bridging therapy. Due to the safety and the ease of uninterrupted warfarin strategy, this approach should be encouraged in patients receiving long-term warfarin who undergo elective transfemoral CAG. © 2017, Wiley Periodicals, Inc.
Lindemans, Caroline A; Te Boome, Liane C J; Admiraal, Rick; Jol-van der Zijde, Els C; Wensing, Anne M; Versluijs, A Birgitta; Bierings, Marc B; Kuball, Jürgen; Boelens, Jaap J
2015-10-01
In haploidentical (haplo)-cord blood (CB) transplantations, early haplo donor engraftment serves as a myeloid bridge to sustainable CB engraftment and is associated with early neutrophil recovery. The conditioning regimens as published for haplo-cord protocols usually contain serotherapy, such as rabbit antithymocyte globulin (ATG) (Thymoglobulin, Genzyme, Cambridge, MA). However, reducing or omitting serotherapy is an important strategy to improve early immune reconstitution after transplantation. The need for serotherapy in successful haplo-cord transplantation, defined as having a haplo-derived myeloid bridge to CB engraftment, has not been investigated before. Two consecutive cohorts of patients underwent transplantation with haplo-CB. The first group underwent transplantation with haplo-CB for active infection and/or an underlying condition with expected difficult engraftment without a conventional donor available. They received a single unit (s) CB and haplo donor cells (CD34(+) selected, 5 × 10(6) CD34(+)/kg). The second cohort included patients with poor-risk malignancies, not eligible for other treatment protocols. They received a sCB and haplo donor cells (CD19/αβTCR-depleted; 5 × 10(6) CD34(+)/kg). Retrospectively in both cohorts, active ATG (Thymoglobulin) levels were measured and post-hematopoietic cell transplantation area under the curve (AUC) was calculated. The influence of ATG exposure for having a successful haplo-myeloid bridge (early haplo donor engraftment before CB engraftment and no secondary neutropenia) and transplantation-related mortality (TRM) were analyzed as primary endpoints. Twenty patients were included (16 in the first cohort and 4 in the second cohort). In 58% of evaluable patients, there was no successful haplo-derived myeloid bridge to CB engraftment, for which a low post-transplantation ATG exposure appeared to be a predictor (P <.001). TRM in the unsuccessful haplo-bridge group was 70% ± 16% versus 12% ± 12% in the successful haplo-bridge group (P = .012). In conclusion, sufficient in vivo T depletion with ATG is required for a successful haplo-myeloid bridge to CB engraftment. Copyright © 2015 American Society for Blood and Marrow Transplantation. Published by Elsevier Inc. All rights reserved.
Cooper, Katelyn M.; Ashley, Michael; Brownell, Sara E.
2017-01-01
National calls to improve student academic success in college have sparked the development of bridge programs designed to help students transition from high school to college. We designed a 2-week Summer Bridge program that taught introductory biology content in an active-learning way. Through a set of exploratory interviews, we unexpectedly identified that Bridge students had developed sophisticated views of active learning, even though this was not an explicit goal of the program. We conducted an additional set of semistructured interviews that focused on active learning and compared the interviews of Bridge students with those from non-Bridge students who had been eligible for but did not participate in the program. We used the constant comparative method to identify themes from the interviews. We found that Bridge students perceived that, because they knew how to approach active learning and viewed it as important, they benefited more from active learning in introductory biology than non-Bridge students. Specifically, Bridge students seemed to be more aware of their own learning gains from participating in active learning. Compared with the majority of non-Bridge students, the majority of Bridge students described using a greater variety of strategies to maximize their experiences in active learning. Finally, in contrast to non-Bridge students, Bridge students indicated that they take an equitable approach to group work. These findings suggest that we may be able to prime students to maximize their own and other’s experiences in active learning. PMID:28232588
Jiang, Yi; Banerjee, Abhijit; Brodie, Peggy J.; Bane, Susan; Kingston, David G. I.; Liotta, Dennis C.
2011-01-01
A series of conformationally restrained epothilone analogs with a short bridge between the methyl groups at C6 and C8 was designed to mimic the binding pose assigned to our recently reported EpoA-microtubule binding model. A versatile synthetic route to these bridged epothilone analogs has been successfully devised and implemented. Biological evaluation of the compounds against A2780 human ovarian cancer and PC3 prostate cancer cell lines suggested that the introduction of a bridge between C6-C8 reduced potency by 25–1000 fold in comparison with natural epothilone D. Tubulin assembly measurements indicate these bridged epothilone analogs to be mildly active, but without significant microtubule stabilization capacity. Molecular mechanics and DFT energy evaluations suggest the mild activity of the bridged epo-analogs may be due to internal conformational strain. PMID:22127984
Ide, Junji; Karasugi, Tatsuki; Okamoto, Nobukazu; Taniwaki, Takuya; Oka, Kiyoshi; Mizuta, Hiroshi
2015-10-01
We compared the outcomes of knotless double-row suture bridge and single-row repairs in patients undergoing arthroscopic repair for anterosuperior rotator cuff tears. We included 61 full-thickness anterosuperior rotator cuff tears treated by arthroscopic repair, namely, single-row repair (group 1: 25 shoulders; mean patient age, 64 years) and the knotless double-row suture bridge repair (group 2: 36 shoulders; mean patient age, 62 years). Preoperative and postoperative magnetic resonance imaging was performed for all shoulders. Clinical outcomes were evaluated for mean follow-up periods of 81 months (range, 72-96 months) in group 1 and 34 months (range, 24-42 months) in group 2, using the University of California, Los Angeles and Japanese Orthopaedic Association assessments. At the final follow-up, both groups showed improvement in the average University of California, Los Angeles and Japanese Orthopaedic Association scores and range of motion, although no intergroup differences were observed. Both groups showed improved abduction strength, and the average score was higher in group 2 (P = .0112). The lift-off and belly-press test results were improved in both groups. Postoperatively, the incidence of positive lift-off tests tended to be lower (P = .075) and that of positive belly-press tests was lower in group 2, P = .049). The repair failure rate tended to be lower in group 2 (14% [5 of 36]) than in group 1 (32% [8 of 25]; P = .0839). Arthroscopic knotless double-row suture bridge repair of anterosuperior rotator cuff tears yielded functional outcomes equivalent to those of single-row repair and may be useful for improving subscapularis function, abduction strength, and tendon healing. Copyright © 2015 Journal of Shoulder and Elbow Surgery Board of Trustees. Published by Elsevier Inc. All rights reserved.
MacKinnon, Christopher J; Smith, Nathan Grant; Henry, Melissa; Berish, Mel; Milman, Evgenia; Körner, Annett; Copeland, Laura S; Chochinov, Harvey M; Cohen, S Robin
2014-01-01
A growing body of scholarship has evaluated the usefulness of meaning-based theories in the context of bereavement counseling. Although scholars have discussed the application of meaning-based theories for individual practice, there is a lack of inquiry regarding its implications when conducting bereavement support groups. The objective of this article is to bridge meaning-based theories with bereavement group practice, leading to a novel intervention and laying the foundation for future efficacy studies. Building on recommendations specified in the literature, this article outlines the theoretical paradigms and structure of a short-term meaning-based group counseling intervention for uncomplicated bereavement.
Poly[mu2-(N-hydroxypyridine-2-carboxamidine)-mu2-nitrato-silver(I)].
Cui, Ai-Li; Han, Peng; Yang, Hui-Juan; Wang, Ru-Ji; Kou, Hui-Zhong
2007-12-01
In the title complex, [Ag(NO3)(C6H7N3O)]n or [Ag(NO3)(pyaoxH2)] (pyaoxH2 is N-hydroxypyridine-2-carboxamidine), the Ag+ ion is bridged by the pyaoxH2 ligands and nitrate anions, giving rise to a two-dimensional molecular structure. Each pyaoxH2 ligand coordinates to two Ag+ ions using its pyridyl and carboxamidine N atoms, and the OH and the NH2 groups are uncoordinated. Each nitrate anion uses two O atoms to coordinate to two Ag+ ions. The Ag...Ag separation via the pyaoxH2 bridge is 2.869 (1) A, markedly shorter than that of 6.452 (1) A via the nitrate bridge. The two-dimensional structure is fishscale-like, and can be described as pyaoxH2-bridged Ag2 nodes that are further linked by nitrate anions. Hydrogen bonding between the amidine groups and the nitrate O atoms connects adjacent layers into a three-dimensional network.
Gujjari, Anil K; Bhatnagar, Vishrut M; Basavaraju, Ravi M
2013-01-01
To evaluate the color stability and flexural strength of poly (methyl methacrylate) (PMMA) and bis-acrylic composite based provisional crown and bridge auto-polymerizing resins exposed to tea, coffee, cola, and food dye. Two provisional crown and bridge resins, one DPI self-cure tooth molding powder (PMMA) (Group A), and one Protemp 4 Temporization Material (bis-acrylic composite) (Group B) were used. Disk-shaped specimens for color stability testing (n = 30 for each material) and bar-shaped specimens for flexural strength testing (n = 30 for each material) were fabricated using a metal mold. The specimens were immersed in artificial saliva, artificial saliva + tea, artificial saliva + coffee, artificial saliva + cola, and artificial saliva + food dye solutions and stored in an incubator at 37°C. Color measurements were taken before immersion, and then after 3 and 7 days of immersion. Flexural strength was evaluated after 7 days of immersion. Group A showed significantly higher color stability as compared to Group B, and artificial saliva + coffee solution had the most staining capacity for the resins. Test solutions had no effect on the flexural strength of Group A, but Group B specimens immersed in artificial saliva + cola showed significantly lower flexural strength values as compared to the control group. The findings of the study showed that for materials used in the study, PMMA was more color stable than bis-acrylic composite based resin. Also, material based on PMMA was more resistant to damage from dietary beverages as compared to bis-acrylic composite based provisional crown and bridge resin.
Lyimo, Elizabeth J.; Todd, Jim; Rickey, Lisa Ann; Njau, Bernard
2014-01-01
This study describes the social networks of secondary school students in Moshi Municipality, and their association with self-rated risk of human immunodeficiency virus (HIV) infection. A cross-sectional analytical study was conducted among 300 students aged 15–24 years in 5 secondary schools in Moshi, Tanzania. Bonding networks were defined as social groupings of students participating in activities within the school, while bridging networks were groups that included students participating in social groupings from outside of the school environs. A structured questionnaire was used to ask about participation in bonding and bridging social networks and self-rated HIV risk behavior. More participants participated in bonding networks (72%) than in bridging networks (29%). Participation in bridging networks was greater among females (25%) than males (12%, p < .005). Of 300 participants, 88 (29%) were sexually experienced, and of these 62 (70%) considered themselves to be at low risk of HIV infection. Factors associated with self-rated risk of HIV included: type of school (p < .003), family structure (p < .008), being sexually experienced (p < .004), having had sex in the past three months (p < .009), having an extra sexual partner (p < .054) and non-condom use in last sexual intercourse (p < .001), but not the presence or type of social capital. The study found no association between bonding and bridging social networks on self-rated risk of HIV among study participants. However, sexually experienced participants rated themselves at low risk of HIV infection despite practicing unsafe sex. Efforts to raise adolescents’ self-awareness of risk of HIV infection through life skills education and HIV/acquired immunodeficiency syndrome risk reduction strategies may be beneficial to students in this at-risk group. PMID:24641669
Pounraj, P; Mohankumar, V; Pandian, M Senthil; Ramasamy, P
2018-01-01
Twenty eight bi-anchored triphenylamine (TH-1 to TH-14) and phenyl modified triphenylamine (PH-TH-1 to PH-TH-14) based metal free organic dyes are designed for DSSC application. The electronic effect of different π-bridge configurations in donor-π-bridge-acceptor (D-π-A) 2 structure was theoretically simulated and verified using density functional theory (DFT) and time dependent density functional theory (TD-DFT). The triphenylamine and phenyl modified triphenylamine groups are used as donor and cyanoacrylic acid group is used as acceptor. Thiophene and cyanovinyl groups are used as π-bridge. The ground state molecular structure was optimized by density functional theory and the electronic absorption spectra were calculated by time dependent density functional theory. The light harvesting efficiency (LHE), dye regeneration energy (ΔG reg ) and electron injection energy (ΔG inject ) are determined by computational examination. It is observed that, when the number of π-bridge increases, the band gap of the dye decreases. Also the absorption maximum and molar extinction coefficient of the dyes are increased. Theoretical result shows that the thiophene-cyanovinyl and thiophene-thiophene-cyanovinyl-cyanovinyl configurations give broader and red shifted absorption spectrum compared to other configurations. Also the results of phenyl modified triphenylamine (PH-TH) dyes clearly show better absorption and dye regeneration energy compared to TH dyes. Copyright © 2017 Elsevier Inc. All rights reserved.
1990-08-16
do you think elicited the Prime Minis- ter’s trust in you? [Kadar] I met Jozsef Antall for the first time when the Hid [ Bridge ] group was formed...general eco- nomic-policy concepts of the various parties, the Blue Ribbon Commission, and the Bridge group. Aside from a few trade union circles...their men’s weapons away from them." There is scarcely a Soviet military man who can imagine Soviet divisions staying on in a reunified Germany
Bridges and Barriers: Adolescent Perceptions of Student-Teacher Relationships
ERIC Educational Resources Information Center
McHugh, Rebecca Munnell; Horner, Christy Galletta; Colditz, Jason B.; Wallace, Tanner LeBaron
2013-01-01
In urban secondary schools where underpreparation and dropping out are real world concerns, students understand that their relationships with teachers affect their learning. Using descriptive coding and thematic analysis of focus group data, we explore adolescents' perceptions of the "bridges" that foster and the "barriers"…
Ciarka, Agnieszka; Edwards, Leah; Nilsson, Johan; Stehlik, Josef; Lund, Lars H
2017-03-15
Numerous cohort analyses suggest rapidly increasing use of mechanical circulatory support (MCS) as a bridge to heart transplantation (HTx), but the role of age in selection for MCS remains unknown. We assessed adult HTx in the International Society for Heart And Lung Transplantation Registry between 2005 and 2013 and we determined MCS use by recipient age group and transplant year. Multivariable logistic regression models were constructed to identify variables associated with continuous flow (CF) left ventricular assist device (LVAD) use within each age group. Among 16,480 HTx recipients the percentage of overall MCS use increased from 23% to 38%, 21% to 41%, and 17% to 42% in age groups 18-39 years, 40-59 years and over 60 years, respectively. This effect was mainly due to an increase in CF LVAD use and primarily in HTx recipients aged over 60. In multivariable analyses, male gender and blood group O were significantly associated with CF LVAD use in all age groups. Bridge to transplant MCS use increased dramatically between 2005 and 2013 primarily due to increased use of CF LVAD and primarily in higher ages. Pre-HTx CF LVAD use was more frequent in men and blood group O. Copyright © 2016 Elsevier Ireland Ltd. All rights reserved.
Imamura, Takeshi; Saiki, Kazunobu; Okamoto, Keishi; Maeda, Junichiro; Matsuo, Hiroaki; Wakebe, Tetsuaki; Ogami, Keiko; Tomita, Masato; Tagami, Atsushi; Shindo, Hiroyuki; Tsurumoto, Toshiyuki
2014-01-01
The aim of this study was to characterize the individuals with sacroiliac joint bridging (SIB) by analyzing the degenerative changes in their whole vertebral column and comparing them with the controls. A total of 291 modern Japanese male skeletons, with an average age at death of 60.8 years, were examined macroscopically. They were divided into two groups: individuals with SIB and those without bridging (Non-SIB). The degenerative changes in their whole vertebral column were evaluated, and marginal osteophyte scores (MOS) of the vertebral bodies and degenerative joint scores in zygapophyseal joints were calculated. SIB was recognized in 30 individuals from a total of 291 males (10.3%). The average of age at death in SIB group was significantly higher than that in Non-SIB group. The values of MOS in the thoracic spines, particularly in the anterior part of the vertebral bodies, were consecutively higher in SIB group than in Non-SIB group. Incidence of fused vertebral bodies intervertebral levels was obviously higher in SIB group than in Non-SIB group. SIB and marginal osteophyte formation in vertebral bodies could coexist in a skeletal population of men. Some systemic factors might act on these degenerative changes simultaneously both in sacroiliac joint and in vertebral column. PMID:25276825
On the multi-reference nature of plutonium oxides: PuO22+, PuO2, PuO3 and PuO2(OH)2.
Boguslawski, Katharina; Réal, Florent; Tecmer, Paweł; Duperrouzel, Corinne; Gomes, André Severo Pereira; Legeza, Örs; Ayers, Paul W; Vallet, Valérie
2017-02-08
Actinide-containing complexes present formidable challenges for electronic structure methods due to the large number of degenerate or quasi-degenerate electronic states arising from partially occupied 5f and 6d shells. Conventional multi-reference methods can treat active spaces that are often at the upper limit of what is required for a proper treatment of species with complex electronic structures, leaving no room for verifying their suitability. In this work we address the issue of properly defining the active spaces in such calculations, and introduce a protocol to determine optimal active spaces based on the use of the Density Matrix Renormalization Group algorithm and concepts of quantum information theory. We apply the protocol to elucidate the electronic structure and bonding mechanism of volatile plutonium oxides (PuO 3 and PuO 2 (OH) 2 ), species associated with nuclear safety issues for which little is known about the electronic structure and energetics. We show how, within a scalar relativistic framework, orbital-pair correlations can be used to guide the definition of optimal active spaces which provide an accurate description of static/non-dynamic electron correlation, as well as to analyse the chemical bonding beyond a simple orbital model. From this bonding analysis we are able to show that the addition of oxo- or hydroxo-groups to the plutonium dioxide species considerably changes the π-bonding mechanism with respect to the bare triatomics, resulting in bent structures with a considerable multi-reference character.
The Memory Bridge Initiative on Service Learners
ERIC Educational Resources Information Center
Wescott, Amy; Healy, Tara C.
2011-01-01
This study evaluated the Memory Bridge Initiative (MBI), an educational, experiential program pairing high school students with older adults who have dementia. A qualitative, single group design with baseline and follow-up measures examined whether or not students would have a positive learning experience while gaining newfound appreciation and…
Focus on Student Success: Components for Effective Summer Bridge Programs
ERIC Educational Resources Information Center
Gonzalez Quiroz, Alicia; Garza, Nora R.
2018-01-01
Using research focused on best practices, focus group information, and data analytics, the Title V: Focus on Student Success (FOSS) Grant created a model for the development, implementation, and evaluation of a summer bridge program. Results included increased academic performance indicators in first-year Hispanic college students. Validation for…
A sustainable dietetics bridging program: development and implementation in Atlantic Canada.
Lordly, Daphne; Guy, Jennifer; Barry, Paula; Garus, Jennifer
2014-01-01
A provincial focus on immigration and improved foreign credential recognition has led to an investigation of best practices and subsequent recommendations for the development and implementation of a sustainable university-based bridging program for internationally educated dietitians in Atlantic Canada. Data were collected from various sources and used to inform program decisions and direction. An advisory framework was established through a core group representing dietetics education and regulation and internationalization. Subsequently, a key stakeholder group was formed. As a result of this collaboration and research, a dietetics bridging framework was developed and a program pilot tested. Lessons learned may inform similar endeavours and highlight the importance of collaborative leadership and collaboration among multiple stakeholders, and of creatively addressing program sustainability issues while keeping learners (internationally educated dietitians) at the centre.
Levy, Aharon; Saguy, Tamar; Halperin, Eran; van Zomeren, Martijn
2017-01-01
The modern era of globalization has been accompanied by a massive growth in interconnections between groups, and has led to the sharing of multiple identities by individuals and groups. Following these developments, research has focused on the issue of multiple identities, and has shed important light on how individuals who hold these complex forms of identity feel and behave, and on the reactions they elicit from members of other groups. However, the potential of groups with such multiple identities (e.g., biracials, immigrants, etc.) to affect the intergroup relations between the groups that represent the respective sources of the different identities (e.g., Blacks and Whites, country of origin and country of residence, etc.) has not been examined to date. Accordingly, in this paper, we first systematically explore the potential of groups in which people identify with multiple social categories, or groups that are perceived as such by others, to play a role in intergroup dynamics. Next, we offer a theoretical framework outlining what functions groups of people with shared multiple identities may serve (as bridges or barriers ) by proposing how their presence may facilitate or deteriorate intergroup relations. Finally, we present recent empirical research examining how groups of people with shared multiple identities can act as gateways and bridge the cleft between two separate groups that represent the respective sources of their different identities, and discuss the theoretical and practical implications for the field of intergroup relations.
Levy, Aharon; Saguy, Tamar; Halperin, Eran; van Zomeren, Martijn
2017-01-01
The modern era of globalization has been accompanied by a massive growth in interconnections between groups, and has led to the sharing of multiple identities by individuals and groups. Following these developments, research has focused on the issue of multiple identities, and has shed important light on how individuals who hold these complex forms of identity feel and behave, and on the reactions they elicit from members of other groups. However, the potential of groups with such multiple identities (e.g., biracials, immigrants, etc.) to affect the intergroup relations between the groups that represent the respective sources of the different identities (e.g., Blacks and Whites, country of origin and country of residence, etc.) has not been examined to date. Accordingly, in this paper, we first systematically explore the potential of groups in which people identify with multiple social categories, or groups that are perceived as such by others, to play a role in intergroup dynamics. Next, we offer a theoretical framework outlining what functions groups of people with shared multiple identities may serve (as bridges or barriers) by proposing how their presence may facilitate or deteriorate intergroup relations. Finally, we present recent empirical research examining how groups of people with shared multiple identities can act as gateways and bridge the cleft between two separate groups that represent the respective sources of their different identities, and discuss the theoretical and practical implications for the field of intergroup relations. PMID:28706501
Suicides by jumping from iconic bridges in Hong Kong.
Wong, P W C; Chan, W S C; Lau, T K; Morgan, P R; Yip, P S F
2009-01-01
Three bridges in Hong Kong have become iconic sites for suicide since their openings 11 years ago. This retrospective record-based study aimed to examine suicides by jumping from a group of three iconic bridges in Hong Kong, and to explore potential preventive strategies on these bridges to prevent future suicide. We examined the Coroner's files of 12 people who killed themselves by jumping from the bridges between 1997 and 2007. We also examined the Coroner's files of other suicides in 2003, and compared them with the bridge suicides. The majority of the suicides were male, middle-age (40-59 years), married or cohabiting, not living alone, employed or self-employed, and in financial difficulty. None of these cases had a reported psychiatric diagnosis or psychiatric care history, and only one case had a history of suicidal attempt. Compared with other suicides in Hong Kong, the bridge jumpers were more likely to be younger, holding a job, indebted, free from a psychiatric and attempt history, and to leave a suicide note (p < .05). The bridge suicide cases in Hong Kong also appeared to be different from the profiles of bridge jumpers in other countries. Erection of an effective safety barrier has been found to prevent bridge suicides in many countries. Given the different characteristics of bridge jumpers in Hong Kong and the technical difficulties, more innovative ways may be needed to prevent suicides by such means. Potential prevention measures are discussed and, hopefully, will better inform the future design and development of bridges of significance.
NASA Astrophysics Data System (ADS)
Agüeros, Marcel A.
2015-01-01
Columbia University's Bridge to the Ph.D. in the Natural Sciences Program aims to enhance the participation of students from underrepresented groups in Ph.D. programs. To achieve this, the Bridge Program provides an intensive research, coursework, and mentoring experience to post-baccalaureates seeking to strengthen their graduate school applications and to prepare for the transition into graduate school. To date, 20 Bridge Program alumni --- including four in astronomy --- have gone on to Ph.D. programs at Columbia, the University of Michigan, Johns Hopkins, the University of Washington, Albert Einstein, Yale, and SUNY-Albany, among others. In this talk, I will touch on some of the connections between Pre-MAP and the Bridge Program, and particularly how my involvement in the former prepared me to lead the latter.
[Equating scores using bridging stations on the clinical performance examination].
Yoo, Dong-Mi; Han, Jae-Jin
2013-06-01
This study examined the use of the Tucker linear equating method in producing an individual student's score in 3 groups with bridging stations over 3 consecutive days of the clinical performance examination (CPX) and compared the differences in scoring patterns by bridging number. Data were drawn from 88 examinees from 3 different CPX groups-DAY1, DAY2, and DAY3-each of which comprised of 6 stations. Each group had 3 common stations, and each group had 2 or 3 stations that differed from other groups. DAY1 and DAY3 were equated to DAY2. Equated mean scores and standard deviations were compared with the originals. DAY1 and DAY3 were equated again, and the differences in scores (equated score-raw score) were compared between the 3 sets of equated scores. By equating to DAY2, DAY1 decreased in mean score from 58.188 to 56.549 and in standard deviation from 4.991 to 5.046, and DAY3 fell in mean score from 58.351 to 58.057 and in standard deviation from 5.546 to 5.856, which demonstrates that the scores of examinees in DAY1 and DAY2 were accentuated after use of the equation. The patterns in score differences between the equated sets to DAY1, DAY2, and DAY3 yielded information on the soundness of the equating results from individual and overall comparisons. To generate equated scores between 3 groups on 3 consecutive days of the CPX, we applied the Tucker linear equating method. We also present a method of equating reciprocal days to the anchoring day as much as bridging stations.
Preliminary evaluation of a load-bearing BMP-2 carrier for segmental defect regeneration.
Chu, Tien-Min G; Sargent, Peter; Warden, Stuart J; Turner, Charles H; Stewart, Rena L
2006-01-01
Large segmental defects in bones can result from tumor removal, massive trauma, congenital malformation, or non-union fractures. Such defects often are difficult to manage and require multiple-phase surgery to achieve adequate union and function. In this study, we propose a novel design of bone morphogenetic protein 2 (BMP-2) carrier for tissue engineering of segmental defect regeneration. The tube-shaped BMP-2 carrier was fabrication from a poly(propylene fumarate)/tricalcium phosphate (PPF/TCP) composite via casting technique developed in our laboratory. An in vitro evaluation showed that the compressive strength of the carrier decreased about 48% in 12 weeks while maintained a pH in the 6.8-7.4 range. In vivo study was conducted by implanting carriers loaded with 10 microg of BMP-2 in 5 mm rat femur gap model for 15 weeks. X-ray evidence of bridging was first found in the BMP group at 3 weeks. Bridging in all animals (N = 4) in the BMP group was found at 9 weeks. No x-ray evidence of bridging was found in the No BMP group (N = 3). pQCT analysis indicated that the bone mineral density of the callus in the BMP group has reached the level of native femur at 15 weeks after implantation, while the callus in the No BMP group has a bone mineral density at a lower level of 84% to the native femur. Histology analysis shows that a normal fatty bone marrow was restored and mineralized callus formed and bridged the segmental defect.
Tílvez, Elkin; Cárdenas-Jirón, Gloria I; Menéndez, María I; López, Ramón
2015-02-16
A thoroughly mechanistic investigation on the [Cp2Mo(OH)(OH2)](+)-catalyzed hydrolysis of ethyl acetate has been performed using density functional theory methodology together with continuum and discrete-continuum solvation models. The use of explicit water molecules in the PCM-B3LYP/aug-cc-pVTZ (aug-cc-pVTZ-PP for Mo)//PCM-B3LYP/aug-cc-pVDZ (aug-cc-pVDZ-PP for Mo) computations is crucial to show that the intramolecular hydroxo ligand attack is the preferred mechanism in agreement with experimental suggestions. Besides, the most stable intermediate located along this mechanism is analogous to that experimentally reported for the norbornenyl acetate hydrolysis catalyzed by molybdocenes. The three most relevant steps are the formation and cleavage of the tetrahedral intermediate immediately formed after the hydroxo ligand attack and the acetic acid formation, with the second one being the rate-determining step with a Gibbs energy barrier of 36.7 kcal/mol. Among several functionals checked, B3LYP-D3 and M06 give the best agreement with experiment as the rate-determining Gibbs energy barrier obtained only differs 0.2 and 0.7 kcal/mol, respectively, from that derived from the experimental kinetic constant measured at 296.15 K. In both cases, the acetic acid elimination becomes now the rate-determining step of the overall process as it is 0.4 kcal/mol less stable than the tetrahedral intermediate cleavage. Apart from clarifying the identity of the cyclic intermediate and discarding the tetrahedral intermediate formation as the rate-determining step for the mechanism of the acetyl acetate hydrolysis catalyzed by molybdocenes, the small difference in the Gibbs energy barrier found between the acetic acid formation and the tetrahedral intermediate cleavage also uncovers that the rate-determining step could change when studying the reactivity of carboxylic esters other than ethyl acetate substrate specific toward molybdocenes or other transition metal complexes. Therefore, in general, the information reported here could be of interest in designing new catalysts and understanding the reaction mechanism of these and other metal-catalyzed hydrolysis reactions.
Hadamitzky, Catarina; Zaitseva, Tatiana S; Bazalova-Carter, Magdalena; Paukshto, Michael V; Hou, Luqia; Strassberg, Zachary; Ferguson, James; Matsuura, Yuka; Dash, Rajesh; Yang, Phillip C; Kretchetov, Shura; Vogt, Peter M; Rockson, Stanley G; Cooke, John P; Huang, Ngan F
2016-09-01
Secondary lymphedema is a common disorder associated with acquired functional impairment of the lymphatic system. The goal of this study was to evaluate the therapeutic efficacy of aligned nanofibrillar collagen scaffolds (BioBridge) positioned across the area of lymphatic obstruction in guiding lymphatic regeneration. In a porcine model of acquired lymphedema, animals were treated with BioBridge scaffolds, alone or in conjunction with autologous lymph node transfer as a source of endogenous lymphatic growth factor. They were compared with a surgical control group and a second control group in which the implanted BioBridge was supplemented with exogenous vascular endothelial growth factor-C (VEGF-C). Three months after implantation, immunofluorescence staining of lymphatic vessels demonstrated a significant increase in lymphatic collectors within close proximity to the scaffolds. To quantify the functional impact of scaffold implantation, bioimpedance was used as an early indicator of extracellular fluid accumulation. In comparison to the levels prior to implantation, the bioimpedance ratio was significantly improved only in the experimental BioBridge recipients with or without lymph node transfer, suggesting restoration of functional lymphatic drainage. These results further correlated with quantifiable lymphatic collectors, as visualized by contrast-enhanced computed tomography. They demonstrate the therapeutic potential of BioBridge scaffolds in secondary lymphedema. Copyright © 2016 Elsevier Ltd. All rights reserved.
Bennett, Misty M; Beehr, Terry A; Lepisto, Lawrence R
2016-09-01
Older employees are increasingly accepting bridge employment, which occurs when older workers take employment for pay after they retire from their main career. This study examined predictors of workers' decisions to engage in bridge employment versus full retirement and career employment. A national sample of 482 older people in the United States was surveyed regarding various work-related and nonwork related predictors of retirement decisions, and their retirement status was measured 5 years later. In bivariate analyses, both work-related variables (career goal achievement and experienced pressure to retire) and nonwork-related variables (psychological distress and traditional gender role orientation) predicted taking bridge employment, but in multinomial logistic regression, only nonwork variables had unique effects. Few predictors differentiated the bridge employed and fully retired groups. Nonwork variables were salient in making the decision to retire, and bridge employment may be conceptually more similar to full retirement than to career employment. © The Author(s) 2016.
Artificial organs versus regenerative medicine: is it true?
Nosé, Yukihiko; Okubo, Hisashi
2003-09-01
Individuals engaged in the fields of artificial kidney and artificial heart have often mistakenly stated that "the era of artificial organs is over; regenerative medicine is the future." Contrarily, we do not believe artificial organs and regenerative medicine are different medical technologies. As a matter of fact, artificial organs developed during the last 50 years have been used as a bridge to regeneration. The only difference between regenerative medicine and artificial organs is that artificial organs for the bridge to regeneration promote tissue regeneration in situ, instead of outside the body (for example, vascular prostheses, neuroprostheses, bladder substitutes, skin prostheses, bone prostheses, cartilage prostheses, ligament prostheses, etc.). All of these artificial organs are successful because tissue regeneration over a man-made prosthesis is established inside the patient's body (artificial organs to support regeneration). Another usage of the group of artificial organs for the bridge to regeneration is to sustain the functions of the patient's diseased organs during the regeneration process of the body's healthy tissues and/or organs. This particular group includes artificial kidney, hepatic assist, respiratory assist, and circulatory assist. Proof of regeneration of these healthy tissues and/or organs is demonstrated in the short-term recovery of end-stage organ failure patients (artificial organs for bridge to regeneration). A third group of artificial organs for the bridge to regeneration accelerates the regenerating process of the patient's healthy tissues and organs. This group includes neurostimulators, artificial blood (red cells) blood oxygenators, and plasmapheresis devices, including hemodiafiltrators. So-called "therapeutic artificial organs" fall into this category (artificial organs to accelerate regeneration). Thus, almost all of today's artificial organs are useful in the bridge to regeneration of healthy natural tissues and organs. It does not matter whether these tissues are cultivated inside or outside the patient's body. Thus, we strongly believe in the need for joint development programs between artificial organ technologies and regenerative medicine technologies. In particular, the importance of using both man-made substitute organ technologies and natural tissue-derived substitute organ technologies is stressed for improved medical care in the future.
Characteristics Of Bridging Oxo And Sulfido Groups In Multinuclear Iron Proteins
NASA Astrophysics Data System (ADS)
Loehr, Thomas M.
1989-07-01
The presence of oxo-bridged dinuclear iron clusters has been established in the respiratory protein, hemerythrin (Hr), and in the DNA-biosynthesis regulatory enzyme, ribonucleotide reductase (Rr). For the iron proteins uteroferrin and purple acid phosphatase (PAP) evidence for μ-oxo-bridged centers is less clear. Resonance Raman (RR) spectra obtained by excitation into an 0(2-) --> Fe(III) CT band may show strong symmetric and weak antisymmetric Fe-0-Fe vibrational modes. We have investigated the spectra of a variety of μ-oxo-bridged Fe(III) complexes to establish the dependence of Raman scattering intensities upon structural parameters. Intensities were found to relate to the nature of the ligand trans to the oxo group: nitrogen ligands with unsaturation (e.g., pyrazole and imidazole) lead to strong scattering, whereas saturated ligands provide only poor scattering. The Fe-0 bonds in Hr and Rr are strong scatterers; the former is known from x-ray crystallography to have a histidyl ligand trans to the μ-oxo group. On this basis, a similar ligand structure is likely in the reductase. In contrast, PAP shows no oxo-bridge with UV and near-UV excitation. We propose that a different structural framework is necessary to account for this result. Hydrogen bonding of protein side chains to oxo and sulfido ligands is proposed to explain changes in frequencies for samples dissolved in water vs. D20. Differences in hydrogen-bond strengths between 0...(D) and S...(D) systems are transferred to the observed Fe-0 and Fe-S bond vibrations.
Design and synthesis of binucleating macrocyclic clefts derived from Schiff-base calixpyrroles.
Givaja, Gonzalo; Volpe, Manuel; Leeland, James W; Edwards, Michael A; Young, Thomas K; Darby, S Barnie; Reid, Stuart D; Blake, Alexander J; Wilson, Claire; Wolowska, Joanna; McInnes, Eric J L; Schröder, Martin; Love, Jason B
2007-01-01
The syntheses, characterisation and complexation reactions of a series of binucleating Schiff-base calixpyrrole macrocycles are described. The acid-templated [2+2] condensations between meso-disubstituted diformyldipyrromethanes and o-phenylenediamines generate the Schiff-base pyrrolic macrocycles H(4)L(1) to H(4)L(6) upon basic workup. The single-crystal X-ray structures of both H(4)L(3).2 EtOH and H(4)L(6).H2O confirm that [2+2] cyclisation has occurred, with either EtOH or H2O hydrogen-bonded within the macrocyclic cleft. A series of complexation reactions generate the dipalladium [Pd2(L)] (L=L(1) to L(5)), dinickel [Ni2(L(1))] and dicopper [Cu2(L)] (L=L(1) to L(3)) complexes. All of these complexes have been structurally characterised in the solid state and are found to adopt wedged structures that are enforced by the rigidity of the aryl backbone to give a cleft reminiscent of the structures of Pacman porphyrins. The binuclear nickel complexes [Ni2(mu-OMe)2Cl2(HOMe)2(H(4)L(1))] and [Ni2(mu-OH)2Cl2(HOMe)(H(4)L(5))] have also been prepared, although in these cases the solid-state structures show that the macrocyclic ligand remains protonated at the pyrrolic nitrogen atoms, and the Ni(II) cations are therefore co-ordinated by the imine nitrogen atoms only to give an open conformation for the complex. The dicopper complex [Cu2(L(3))] was crystallised in the presence of pyridine to form the adduct [Cu2(py)(L(3))], in which, in the solid state, the pyridine ligand is bound within the binuclear molecular cleft. Reaction between H(4)L(1) and [Mn(thf){N(SiMe(3))2}2] results in clean formation of the dimanganese complex [Mn2(L(1))], which, upon crystallisation, formed the mixed-valent complex [Mn2(mu-OH)(L(1))] in which the hydroxo ligand bridges the metal centres within the molecular cleft.
Identifying hidden sexual bridging communities in Chicago.
Youm, Yoosik; Mackesy-Amiti, Mary Ellen; Williams, Chyvette T; Ouellet, Lawrence J
2009-07-01
Bridge populations can play a central role in the spread of human immunodeficiency virus (HIV) by providing transmission links between higher and lower prevalence populations. While social network methods are well suited to the study of bridge populations, analyses tend to focus on dyads (i.e., risk between drug and/or sex partners) and ignore bridges between distinct subpopulations. This study takes initial steps toward moving the analysis of sexual network linkages beyond individual and risk group levels to a community level in which Chicago's 77 community areas are examined as subpopulations for the purpose of identifying potential bridging communities. Of particular interest are "hidden" bridging communities; that is, areas with above-average levels of sexual ties with other areas but whose below-average AIDS prevalence may hide their potential importance for HIV prevention. Data for this analysis came from the first wave of recruiting at the Chicago Sexual Acquisition and Transmission of HIV Cooperative Agreement Program site. Between August 2005 through October 2006, respondent-driven sampling was used to recruit users of heroin, cocaine, or methamphetamine, men who have sex with men regardless of drug use, the sex partners of these two groups, and sex partners of the sex partners. In this cross-sectional study of the sexual transmission of HIV, participants completed a network-focused computer-assisted self-administered interview, which included questions about the geographic locations of sexual contacts with up to six recent partners. Bridging scores for each area were determined using a matrix representing Chicago's 77 community areas and were assessed using two measures: non-redundant ties and flow betweenness. Bridging measures and acquired immunodeficiency syndrome (AIDS) case prevalence rates were plotted for each community area on charts representing four conditions: below-average bridging and AIDS prevalence, below-average bridging and above-average AIDS prevalence, above-average bridging and AIDS prevalence, and above-average bridging and below-average AIDS prevalence (hidden bridgers). The majority of the 1,068 study participants were male (63%), African American (74%), and very poor, and the median age was 44 years. Most (85%) were sexually active, and 725 provided useable geographic information regarding 1,420 sexual partnerships that involved 57 Chicago community areas. Eight community areas met or came close to meeting the definition of hidden bridgers. Six areas were near the city's periphery, and all eight areas likely had high inflows or outflows of low-income persons displaced by gentrification. The results suggest that further research on this method is warranted, and we propose a means for public health officials in other cities to duplicate the analysis.
Impact of Emerging Public Policy on Educational Planning.
ERIC Educational Resources Information Center
Jordan, Barbara
The 94th Congress tends to view education as a bridge, a bridge that will make the labor market more accessible to the ignorant, the unskilled, the poor, the unemployed, the handicapped. Each of these groups constitutes a constituency in and of itself. The magnitude of education appropriations especially for vocational and higher education is…
Bridging the Gap between Research and Practice: Voice of Mediators
ERIC Educational Resources Information Center
Mehrani, Mehdi B.
2014-01-01
The present study aimed to explore the strategies that could be potentially employed in the Iranian ELT context to bridge the gap between research and practice. Data were collected through conducting a "focus group discussion" with a number of practitioner-researchers. The findings showed that to improve the relationship between…
DOE Office of Scientific and Technical Information (OSTI.GOV)
Siahrostami, Samira; Li, Guo-Ling; Nørskov, Jens K.
Herein we study the effect of strain on the catalytic activity of different Pt-doped single wall metallic carbon nanotubes (SWCNT) towards the oxygen reduction reaction (ORR). We consider the possibility of the Pt-doped at single vacancy inside the SWCNT to investigate the effect of confinement on the reaction mechanism. Density functional theory calculations indicate that for the SWCNTs with tube diameters below 7 Å, the strain energy varies significantly influencing the adsorption energies of the key intermediates of the ORR reaction. For the SWCNTs with tube diameters above 7 Å, on the other hand, both the calculated strain and themore » adsorption energies are almost constant. We furthermore find that the adsorption energies are strongly affected by confinement effects as shown for Pt-doped systems that are located inside the SWCNT. We show that the Pt-doped at single vacancy of the SWCNT strongly binds the oxygenated species under ORR potentials and therefore the active species is covered by oxo- or hydroxo group. Because the presence of Pt atoms doped at the single and double vacancies of the SWCNT is equivalently probable we also studied the Pt-doped at double vacancy. We find that the most active motif is the Pt-doped at double vacancy of SWCNT with 0.24V overpotenital.« less
Siahrostami, Samira; Li, Guo-Ling; Nørskov, Jens K.; ...
2017-09-30
Herein we study the effect of strain on the catalytic activity of different Pt-doped single wall metallic carbon nanotubes (SWCNT) towards the oxygen reduction reaction (ORR). We consider the possibility of the Pt-doped at single vacancy inside the SWCNT to investigate the effect of confinement on the reaction mechanism. Density functional theory calculations indicate that for the SWCNTs with tube diameters below 7 Å, the strain energy varies significantly influencing the adsorption energies of the key intermediates of the ORR reaction. For the SWCNTs with tube diameters above 7 Å, on the other hand, both the calculated strain and themore » adsorption energies are almost constant. We furthermore find that the adsorption energies are strongly affected by confinement effects as shown for Pt-doped systems that are located inside the SWCNT. We show that the Pt-doped at single vacancy of the SWCNT strongly binds the oxygenated species under ORR potentials and therefore the active species is covered by oxo- or hydroxo group. Because the presence of Pt atoms doped at the single and double vacancies of the SWCNT is equivalently probable we also studied the Pt-doped at double vacancy. We find that the most active motif is the Pt-doped at double vacancy of SWCNT with 0.24V overpotenital.« less
Zhou, Bin; Huang, QiuChen; Zheng, Tao; Huo, Ming; Maruyama, Hitoshi
2015-05-01
[Purpose] This study examined the effects of neuromuscular joint facilitation on bridging exercises by assessing the cross-sectional area of the multifidus muscle and thickness of the musculus transversus abdominis. [Subjects] Twelve healthy men. [Methods] Four exercises were evaluated: (a) supine resting, (b) bridging resistance exercise involving posterior pelvic tilting, (c) bridging resistance exercise involving anterior pelvic tilting, and (d) bridging resistance exercise involving neuromuscular joint facilitation. The cross-sectional area of the multifidus muscle and thickness of the musculus transversus abdominis were measured during each exercise. [Results] The cross-sectional area of the multifidus muscle and thickness of the musculus transversus abdominis were significantly greater in the neuromuscular joint facilitation group than the others. [Conclusion] Neuromuscular joint facilitation intervention improves the function of deep muscles such as the multifidus muscle and musculus transversus abdominis. Therefore, it can be recommended for application in clinical treatments such as that for back pain.
Giordano, Salvatore; Garvey, Patrick B; Baumann, Donald P; Liu, Jun; Butler, Charles E
2017-02-01
Previous studies suggest that bridged mesh repair for abdominal wall reconstruction may result in worse outcomes than mesh-reinforced, primary fascial closure, particularly when acellular dermal matrix is used. We compared our outcomes of bridged versus reinforced repair using ADM in abdominal wall reconstruction procedures. This retrospective study included 535 consecutive patients at our cancer center who underwent abdominal wall reconstruction either for an incisional hernia or for abdominal wall defects left after excision of malignancies involving the abdominal wall with underlay mesh. A total of 484 (90%) patients underwent mesh-reinforced abdominal wall reconstruction and 51 (10%) underwent bridged repair abdominal wall reconstruction. Acellular dermal matrix was used, respectively, in 98% of bridged and 96% of reinforced repairs. We compared outcomes between these 2 groups using propensity score analysis for risk-adjustment in multivariate analysis and for 1-to-1 matching. Bridged repairs had a greater hernia recurrence rate (33.3% vs 6.2%, P < .001), a greater overall complication rate (59% vs 30%, P = .001), and worse freedom from hernia recurrence (log-rank P <.001) than reinforced repairs. Bridged repairs also had a greater rate of wound dehiscence (26% vs 14%, P = .034) and mesh exposure (10% vs 1%, P = .003) than mesh-reinforced abdominal wall reconstruction. When the treatment method was adjusted for propensity score in the propensity-score-matched pairs (n = 100), we found that the rates of hernia recurrence (32% vs 6%, P = .002), overall complications (32% vs 6%, P = .002), and freedom from hernia recurrence (68% vs 32%, P = .001) rates were worse after bridged repair. We did not observe differences in wound healing and mesh complications between the 2 groups. In our population of primarily cancer patients at MD Anderson Cancer Center bridged repair for abdominal wall reconstruction is associated with worse outcomes than mesh-reinforced abdominal wall reconstruction. Particularly when employing acellular dermal matrix, reinforced repairs should be used for abdominal wall reconstruction whenever possible. Copyright © 2016 Elsevier Inc. All rights reserved.
Lateral Meniscal Allograft Transplant via a Medial Approach Leads to Less Extrusion.
Choi, Nam-Hong; Choi, Jeong-Ki; Yang, Bong-Seok; Lee, Doe-Hyun; Victoroff, Brian N
2017-10-01
Accurate positioning of the bony bridge is crucial to prevent extrusion of meniscal allografts after transplant. However, oblique or lateralized placement of the bony bridge of the lateral meniscal allograft may occur due to technical error or a limited visual field. The patellar tendon may be an obstacle to approaching the anterior horn of the lateral meniscus, resulting in a laterally placed allograft. Therefore, lateral meniscal transplant through a medial arthrotomy would be an alternative approach. However, no report exists regarding allograft extrusion when comparing medial and lateral arthrotomy techniques in lateral meniscal transplants. Extrusion of the midbody of the allograft is less severe and the rotation of the bony bridge is less oblique in lateral meniscal allograft transplants through the medial parapatellar approach than those through the lateral approach. Cohort study; Level of evidence, 3. A bony bridge was used to perform 55 lateral meniscal transplants through either a medial or a lateral arthrotomy. Thirty-two allografts were transplanted through a medial arthrotomy and 23 were transplanted through a lateral arthrotomy, not randomly. Because correct positioning of the bony trough through the medial arthrotomy was easier than that through the lateral arthrotomy, the method of the arthrotomy was changed for the latter. The procedure for both groups was identical except for the arthrotomy technique, and rehabilitation was identical for both groups. Follow-up magnetic resonance imaging was conducted for all patients to measure the postoperative extrusion and obliquity of the bony bridge of the allograft. On the coronal view, extrusion was measured as the distance between the outer edge of the articular cartilage of the lateral tibial plateau and the outer edge of the meniscal allograft. On the axial view, a line (line B) was drawn along the longitudinal axis of the bony bridge. The posterior tibial condylar tangential line was drawn between the medial and lateral posterior tibial condylar cortices. A line (line T) was drawn perpendicular to the posterior tibial condylar tangential line. The angle (trough angle) between lines B and T was measured. Postoperative extrusion and the trough angle were compared between the medial and lateral arthrotomy groups. The median extrusion of the midbody of the allograft was 2.2 mm (interquartile range [IQR], 2.4 mm; range, 0-4.6 mm) in the medial arthrotomy group and 3.1 mm (IQR, 1.5 mm; range, 0-5.3 mm) in the lateral arthrotomy group ( P = .001). Seven (21.9%) patients demonstrated extrusion in the medial arthrotomy group, and 15 (65.2%) patients had extrusion in the lateral group ( P = .002). The median trough angle was 0.9° (IQR, 9.3°; range, -8.8-15.8°) in the medial arthrotomy group and 11.6° (IQR, 2.8°; range, 3-19.8°) in the lateral arthrotomy group ( P < .001). Based on this experience, lateral meniscal allograft transplant through a medial arthrotomy is preferred to decrease postoperative extrusion of the allograft.
Bayesian Group Bridge for Bi-level Variable Selection.
Mallick, Himel; Yi, Nengjun
2017-06-01
A Bayesian bi-level variable selection method (BAGB: Bayesian Analysis of Group Bridge) is developed for regularized regression and classification. This new development is motivated by grouped data, where generic variables can be divided into multiple groups, with variables in the same group being mechanistically related or statistically correlated. As an alternative to frequentist group variable selection methods, BAGB incorporates structural information among predictors through a group-wise shrinkage prior. Posterior computation proceeds via an efficient MCMC algorithm. In addition to the usual ease-of-interpretation of hierarchical linear models, the Bayesian formulation produces valid standard errors, a feature that is notably absent in the frequentist framework. Empirical evidence of the attractiveness of the method is illustrated by extensive Monte Carlo simulations and real data analysis. Finally, several extensions of this new approach are presented, providing a unified framework for bi-level variable selection in general models with flexible penalties.
Cooper, Katelyn M; Ashley, Michael; Brownell, Sara E
2017-01-01
National calls to improve student academic success in college have sparked the development of bridge programs designed to help students transition from high school to college. We designed a 2-week Summer Bridge program that taught introductory biology content in an active-learning way. Through a set of exploratory interviews, we unexpectedly identified that Bridge students had developed sophisticated views of active learning, even though this was not an explicit goal of the program. We conducted an additional set of semistructured interviews that focused on active learning and compared the interviews of Bridge students with those from non-Bridge students who had been eligible for but did not participate in the program. We used the constant comparative method to identify themes from the interviews. We found that Bridge students perceived that, because they knew how to approach active learning and viewed it as important, they benefited more from active learning in introductory biology than non-Bridge students. Specifically, Bridge students seemed to be more aware of their own learning gains from participating in active learning. Compared with the majority of non-Bridge students, the majority of Bridge students described using a greater variety of strategies to maximize their experiences in active learning. Finally, in contrast to non-Bridge students, Bridge students indicated that they take an equitable approach to group work. These findings suggest that we may be able to prime students to maximize their own and other's experiences in active learning. © 2017 K. M. Cooper et al. CBE—Life Sciences Education © 2017 The American Society for Cell Biology. This article is distributed by The American Society for Cell Biology under license from the author(s). It is available to the public under an Attribution–Noncommercial–Share Alike 3.0 Unported Creative Commons License (http://creativecommons.org/licenses/by-nc-sa/3.0).
Tacir, Ibrahim H; Dirihan, Roda S; Polat, Zelal Seyfioglu; Salman, Gizem Ön; Vallittu, Pekka; Lassila, Lippo; Ayna, Emrah
2018-06-28
BACKGROUND The aim of this study was to investigate and compare the load-bearing capacities of three-unit direct resin-bonded fiber-reinforced composite fixed dental prosthesis with different framework designs. MATERIAL AND METHODS Sixty mandibular premolar and molar teeth without caries were collected and direct glass fiber-resin fixed FDPs were divided into 6 groups (n=10). Each group was restored via direct technique with different designs. In Group 1, the inlay-retained bridges formed 2 unidirectional FRC frameworks and pontic-reinforced transversal FRC. In Group 2, the inlay-retained bridges were supported by unidirectional lingual and occlusal FRC frameworks. Group 3, had buccal and lingual unidirectional FRC frameworks without the inlay cavities. Group 4 had reinforced inlay cavities and buccal-lingual FRC with unidirectional FRC frameworks. Group 5, had a circular form of fiber reinforcement around cusps in addition to buccal-lingual FRC frameworks. Group 6 had a circular form of fiber reinforcement around cusps with 2 bidirectional FRC frameworks into inlay cavities. All groups were loaded until final fracture using a universal testing machine at a crosshead speed of 1 mm/min. RESULTS Mean values of the groups were determined with ANOVA and Tukey HSD. When all data were evaluated, Group 6 had the highest load-bearing capacities and revealed significant differences from Group 3 and Group 4. Group 6 had the highest strain (p>0.05). When the fracture patterns were investigated, Group 6 had the durability to sustain fracture propagation within the restoration. CONCLUSIONS The efficiency of fiber reinforcement of the restorations alters not only the amount of fiber, but also the design of the restoration with fibers.
Ileostomy rod--is it a bridge too far?
Speirs, M; Leung, E; Hughes, D; Robertson, I; Donnelly, L; Mackenzie, I; Macdonald, A
2006-07-01
Defunctioning loop ileostomies are used commonly to protect low colorectal anastomoses and thereby reducing the serious complications of leakage. However, they are associated with specific complications such as retraction. Traditionally, a supporting rod is placed as a bridge to support both limbs of the stoma in the hope of reducing the incidence of stomal retraction. There is little evidence in the published literature to support this practice. The aim of this study was to determine whether using an ileostomy rod would reduce the incidence of stomal retraction. A prospective, randomised controlled trial was performed in 60 consecutive patients who required a defunctioning loop ileostomy. Patients were allocated to either a 'bridge' or 'bridge-less' protocol. All the patients were assessed by dedicated stoma nurses for at least 3 months and until their stomas were closed. Their postoperative symptoms, including stoma activity and retraction rate, were recorded. Between May 2001 and June 2004, 57 patients completed the study (28 bridge; 29 bridge-less). There were no significant differences in the retraction rate between the groups. No clinical anastomotic leakage was recorded and none of the patients required early closure. If a loop ileostomy is constructed properly, stomal retraction is uncommon and routine use of a bridge is unnecessary.
Hollman, John H; Berling, Tyler A; Crum, Ellen O; Miller, Kelsie M; Simmons, Brent T; Youdas, James W
2018-03-01
Hip extension with hamstring-dominant rather than gluteus maximus-dominant recruitment may increase anterior femoracetabular forces and contribute to conditions that cause hip pain. Cueing methods during hip extension exercises may facilitate greater gluteus maximus recruitment. We examined whether specific verbal and tactile cues facilitate gluteus maximus recruitment while inhibiting hamstring recruitment during a bridging exercise. Randomized controlled trial. Biomechanics laboratory. 30 young adult women (age 24 [3] y; BMI 22.2 [2.4] kg/m 2 ). Participants were tested over 2 sessions, 1 week apart, while performing 5 repetitions of a bridging exercise. At their second visit, participants in the experimental group received verbal and tactile cues intended to facilitate gluteus maximus recruitment and inhibit hamstring recruitment. Control group participants received no additional cues beyond original instructions. Gluteus maximus and hamstring recruitment were measured with surface electromyography, normalized to maximal voluntary isometric contractions (MVICs). Gluteus maximus recruitment was unchanged in the control group and increased from 16.8 to 33.0% MVIC in the cueing group (F = 33.369, P < .001). Hamstring recruitment was unchanged in the control group but also increased from 16.5 to 29.8% MVIC in the cueing group (F = 6.400, P = .02). The effect size of the change in gluteus maximus recruitment in the cueing group (Cohen's d = 1.5, 95% CI = 0.9 to 2.2) was not significantly greater than the effect size in hamstring recruitment (Cohen's d = 0.8, 95% CI = 0.1 to 1.5). Verbal and tactile cues hypothesized to facilitate gluteus maximus recruitment yielded comparable increases in both gluteus maximus and hamstring recruitment. If one intends to promote hip extension by facilitating gluteus maximus recruitment while inhibiting hamstring recruitment during bridging exercises, the cueing methods employed in this study may not produce desired effects.
NASA Astrophysics Data System (ADS)
Hong, Sung Y.; Song, Jung M.
1997-12-01
A theoretical study of a variety of tricyclic polymers [-(C8H2X2Y)n-] with two different types of bridging groups was performed, X=S and Y=CH2, SiH2, C=O, C=S, or C=CH2 for the fused bithiophene system and vice versa for the thieno-bicyclic system. These two types of the bridging groups are different from each other in that S favors the aromatic form of a cyclic polymer and the other groups prefer the quinonoid form. Geometrical structures of the polymers were obtained from semiempirical self-consistent-field (SCF) band calculations and the electronic properties from the modified extended Hückel band calculations. It is found that the ground-state geometrical structures of the tricyclic polymers are determined by the bridging groups in the outer rings. That is, the fused bithiophene system is aromatic in the ground state and the thieno-bicyclic system is quinonoid. The ground-state band gaps (which correspond to the absorption peaks of π-π* band transition) of the polymers were estimated to be in the range of 0.7-2.0 eV. The band gaps were analyzed in terms of the bond-length alternation along the conjugated carbon backbone, the C1-C4 interactions, and the electronic effect of the bridging groups. We also investigated the geometrical and electronic structures of polydicyanomethylene-cyclopenta-dicyclopentadiene (PDICNCY). Unlike the theoretical predictions of Toussaint and Bredas [Synth. Met. 69, 637 (1995)], PDICNCY in the ground state was estimated to be of the quinonoid form and to possess a large band gap (2.55 eV) comparable with the gap of polythiophene.
ERIC Educational Resources Information Center
Teaching Science, 2015
2015-01-01
This project is for a team of students (groups of two or three are ideal) to design and construct a model of a single-span bridge, using plastic drinking straws as the building material. All steps of the design, construction, testing and critiquing stages should be recorded by students in a journal. Students may like to include labelled diagrams,…
ERIC Educational Resources Information Center
Tomasko, David L.; Ridgway, Judith S.; Waller, Rocquel J.; Olesik, Susan V.
2016-01-01
Retention of students to science, technology, engineering, and mathematics (STEM) major has been studied for four cohorts participating in a summer bridge program supported by the National Science Foundation. Students participated in a 6-week program prior to their first term of enrollment at a research-intensive land grant university. Comparisons…
From Both Sides of the Indigenous-Settler Hyphen in Aotearoa New Zealand
ERIC Educational Resources Information Center
Stewart, Georgina
2018-01-01
The idea of the 'intercultural hyphen' is likened to a gap or bridge between ethnic groups, created from the ongoing intertwining of sociopolitical and intellectual histories. This 'gap or bridge' wording captures the paradoxical nature of the intercultural space, for which the 'hyphen' is a shorthand symbol or sign. There are options on either…
Engineering Habits of Mind… for Better or Worse?
ERIC Educational Resources Information Center
Hodgson, Dan; Cloran, Peter; Johnson, Rory
2017-01-01
Engineering Habits of Mind (EHoMs) were first introduced to a target group of Year 9 (age 14) students who the authors felt were disengaged with science, technology, and computing. These students were invited to take part in an engineering challenge with a school in Qatar. This involved making a bridge and rolling a marble over the bridge. The…
Nosrat, Ali; Peimani, Ali; Asgary, Saeed
2013-11-01
The purpose of the study was to evaluate human dental pulp response to pulpotomy with calcium hydroxide (CH), mineral trioxide aggregate (MTA), and calcium enriched mixture (CEM) cement. A total of nine erupted third molars were randomly assigned to each pulpotomy group. The same clinician performed full pulpotomies and coronal restorations. The patients were followed clinically for six months; the teeth were then extracted and prepared for histological assessments. The samples were blindly assessed by an independent observer for pulp vitality, pulp inflammation, and calcified bridge formation. All patients were free of clinical signs/symptoms of pulpal/periradicular diseases during the follow up period. In CH group, one tooth had necrotic radicular pulp; other two teeth in this group had vital uninflamed pulps with complete dentinal bridge formation. In CEM cement and MTA groups all teeth had vital uninflamed radicular pulps. A complete dentinal bridge was formed beneath CEM cement and MTA in all roots. Odontoblast-like cells were present beneath CEM cement and MTA in all samples. This study revealed that CEM cement and MTA were reliable endodontic biomaterials in full pulpotomy treatment. In contrast, the human dental pulp response to CH might be unpredictable.
Lee, Kwang Won; Yang, Dae Suk; Lee, Gyu Sang; Ma, Chang Hyun; Choy, Won Sik
2018-05-23
This retrospective study compared the clinical and radiologic outcomes of patients who underwent arthroscopic rotator cuff repairs by the suture-bridge and double-row modified Mason-Allen techniques. From January 2012 to May 2013, 76 consecutive cases of full-thickness rotator cuff tear, 1 to 4 cm in the sagittal plane, for which arthroscopic rotator cuff repair was performed, were included. The suture-bridge technique was used in 37 consecutive shoulders; and the double-row modified Mason-Allen technique, in 39 consecutive shoulders. Clinical outcomes at a minimum of 2 years (mean, 35.7 months) were evaluated postoperatively using the visual analog scale; University of California, Los Angeles Shoulder Scale; American Shoulder and Elbow Surgeons Subjective Shoulder Scale; and Constant score. Postoperative cuff integrity was evaluated at a mean of 17.7 months by magnetic resonance imaging. At the final follow-up, the clinical outcomes improved in both groups (all P < .001) but with no significant differences between the 2 groups (all P > .05). The retear rate was 18.9% in the shoulders subjected to suture-bridge repair and 12.8% in the double-row modified Mason-Allen group; the difference was not significant (P = .361). Despite the presence of fewer suture anchors, the patients who underwent double-row modified Mason-Allen repair had comparable shoulder functional outcomes and a comparable retear rate with those who underwent suture-bridge repair. Therefore, the double-row modified Mason-Allen repair technique can be considered an effective treatment for patients with medium- to large-sized full-thickness rotator cuff tears. Copyright © 2018 Journal of Shoulder and Elbow Surgery Board of Trustees. Published by Elsevier Inc. All rights reserved.
Seismic fragility curves of bridge piers accounting for ground motions in Korea
NASA Astrophysics Data System (ADS)
Nguyen, Duy-Duan; Lee, Tae-Hyung
2018-04-01
Korea is located in a slight-to-moderate seismic zone. Nevertheless, several studies pointed that the peak earthquake magnitude in the region can be reached to approximately 6.5. Accordingly, a seismic vulnerability evaluation of the existing structures accounting for ground motions in Korea is momentous. The purpose of this paper is to develop seismic fragility curves for bridge piers of a steel box girder bridge equipped with and without base isolators based on a set of ground motions recorded in Korea. A finite element simulation platform, OpenSees, is utilized to perform nonlinear time history analyses of the bridges. A series of damage states is defined based on a damage index which is expressed in terms of the column displacement ductility ratio. The fragility curves based on Korean motions were thereafter compared with the fragility curves generated using worldwide earthquakes to assess the effect of the two ground motion groups on the seismic fragility curves of the bridge piers. The results reveal that both non- and base-isolated bridge piers are less vulnerable during the Korean ground motions than that under worldwide earthquakes.
Zarate, Ximena; Saavedra-Torres, Mario; Rodriguez-Serrano, Angela; Gomez, Tatiana; Schott, Eduardo
2018-04-30
The possibility of dye charge recombination in DSSCs remains a challenge for the field. This consists of: (a) back-transfer from the TiO 2 to the oxidized dye and (b) intermolecular electron transfer between dyes. The latter is attributed to dye aggregation due to dimeric conformations. This leads to poor electron injection which decreases the photocurrent conversion efficiency. Most organic sensitizers are characterized by an Acceptor-Bridge-Donor (A-Bridge-D) arrangement that is commonly employed to provide charge separation and, therefore, lowering the unwanted back-transfer. Here, we address the intermolecular electron transfer by studying the dimerization and photovoltaic performance of a group of A-Bridge-D structured dyes. Specifically, eight famous sulfur containing π-bridges were analyzed (A and D remained fixed). Through quantum mechanical and molecular dynamics approaches, it was found that the formation of weakly stabilized dimers is allowed. The dyes with covalently bonded and fused thiophene rings as Bridges, 6d and 7d as well as 8d with a fluorene, would present high aggregation and, therefore, high probability of recombination processes. Conversely, using TiO 2 cluster and surface models, delineated the shortest bridges to improve the adsorption energy and the stability of the system. Finally, the elongation of the bridge up to 2 and 3 units and their photovoltaic parameters were studied. These results showed that all the sensitizers are able to provide similar photocurrent outcomes, regardless of whether the bridge is elongated. © 2017 Wiley Periodicals, Inc. © 2017 Wiley Periodicals, Inc.
NASA Technical Reports Server (NTRS)
Peyghambarian, Nasser (Inventor); Hendrickx, Eric (Inventor); Volodin, Boris (Inventor); Marder, Seth R. (Inventor); Kippelen, Bernard (Inventor)
2000-01-01
Fused ring bridge, ring locked dyes that form thermally stable photorfractive compositions. The fused ring bridge structures are .pi.-conjugated bonds in benzene-, naphthalene- or anthracene-derived fused ring systems that connect donor and acceptor groups. The donor and acceptor groups contribute to a high molecular dipole moment and linear polarizability anisotropy. The polarization characteristics of the dye molecules are stabilized since the bonds in the fused ring bridge are not susceptible to rotation, reducing the opportunity for photoisomerization. The dyes are compatible with polymeric compositions, including thermoplastics. The dyes are electrically neutral but have charge transport, electronic and orientational properties such that upon illumination of a composition containing the dye, the dye facilitates refractive index modulation and a photorefractive effect that can be utilized advantageously in numerous applications such as in optical quality devices and biological imaging.
Thermally stable molecules with large dipole moments and polarizabilities and applications thereof
NASA Technical Reports Server (NTRS)
Marder, Seth R. (Inventor); Peyghambarian, Nasser (Inventor); Kippelen, Bernard (Inventor); Volodin, Boris (Inventor); Hendrickx, Eric (Inventor)
2002-01-01
Disclosed are fused ring bridge, ring-locked dyes that form thermally stable photorefractive compositions. The fused ring bridge structures are .pi.-conjugated bonds in benzene-, naphthalene- or anthracene-derived fused ring systems that connect donor and acceptor groups. The donor and acceptor groups contribute to a high molecular dipole moment and linear polarizability anisotropy. The polarization characteristics of the dye molecules are stabilized since the bonds in the fused ring bridge are not susceptible to rotation, reducing the opportunity for photoisomerization. The dyes are compatible with polymeric compositions, including thermoplastics. The dyes are electrically neutral but have charge transport, electronic and orientational properties such that upon illumination of a composition containing the dye, the dye facilitates refractive index modulation and a photorefractive effect that can be utilized advantageously in numerous applications such as in optical quality devices and biological imaging.
Dianati, Vahid; Shamloo, Azar; Kwiatkowska, Anna; Desjardins, Roxane; Soldera, Armand; Day, Robert; Dory, Yves L
2017-08-08
PACE4, a member of the proprotein convertases (PCs) family of serine proteases, is a validated target for prostate cancer. Our group has developed a potent and selective PACE4 inhibitor: Ac-LLLLRVKR-NH 2 . In seeking for modifications to increase the selectivity of this ligand toward PACE4, we replaced one of its P3 Val methyl groups with a basic group capable of forming a salt bridge with D160 of PACE4. The resulting inhibitor is eight times more potent than the P3 Val parent inhibitor and two times more selective over furin, because the equivalent salt bridge with furin E257 is not optimal. Moreover, the β-branched nature of the new P3 residue favors the extended β-sheet conformation usually associated with substrates of proteases. This work provides new insight for better understanding of β-sheet backbone-backbone interactions between serine proteases and their peptidic ligands. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
Assessing the Impact of the Three-Year Ohio Teen B.R.I.D.G.E.S. AmeriCorps Program.
ERIC Educational Resources Information Center
Safrit, R. Dale; Schmiesing, Ryan; King, Jeffrey E.; Villard, Judy; Wells, Betty
2003-01-01
Ohio Teen B.R.I.D.G.E.S (Building Responsibility In teen Drivers through Growth in self-Esteem and Safety) was evaluated using 12 focus groups. Program impacts included heightened awareness of vehicular safety issues among teens and communities, enhanced public speaking for youth volunteers, and meaningful leadership and volunteer opportunities…
Copolyimide with a combination of flexibilizing groups
NASA Technical Reports Server (NTRS)
Stclair, Terry L. (Inventor); Burks, Harold D. (Inventor); Progar, Donald J. (Inventor)
1989-01-01
Copolyimides are prepared by reacting one or more aromatic dianhydrides with a meta-substituted phenylene diamine and an aromatic bridged diamine. The incorporation of meta-substituted phenylene diamine derived units and bridged aromatice diamine derived units into the linear aromatic polymer backbone results in a copolyimide of improved flexibility, processability, and melt-flow characteristics. The copolyimides are especially useful as thermoplastic hot-melt adhesives.
DOE Office of Scientific and Technical Information (OSTI.GOV)
O'Sullivan, R.B.
1981-01-01
The San Rafael Group of Middle Jurassic age form extensive dip slopes on the north side of Salt Valley and crops out in bold cliffs from Salt Wash eastward to Dewey Bridge. In the San Rafael Swell about 70 km west of Salt Valley; the San Rafael Group consists in ascending order of Page Sandstone, Carmel Formation, Entrada Sandstone, and the Curtis and Summerville Formations. Fifteen stratigraphic sections are included on the map interpretation of the stratigraphy aids petroleum and natural gas investigations. (DP)
Two radiation-induced chromosomal inversions in mice (Mus musculus).
Roderick, T H; Hawes, N L
1970-10-01
Whole-body x-irradiation of male mice has produced presumptive paracentric inversions in 15 animals, as evidenced by high frequencies of first meiotic anaphase bridges. Two of the highest frequencies observed have been propagated through several generations and found to behave as dominant genes. Acentric fragments were observed associated with about 10% of the bridges. The first inversion, in linkage group XIII, has been designated In(13)1Rk, and the second, in linkage group XVII, In(17)2Rk. For In(13)1Rk, recombination was reduced between loci inside and outside the inverted segment.
Criteria for assessment of bridge aesthetic and visual quality
NASA Astrophysics Data System (ADS)
Rozentale, I.; Paeglitis, A.
2017-10-01
The bridge designers should find an ideal balance between structure, economy, buildability, aesthetics, durability and harmony with industrial or natural landscape. During the last years, the society has adopted documents providing procedures for evaluation of the impact of the structural appearance on surrounding landscape. The European Landscape Convention defines the landscape as an area perceived by people, whose character is the result of the action and interaction of natural and/or human factors. The Convention indicates the methods for clear and objective assessment of the landscape’s visual qualities. The esthetical qualities of bridge structures, appearance and attraction should satisfy not only the technicians - engineers and architects, but mostly the surrounding population. Each of these groups has a different perception of esthetical qualities of structure. Many authors have used different methods and criteria for assessment of bridge aesthetics. The aim of this paper is to provide an overview of the bridge aesthetic and visual quality assessment methods and criteria.
Smith, Geoffrey C S; Bouwmeester, Theresia M; Lam, Patrick H
2017-12-01
In double-row SutureBridge (Arthrex, Naples, FL, USA) rotator cuff repairs, increasing tendon load may generate progressively greater compression forces at the repair footprint (self-reinforcement). SutureBridge rotator cuff repairs using tied horizontal mattress sutures medially may limit this effect compared with a knotless construct. Rotator cuff repairs were performed in 9 pairs of ovine shoulders. One group underwent repair with a double-row SutureBridge construct with tied horizontal medial-row mattress sutures. The other group underwent repair in an identical fashion except that medial-row knots were not tied. Footprint contact pressure was measured at 0° and 20° of abduction under loads of 0 to 60 N. Pull-to-failure tests were then performed. In both repair constructs, each 10-N increase in rotator cuff tensile load led to a significant increase in footprint contact pressure (P < .0001). The rate of increase in footprint contact pressure was greater in the knotless construct (P < .00022; ratio, 1.69). The yield point approached the ultimate load to failure more closely in the knotless model than in the knotted construct (P = .00094). There was no difference in stiffness, ultimate failure load, or total energy to failure between the knotless and knotted techniques. In rotator cuff repair with a double-row SutureBridge configuration, self-reinforcement is seen in repairs with and without medial-row knots. Self-reinforcement is greater with the knotless technique. Copyright © 2017 Journal of Shoulder and Elbow Surgery Board of Trustees. Published by Elsevier Inc. All rights reserved.
Stith, David A.
1981-01-01
The chemical composition and stratigraphy of the Black River Group in southwestern Ohio were studied. Chemical analyses were done on two cores of the Black River from Adams and Brown Counties, Ohio. These studies show that substantial reserves of high-carbonate rock are present in the Black River at depths of less than 800 ft, in proximity to Cincinnati and the Ohio River. Stratigraphic studies show that the Black River Group has eight marker beds in its middle and upper portions and three distinct lithologic units in its lower portion; these marker beds and units are present throughout southwestern Ohio. The Black River Group correlates well with the High Bridge Group of Kentucky. Depositional environments of the Black River are similar to those of the High Bridge and to present-day tidal flats in the Bahamas.-Author
Itooka, Ryoh; Iguchi, Yuki; Miyaura, Norio
2003-07-25
The effects of ligands and bases in the rhodium(I)-catalyzed 1,4-addition of arylboronic acids to alpha,beta-unsaturated carbonyl compounds were reinvestigated to carry out the reaction under mild conditions. Rhodium(I) complexes possessing a 1,5-cyclooctadiene (cod) and a hydroxo ligand such as [RhOH(cod)](2) exhibited excellent catalyst activities compared to those of the corresponding rhodium-acac or -chloro complexes and their phosphine derivatives. The reaction was further accelerated in the presence of KOH, thus allowing the 1,4-addition even at 0 degrees C. A cationic rhodium(I)-(R)-binap complex, [Rh(R-binap)(nbd)]BF(4), catalyzed the reaction at 25-50 degrees C in the presence of Et(3)N with high enantioselectivities of up to 99% ee for alpha,beta-unsaturated ketones, 92% for aldehydes, 94% for esters, and 92% for amides.
Gomez-Mingot, Maria; Porcher, Jean-Philippe; Todorova, Tanya K; Fogeron, Thibault; Mellot-Draznieks, Caroline; Li, Yun; Fontecave, Marc
2015-10-29
Bis(dithiolene)tungsten complexes, W(VI)O2 (L = dithiolene)2 and W(IV)O (L = dithiolene)2, which mimic the active site of formate dehydrogenases, have been characterized by cyclic voltammetry and controlled potential electrolysis in acetonitrile. They are shown to be able to catalyze the electroreduction of protons into hydrogen in acidic organic media, with good Faradaic yields (75-95%) and good activity (rate constants of 100 s(-1)), with relatively high overpotentials (700 mV). They also catalyze proton reduction into hydrogen upon visible light irradiation, in combination with [Ru(bipyridine)3](2+) as a photosensitizer and ascorbic acid as a sacrificial electron donor. On the basis of detailed DFT calculations, a reaction mechanism is proposed in which the starting W(VI)O2 (L = dithiolene)2 complex acts as a precatalyst and hydrogen is further formed from a key reduced W-hydroxo-hydride intermediate.
Dynamics of photogenerated holes in surface modified α-Fe2O3 photoanodes for solar water splitting
Barroso, Monica; Mesa, Camilo A.; Pendlebury, Stephanie R.; Cowan, Alexander J.; Hisatomi, Takashi; Sivula, Kevin; Grätzel, Michael; Klug, David R.; Durrant, James R.
2012-01-01
This paper addresses the origin of the decrease in the external electrical bias required for water photoelectrolysis with hematite photoanodes, observed following surface treatments of such electrodes. We consider two alternative surface modifications: a cobalt oxo/hydroxo-based (CoOx) overlayer, reported previously to function as an efficient water oxidation electrocatalyst, and a Ga2O3 overlayer, reported to passivate hematite surface states. Transient absorption studies of these composite electrodes under applied bias showed that the cathodic shift of the photocurrent onset observed after each of the surface modifications is accompanied by a similar cathodic shift of the appearance of long-lived hematite photoholes, due to a retardation of electron/hole recombination. The origin of the slower electron/hole recombination is assigned primarily to enhanced electron depletion in the Fe2O3 for a given applied bias. PMID:22802673
Cheung, Tan To; Fan, Sheung Tat; Chan, See Ching; Chok, Kenneth S H; Chu, Ferdinand S K; Jenkins, Caroline R; Lo, Regina C L; Fung, James Y Y; Chan, Albert C Y; Sharr, William W; Tsang, Simon H Y; Dai, Wing Chiu; Poon, Ronnie T P; Lo, Chung Mau
2013-05-28
To analyze whether high-intensity focused ultrasound (HIFU) ablation is an effective bridging therapy for patients with hepatocellular carcinoma (HCC). From January 2007 to December 2010, 49 consecutive HCC patients were listed for liver transplantation (UCSF criteria). The median waiting time for transplantation was 9.5 mo. Twenty-nine patients received transarterial chemoembolization (TACE) as a bringing therapy and 16 patients received no treatment before transplantation. Five patients received HIFU ablation as a bridging therapy. Another five patients with the same tumor staging (within the UCSF criteria) who received HIFU ablation but not on the transplant list were included for comparison. Patients were comparable in terms of Child-Pugh and model for end-stage liver disease scores, tumor size and number, and cause of cirrhosis. The HIFU group and TACE group showed no difference in terms of tumor size and tumor number. One patient in the HIFU group and no patient in the TACE group had gross ascites. The median hospital stay was 1 d (range, 1-21 d) in the TACE group and two days (range, 1-9 d) in the HIFU group (P < 0.000). No HIFU-related complication occurred. In the HIFU group, nine patients (90%) had complete response and one patient (10%) had partial response to the treatment. In the TACE group, only one patient (3%) had response to the treatment while 14 patients (48%) had stable disease and 14 patients (48%) had progressive disease (P = 0.00). Seven patients in the TACE group and no patient in the HIFU group dropped out from the transplant waiting list (P = 0.559). HIFU ablation is safe and effective in the treatment of HCC for patients with advanced cirrhosis. It may reduce the drop-out rate of liver transplant candidate.
ERIC Educational Resources Information Center
Pearson, Patricia, Ed.
Proceedings drawn from a conference on business communication, the 21 papers in this collection are grouped under the headings Corporate Tower Views, Bridging the Gap, and Ivory Tower Views to better reflect the joint concerns of professional communicators on the job as well as the concerns of those who teach business communication. Among the…
Peimani, Ali; Asgary, Saeed
2013-01-01
Objectives The purpose of the study was to evaluate human dental pulp response to pulpotomy with calcium hydroxide (CH), mineral trioxide aggregate (MTA), and calcium enriched mixture (CEM) cement. Materials and Methods A total of nine erupted third molars were randomly assigned to each pulpotomy group. The same clinician performed full pulpotomies and coronal restorations. The patients were followed clinically for six months; the teeth were then extracted and prepared for histological assessments. The samples were blindly assessed by an independent observer for pulp vitality, pulp inflammation, and calcified bridge formation. Results All patients were free of clinical signs/symptoms of pulpal/periradicular diseases during the follow up period. In CH group, one tooth had necrotic radicular pulp; other two teeth in this group had vital uninflamed pulps with complete dentinal bridge formation. In CEM cement and MTA groups all teeth had vital uninflamed radicular pulps. A complete dentinal bridge was formed beneath CEM cement and MTA in all roots. Odontoblast-like cells were present beneath CEM cement and MTA in all samples. Conclusions This study revealed that CEM cement and MTA were reliable endodontic biomaterials in full pulpotomy treatment. In contrast, the human dental pulp response to CH might be unpredictable. PMID:24303358
MacInnis, Morgan C; McDonald, Robert; Ferguson, Michael J; Tobisch, Sven; Turculet, Laura
2011-08-31
Unprecedented diamagnetic, four-coordinate, formally 14-electron (Cy-PSiP)RuX (Cy-PSiP = [κ(3)-(2-R(2)PC(6)H(4))(2)SiMe](-); X = amido, alkoxo) complexes that do not require agostic stabilization and that adopt a highly unusual trigonal pyramidal coordination geometry are reported. The tertiary silane [(2-Cy(2)PC(6)H(4))(2)SiMe]H ((Cy-PSiP)H) reacted with 0.5 [(p-cymene)RuCl(2)](2) in the presence of Et(3)N and PCy(3) to afford [(Cy-PSiP)RuCl](2) (1) in 74% yield. Treatment of 1 with KO(t)Bu led to the formation of (Cy-PSiP)RuO(t)Bu (2, 97% yield), which was crystallographically characterized and shown to adopt a trigonal pyramidal coordination geometry in the solid state. Treatment of 1 with NaN(SiMe(3))(2) led to the formation of (Cy-PSiP)RuN(SiMe(3))(2) (3, 70% yield), which was also found to adopt a trigonal pyramidal coordination geometry in the solid state. The related anilido complexes (Cy-PSiP)RuNH(2,6-R(2)C(6)H(3)) (4, R = H; 5, R = Me) were also prepared in >90% yields by treating 1 with LiNH(2,6-R(2)C(6)H(3)) (R = H, Me) reagents. The solid state structure of 5 indicates a monomeric trigonal pyramidal complex that features a C-H agostic interaction. Complexes 2 and 3 were found to react readily with 1 equiv of H(2)O to form the dimeric hydroxo-bridged complex [(Cy-PSiP)RuOH](2) (6, 94% yield), which was crystallographically characterized. Complexes 2 and 3 also reacted with 1 equiv of PhOH to form the new 18-electron η(5)-oxocyclohexadienyl complex (Cy-PSiP)Ru(η(5)-C(6)H(5)O) (7, 84% yield). Both amido and alkoxo (Cy-PSiP)RuX complexes reacted with H(3)B·NHRR' reagents to form bis(σ-B-H) complexes of the type (Cy-PSiP)RuH(η(2):η(2)-H(2)BNRR') (8, R = R' = H; 9, R = R' = Me; 10, R = H, R' = (t)Bu), which illustrates that such four-coordinate (Cy-PSiP)RuX (X = amido, alkoxo) complexes are able to undergo multiple E-H (E = main group element) bond activation steps. Computational methods were used to investigate structurally related PCP, PPP, PNP, and PSiP four-coordinate Ru complexes and confirmed the key role of the strongly σ-donating silyl group of the PSiP ligand set in enforcing the unusual trigonal pyramidal coordination geometry featured in complexes 2-5, thus substantiating a new strategy for the synthesis of low-coordinate Ru species. The mechanism of the activation of ammonia-borane by such low-coordinate (R-PSiP)RuX (X = amido, alkoxo) species was also studied computationally and was determined to proceed most likely in a stepwise fashion via intramolecular deprotonation of ammonia and subsequent borane B-H bond oxidative addition steps.
Mandić-Gajić, Gordana
2016-07-01
War veterans with chronic post-traumatic stress disorder (PTSD) have poorer family and parenting functioning, but little research has focused on these impairments. This paper presented how the series of drawings and the group art therapy process enhanced bridging the psychological barriers of a 33-year-old male PTSD war veteran to engagement with the child. After two years of deployment he returned home and suffered mostly from PTSD numbness and avoidance symptoms. The veteran had the family readjustment difficulties and felt guilty for being detached from his 3-year-old son. He under-went integrative treatment in the Day Unit Program. The drawings series were made by free associations. Clinical observations and group discussions were recorded in the group art therapy protocols. The presented patient got gratifications and support from the group members for his illustration of popular cartoon heroes, and decided to draw Mickey Mouse at home. On the next session he shared his satisfaction for bridging the gap between him and his son, having done the same drawings with his son at home. Beck's depression inventory (BDI) was used for self-rating of depression and a reduction of BDI score from 18 to 6 during the treatment course was recorded. Series of drawings illustrated shift from war related past toward current family life of the war veteran. Group art therapy gave him gratification and support with hope and a sense of belonging, thus facilitated his parenting readjustment.
McAdon, Mark H.; Nickias, Peter N.; Marks, Tobin J.; Schwartz, David J.
2001-01-01
A catalyst activator particularly adapted for use in the activation of metal complexes of metals of Group 3-10 for polymerization of ethylenically unsaturated polymerizable monomers, especially olefins, comprising two Group 13 metal or metalloid atoms and a ligand structure including at least one bridging group connecting ligands on the two Group 13 metal or metalloid atoms.
Interrelationship of Personality Disorders: Theoretical Formulations and Anecdotal Evidence.
ERIC Educational Resources Information Center
Vincent, Ken R.
1987-01-01
Attempts to define interrelationship of personality disorders. Discusses relationships between and among three major groupings of Diagnostic and Statistical Manual of Mental Disorders. Suggests that passive aggressive, avoidant, and borderline personality disorders serve as bridges between these groupings. Discusses placement within groupings with…
Mothia, Begum; Appleyard, Antony N; Wadman, Sjoerd; Tabor, Alethea B
2011-08-19
A methodology for the solid-phase synthesis of the overlapping lanthionine bridges found in many lantibiotics has been developed. A novel Teoc/TMSE-protected lanthionine derivative has been synthesized, and this lanthionine, and an Aloc/allyl-protected lanthionine derivative, have been incorporated into a linear peptide using solid-phase peptide synthesis. Selective deprotection of the silyl protecting groups, followed by sequential cyclization, deprotection of the allyl protecting groups, and further cyclization, enabled the regioselective formation of an analogue of rings D and E of nisin. © 2011 American Chemical Society
Zhang, Xuepeng; Liu, Xueping; Phillips, David Lee; Zhao, Cunyuan
2016-01-28
The hydrolysis mechanisms of DNA dinucleotide analogue BNPP(-) (bis(p-nitrophenyl) phosphate) catalyzed by mononuclear/dinuclear facial copper(ii) complexes bearing single alkyl guanidine pendants were investigated using density functional theory (DFT) calculations. Active catalyst forms have been investigated and four different reaction modes are proposed accordingly. The [Cu2(L(1))2(μ-OH)](3+) (L(1) is 1-(2-guanidinoethyl)-1,4,7-triazacyclononane) complex features a strong μ-hydroxo mediated antiferromagnetic coupling between the bimetallic centers and the corresponding more stable open-shell singlet state. Three different reaction modes involving two catalysts and a substrate were proposed for L(1) entries and the mode 1 in which an inter-complex nucleophilic attack by a metal bound hydroxide was found to be more favorable. In the L(3)-involved reactions (L(3) is 1-(4-guanidinobutyl)-1,4,7-triazacyclononane), the reaction mode in which an in-plane intracomplex scissoring-like nucleophilic attack by a Cu(ii)-bound hydroxide was found to be more competitive. The protonated guanidine pendants in each proposed mechanism were found to play crucial roles in stabilizing the reaction structures via hydrogen bonds and in facilitating the departure of the leaving group via electrostatic attraction. The calculated results are consistent with the experimental observations that the Cu(ii)-L(3) complexes are hydrolytically more favorable than their L(1)-involved counterparts.
Associative polymers bridging between layers of multilamellar vesicles.
NASA Astrophysics Data System (ADS)
Choi, Seo; Bhatia, Surita
2006-03-01
Multilamellar vesicles can be found in a variety of pharmaceutical formulations, personal care products, and home care products. Hydrophobically modified associative polymers are often used to stabilize the vesicles or to control the rheological properties of these formulations. The hydrophobic groups are expected to insert themselves into the vesicle bilayers. Recent experimental work shows that hydrophobically modified polymers may from bridges between vesicles or may bridge between layers of a single vesicle. The latter configuration forces an interlayer spacing roughly equal to the radius of gyration of the backbone between associative groups. We have performed simple mean-field calculations on ideal telechelic associative polymers between concentric spherical surfaces. We find that the free energy per chain has an attractive minimum when the layer spacing is approximately N^1/2l, which is consistent with experimental results. The depth of the minimum depends on both chain length and curvature, and as expected when the curvature becomes small, the result for telechelic chains between flat surfaces is recovered.
Multiphase power supply when inverting currents for group of Peltier elements
NASA Astrophysics Data System (ADS)
Osintsev, A. V.; Sobko, A. A.; Komnatnov, M. E.
2018-05-01
The use of multiphase power supply of a group of Peltier elements (PE) is considered to reduce the load on the power source. Schemes and a control layout with the use of the H-bridge, allowing the invert of the current through the PE, are given. The analysis of the operation of the used H-bridges and PE in the frequency range of the control PWM signal from 30 Hz to 32 kHz is performed. The algorithm for monitoring the current sensors is presented and the time diagrams of the currents are represented through the PE and H-bridges using a two-phase and four-phase control PWM signal for one, two and four phases of the supply. The results showed stable heating and cooling of the PE at frequencies from 30 Hz to 1 kHz. The use of multiphase power supply of PE made it possible to significantly reduce the load on the power source.
Center Director Bridges visits Disability Awareness and Action working Group Technology Fair
NASA Technical Reports Server (NTRS)
1999-01-01
Center Director Roy Bridges stops at the Stewart Eye Institute table at the Disability Awareness and Action Working Group (DAAWG) 1999 Technology Fair being held Oct. 20-21 at Kennedy Space Center. Behind Bridges is Sterling Walker, director of Engineering Development at KSC and chairman of DAAWG. At the near right are George and Marian Hall, who are with the Institute. At the left is Nancie Strott, a multi-media specialist with Dynacs and chairperson of the Fair. The Fair is highlighting vendors demonstrating mobility, hearing, vision and silent disability assistive technology. The purpose is to create an awareness of the types of technology currently available to assist people with various disabilities in the workplace. The theme is that of this year's National Disability Employment Awareness Month, 'Opening Doors to Ability.' Some of the vendors participating are Canine Companions for Independence, Goodwill Industries, Accessible Structures, Division of Blind Services, Space Coast Center for Independent Living, KSC Fitness Center and Delaware North Parks Services.
Center Director Bridges visits Disability Awareness and Action working Group Technology Fair
NASA Technical Reports Server (NTRS)
1999-01-01
Center Director Roy Bridges stops to pet one of the dogs that serves with Canine Companions for Independence, a vendor displaying its capabilities at the Disability Awareness and Action Working Group (DAAWG) 1999 Technology Fair being held Oct. 20-21 at Kennedy Space Center. Standing at the right is Carol Cavanaugh, with KSC Public Services; behind Bridges is Nancie Strott (left), a multi-media specialist with Dynacs and chairperson of the Fair, and Sterling Walker (right), director of Engineering Development and chairman of DAAWG. The Fair is highlighting vendors demonstrating mobility, hearing, vision and silent disability assistive technology. The purpose is to create an awareness of the types of technology currently available to assist people with various disabilities in the workplace. The theme is that of this year's National Disability Employment Awareness Month, 'Opening Doors to Ability.' Some of the other vendors participating are Goodwill Industries, Accessible Structures, Division of Blind Services, Space Coast Center for Independent Living, KSC Fitness Center and Delaware North Parks Services.
NASA Astrophysics Data System (ADS)
Koch, Angira; Kumar, Arvind; Singh, Suryabhan; Borthakur, Rosmita; Basumatary, Debajani; Lal, Ram A.; Shangpung, Sankey
2015-03-01
The synthesis of the heterobinuclear copper-zinc complex [CuZn(bz)3(bpy)2]ClO4 (bz = benzoate) from benzoic acid and bipyridine is described. Single crystal X-ray diffraction studies of the heterobinuclear complex reveals the geometry of the benzoato bridged Cu(II)-Zn(II) centre. The copper or zinc atom is pentacoordinate, with two oxygen atoms from bridging benzoato groups and two nitrogen atoms from one bipyridine forming an approximate plane and a bridging oxygen atom from a monodentate benzoate group. The Cu-Zn distance is 3.345 Å. The complex is normal paramagnetic having μeff value equal to 1.75 BM, ruling out the possibility of Cu-Cu interaction in the structural unit. The ESR spectrum of the complex in CH3CN at RT exhibit an isotropic four line spectrum centred at g = 2.142 and hyperfine coupling constants Aav = 63 × 10-4 cm-1, characteristic of a mononuclear square-pyramidal copper(II) complexes. At LNT, the complex shows an isotropic spectrum with g|| = 2.254 and g⊥ = 2.071 and A|| = 160 × 10-4 cm-1. The Hamiltonian parameters are characteristic of distorted square pyramidal geometry. Cyclic voltammetric studies of the complex have indicated quasi-reversible behaviour in acetonitrile solution.
NASA Astrophysics Data System (ADS)
Godinez-Azcuaga, Valery F.; Farmer, Justin; Ziehl, Paul H.; Giurgiutiu, Victor; Nanni, Antonio; Inman, Daniel J.
2012-04-01
This paper discusses the development status of a self-powered wireless sensor node for steel and concrete bridges monitoring and prognosis. By the end of the third year in this four-year cross-disciplinary project, the 4-channel acoustic emission wireless node, developed by Mistras Group Inc, has already been deployed in concrete structures by the University of Miami. Also, extensive testing is underway with the node powered by structural vibration and wind energy harvesting modules developed by Virginia Tech. The development of diagnosis tools and models for bridge prognosis, which will be discussed in the paper, continues and the diagnosis tools are expected to be programmed in the node's AVR during the 4th year of the project. The impact of this development extends beyond the area of bridge health monitoring into several fields, such as offshore oil platforms, composite components on military ships and race boats, combat deployable bridges and wind turbine blades. Some of these applications will also be discussed. This project was awarded to a joint venture formed by Mistras Group Inc, Virginia Tech, University of South Carolina and University of Miami by the National Institute of Standards and Technology through its Technology Innovation Program Grant #70NANB9H007.
Comparative proteomic analysis of male and female venoms from the Cuban scorpion Rhopalurus junceus.
Rodríguez-Ravelo, Rodolfo; Batista, Cesar V F; Coronas, Fredy I V; Zamudio, Fernando Z; Hernández-Orihuela, Lorena; Espinosa-López, Georgina; Ruiz-Urquiola, Ariel; Possani, Lourival D
2015-12-01
A complete mass spectrometry analysis of venom components from male and female scorpions of the species Rhophalurus junceus of Cuba is reported. In the order of 200 individual molecular masses were identified in both venoms, from which 63 are identical in male and females genders. It means that a significant difference of venom components exists between individuals of different sexes, but the most abundant components are present in both sexes. The relative abundance of identical components is different among the genders. Three well defined groups of different peptides were separated and identified. The first group corresponds to peptides with molecular masses of 1000-2000 Da; the second to peptides with 3500-4500 Da molecular weight, and the third with 6500-8000 Da molecular weights. A total of 86 peptides rich in disulfide bridges were found in the venoms, 27 with three disulfide bridges and 59 with four disulfide bridges. LC-MS/MS analysis allowed the identification and amino acid sequence determination of 31 novel peptides in male venom. Two new putative K(+)-channel peptides were sequences by Edman degradation. They contain 37 amino acid residues, packed by three disulfide bridges and were assigned the systematic numbers: α-KTx 1.18 and α-KTx 2.15. Copyright © 2015 Elsevier Ltd. All rights reserved.
Electrical Rectification in Betaine Derivatives
DOE Office of Scientific and Technical Information (OSTI.GOV)
Sumpter, Bobby G; Meunier, Vincent; Filho, Antonio G. Souza
2008-01-01
We theoretically investigate the electric rectification in an organic two terminal push-pull molecular device using a combination of ab initio techniques. Our main finding is that the electric rectification is extremely sensitive to the length of the chain, undergoing a complete switching after a specific chain length. This unique process occurs for betainelike donor- bridge-acceptor systems and is directly associated with a conjugated bridge in the presence of an external electric field. The conjugated bridge between the donor and acceptor groups is composed of oligoethylene with sizes ranging from zero to ten C=C units. The appearance of electric rectification occursmore » when the bridge size is equal to 5 units and is complete for those larger than 6 units (i.e. full inversion). This new electronic effect is advantageous for the design of large hybrid organic/inorganic circuits with anincreased majority carrier flow that is necessary for the emerging needs of nanotechnology.« less
Booth, Justin H; Garvey, Patrick B; Baumann, Donald P; Selber, Jesse C; Nguyen, Alexander T; Clemens, Mark W; Liu, Jun; Butler, Charles E
2013-12-01
Many surgeons believe that primary fascial closure with mesh reinforcement should be the goal of abdominal wall reconstruction (AWR), yet others have reported acceptable outcomes when mesh is used to bridge the fascial edges. It has not been clearly shown how the outcomes for these techniques differ. We hypothesized that bridged repairs result in higher hernia recurrence rates than mesh-reinforced repairs that achieve fascial coaptation. We retrospectively reviewed prospectively collected data from consecutive patients with 1 year or more of follow-up, who underwent midline AWR between 2000 and 2011 at a single center. We compared surgical outcomes between patients with bridged and mesh-reinforced fascial repairs. The primary outcomes measure was hernia recurrence. Multivariate logistic regression analysis was used to identify factors predictive of or protective for complications. We included 222 patients (195 mesh-reinforced and 27 bridged repairs) with a mean follow-up of 31.1 ± 14.2 months. The bridged repairs were associated with a significantly higher risk of hernia recurrence (56% vs 8%; hazard ratio [HR] 9.5; p < 0.001) and a higher overall complication rate (74% vs 32%; odds ratio [OR] 3.9; p < 0.001). The interval to recurrence was more than 9 times shorter in the bridged group (HR 9.5; p < 0.001). Multivariate Cox proportional hazard regression analysis identified bridged repair and defect width > 15 cm to be independent predictors of hernia recurrence (HR 7.3; p < 0.001 and HR 2.5; p = 0.028, respectively). Mesh-reinforced AWRs with primary fascial coaptation resulted in fewer hernia recurrences and fewer overall complications than bridged repairs. Surgeons should make every effort to achieve primary fascial coaptation to reduce complications. Published by Elsevier Inc.
ERIC Educational Resources Information Center
Cen, Ling; Ruta, Dymitr; Powell, Leigh; Hirsch, Benjamin; Ng, Jason
2016-01-01
The benefits of collaborative learning, although widely reported, lack the quantitative rigor and detailed insight into the dynamics of interactions within the group, while individual contributions and their impacts on group members and their collaborative work remain hidden behind joint group assessment. To bridge this gap we intend to address…
Malagù, Michele; Trevisan, Filippo; Scalone, Antonella; Marcantoni, Lina; Sammarco, Giuseppe; Bertini, Matteo
2017-04-01
In patients undergoing cardiac device implantation, anticoagulant and antiplatelet therapy are associated with an increased risk of pocket hematoma. In case of vitamin K antagonist therapy, a strategy of continued warfarin with no heparin bridge showed a reduction of pocket hematoma. Evidence regarding antiplatelet therapy management is limited. This is a single-center observational study which reflects our systematic approach to the problem. In 2012, we proposed an improved management protocol for anticoagulant and antiplatelet therapy (no-bridge protocol) based on individual thromboembolic risk stratification, noninterruption of oral anticoagulation, no bridge with heparin and elastic adherence compression bandage. The primary end point was the incidence of clinically significant pocket hematoma in the first 30 days after implantation. A total of 1,035 patients were enrolled, of whom 522 received the standard management and 513 the new protocol. The primary end point occurred in 34 patients of the standard management group and 8 patients of the no-bridge protocol group (6.5% vs 1.6%, p <0.001). Patients in the standard management group had a higher incidence of pocket infections (2.3% vs 0.6%, p = 0.02), lead dislodgements (4.8% vs 2.1%, p = 0.02), and thromboembolic events (1.3% vs 0.0%, p <0.01). On a multivariate analysis, heparin and coronary artery disease were independent predictors of pocket hematoma (relative risk [RR] 3.48, 95% confidence interval [CI] 1.55 to 7.83 and RR 2.43, 95% CI 1.25 to 4.76, respectively), whereas the no-bridge protocol was associated with a reduction of pocket hematoma (RR 0.33, 95% CI 0.14 to 0.76). New anticoagulant and antiplatelet therapy management protocol was associated with a reduced incidence of clinically significant pocket hematomas, thromboembolic events, pocket infections, and lead dislodgements. Copyright © 2017 Elsevier Inc. All rights reserved.
Bridging the practitioner-scientist gap in group psychotherapy research.
Lau, Mark A; Ogrodniczuk, John; Joyce, Anthony S; Sochting, Ingrid
2010-04-01
Bridging the practitioner-scientist gap requires a different clinical research paradigm: participatory research that encourages community agency-academic partnerships. In this context, clinicians help define priorities, determine the type of evidence that will have an impact on their practice (affecting the methods that are used to produce the evidence), and develop strategies for translating, implementing, and disseminating their findings into evidence-based practice. Within this paradigm, different roles are assumed by the partners, and sometimes these roles are blended. This paper will consider the perspectives of people who assume these different roles (clinician, researcher, and clinician-researcher) with group psychotherapy as the specific focus. Finally, the establishment of a practice-research network will be discussed as a potentially promising way to better engage group therapists in research.
Teaching Small Group Communication: The Do Good Project
ERIC Educational Resources Information Center
Minei, Elizabeth M.
2016-01-01
This paper focuses on the parameters of a semester-long project called the "Do Good" project, geared towards developing small group communication skills in undergraduate students. This project highlights participation in a social engagement project that allows students to bridge concepts learned in small group communication lectures…
The dangerous role of silence in the relationship between trauma and violence: a group response.
Phillips, Suzanne B
2015-01-01
This article considers that somewhere in the space between violence and trauma is dangerous silence. Silence intensifies the impact of trauma, and trauma that goes unspoken, un-witnessed, and unclaimed too often "outs itself" as more violence to self or others. Relevant empirical evidence on the impact of civilian interpersonal violence, combat trauma, school shootings, bullying, and domestic violence confirms this tragic cycle. Crucial to addressing the danger of silence in this cycle, the article examines the centrality of silence existentially, neuropsychologically, psychologically, developmentally, interpersonally, and culturally in relation to violence. The bridge to voicing and assimilating the unspeakable is empathic connection with others. Drawing upon two different types of group programs, the article demonstrates that group can serve as that bridge. Group process has the potential to undo the dangerous role of silence in the relationship of trauma and violence.
Two-photon or higher-order absorbing optical materials and methods of use
NASA Technical Reports Server (NTRS)
Marder, Seth (Inventor); Perry, Joseph (Inventor)
2012-01-01
Compositions capable of simultaneous two-photon absorption and higher order absorptivities are provided. Compounds having a donor-pi-donor or acceptor-pi-acceptor structure are of particular interest, where the donor is an electron donating group, acceptor is an electron accepting group, and pi is a pi bridge linking the donor and/or acceptor groups. The pi bridge may additionally be substituted with electron donating or withdrawing groups to alter the absorptive wavelength of the structure. Also disclosed are methods of generating an excited state of such compounds through optical stimulation with light using simultaneous absorption of photons of energies individually insufficient to achieve an excited state of the compound, but capable of doing so upon simultaneous absorption of two or more such photons. Applications employing such methods are also provided, including controlled polymerization achieved through focusing of the light source(s) used.
A single molecule rectifier with strong push-pull coupling
NASA Astrophysics Data System (ADS)
Saraiva-Souza, Aldilene; Macedo de Souza, Fabricio; Aleixo, Vicente F. P.; Girão, Eduardo Costa; Filho, Josué Mendes; Meunier, Vincent; Sumpter, Bobby G.; Souza Filho, Antônio Gomes; Del Nero, Jordan
2008-11-01
We theoretically investigate the electronic charge transport in a molecular system composed of a donor group (dinitrobenzene) coupled to an acceptor group (dihydrophenazine) via a polyenic chain (unsaturated carbon bridge). Ab initio calculations based on the Hartree-Fock approximations are performed to investigate the distribution of electron states over the molecule in the presence of an external electric field. For small bridge lengths (n =0-3) we find a homogeneous distribution of the frontier molecular orbitals, while for n >3 a strong localization of the lowest unoccupied molecular orbital is found. The localized orbitals in between the donor and acceptor groups act as conduction channels when an external electric field is applied. We also calculate the rectification behavior of this system by evaluating the charge accumulated in the donor and acceptor groups as a function of the external electric field. Finally, we propose a phenomenological model based on nonequilibrium Green's function to rationalize the ab initio findings.
Wu, Qiong; Kou, Bo; Hang, Zusheng; Zhu, Weihua
2017-06-01
In this work, six (A-F) nitramino (-NHNO 2 )-substituted ditetrazole 2-N-oxides with different bridging groups (-CH 2 -, -CH 2 -CH 2 -, -NH-, -N=N-, and -NH-NH-) were designed. The six compounds were based on the parent compound tetrazole 2-N-oxide, which possesses a high oxygen balance and high density. The structure, heat of formation, density, detonation properties (detonation velocity D and detonation pressure P), and the sensitivity of each compound was investigated systematically via density functional theory, by studying the electrostatic potential, and using molecular mechanics. The results showed that compounds A-F all have outstanding energetic properties (D: 9.1-10.0 km/s; P: 38.0-46.7 GPa) and acceptable sensitivities (h 50 : 28-37 cm). The bridging group present was found to greatly affect the detonation performance of each ditetrazole 2-N-oxide, and the compound with the -NH-NH- bridging group yielded the best results. Indeed, this compound (F) was calculated to have comparable sensitivity to the famous and widely used high explosive 1,3,5,7-tetranitro-1,3,5,7-tetrazocane (HMX), but with values of D and P that were about 8.7% and 19.4% higher than those for HMX, respectively. The present study shows that tetrazole 2-N-oxide is a useful parent compound which could potentially be used in the design of new and improved high-energy compounds to replace existing energetic compounds such as HMX.
ERIC Educational Resources Information Center
Bowles, Laura; Piggott, Gail B.
The Employers' Child Care Alliance, a group of major employers in Lee County, Alabama, developed the "Bridges" program, an innovative program for children ages 10-14 during out-of-school time. The program focuses on the growth of the whole child, specifically in areas not traditionally focused on in school, such as creative development, cultural…
Shake table test of soil-pile groups-bridge structure interaction in liquefiable ground
NASA Astrophysics Data System (ADS)
Tang, Liang; Ling, Xianzhang; Xu, Pengju; Gao, Xia; Wang, Dongsheng
2010-03-01
This paper describes a shake table test study on the seismic response of low-cap pile groups and a bridge structure in liquefiable ground. The soil profile, contained in a large-scale laminar shear box, consisted of a horizontally saturated sand layer overlaid with a silty clay layer, with the simulated low-cap pile groups embedded. The container was excited in three El Centro earthquake events of different levels. Test results indicate that excessive pore pressure (EPP) during slight shaking only slightly accumulated, and the accumulation mainly occurred during strong shaking. The EPP was gradually enhanced as the amplitude and duration of the input acceleration increased. The acceleration response of the sand was remarkably influenced by soil liquefaction. As soil liquefaction occurred, the peak sand displacement gradually lagged behind the input acceleration; meanwhile, the sand displacement exhibited an increasing effect on the bending moment of the pile, and acceleration responses of the pile and the sand layer gradually changed from decreasing to increasing in the vertical direction from the bottom to the top. A jump variation of the bending moment on the pile was observed near the soil interface in all three input earthquake events. It is thought that the shake table tests could provide the groundwork for further seismic performance studies of low-cap pile groups used in bridges located on liquefiable groun.
Influence of functional groups on the C α-C β chain of L-phenylalanine and its derivatives
NASA Astrophysics Data System (ADS)
Ganesan, Aravindhan; Brunger, Michael; Wang, Feng
2010-07-01
L-phenylalanine ( L-phe) consists of three different functional groups, i.e., phenyl, carboxyl (-COOH) and amino (-NH 2), joining through the C α-C β bridge. Substitution of these groups produces 2-phenethylamine (PEA) and 3-phenylpropionic acid (PPA). Electronic structures of L-phe, PEA and PPA together with smaller "fragments" L-alanine and benzene were determined using density functional theory (DFT), from which core and valence shell ionization spectra were simulated. Comparison of the spectra reveals that core shell ionization energies clearly indicate that the carbon bridge is significantly affected by their functional group substitutions particularly at the C α site. In the valence space, quite unexpectedly, the frontier orbitals are concentrated on the benzene group although some energy splitting is observed. The orbitals which significantly affect the C α-C β carbon backbone are from the inner valence shell in the ionization energy region of 20-26 eV of the molecules.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Das, A.; Jeffery, J.C.; Maher, J.P.
The authors have prepared the new monodentate ligands 4-(4-methoxyphenyl)pyridine, 1-(4-pyridyl)-2-(4-methoxyphenyl)ethene, 1-(4-pyridyl)-2-(3-methoxyphenyl)ethene, and 1-(3-pyridyl)-2-(4-methoxyphenyl)ethene (L[sup 5]-L[sup 8]); demethylation of the methoxy group in each case afforded the new bridging bidentate ligands HL[sup 1]-HL[sup 4], which contain one pyridyl and one phenolate donor. Attachment of a MoL*(NO)Cl [L* = hydrotris(3,5-dimethylpyrazolyl)borate] moiety to the pyridyl groups of L[sup 5]-L[sup 8] gave the 17-electron complexes [Mo(NO)L*ClL[prime
Micro-bridge defects: characterization and root cause analysis
NASA Astrophysics Data System (ADS)
Santoro, Gaetano; Van den Heuvel, Dieter; Braggin, Jennifer; Rosslee, Craig; Leray, Philippe J.; Cheng, Shaunee; Jehoul, Christiane; Schreutelkamp, Robert; Hillel, Noam
2010-03-01
Defect review of advanced lithography processes is becoming more and more challenging as feature sizes decrease. Previous studies using a defect review SEM on immersion lithography generated wafers have resulted in a defect classification scheme which, among others, includes a category for micro-bridges. Micro-bridges are small connections between two adjacent lines in photo-resist and are considered device killing defects. Micro-bridge rates also tend to increase as feature sizes decrease, making them even more important for the next technology nodes. Especially because micro-bridge defects can originate from different root causes, the need to further refine and split up the classification of this type of defect into sub groups may become a necessity. This paper focuses on finding the correlation of the different types of micro-bridge defects to a particular root cause based on a full characterization and root cause analysis of this class of defects, by using advanced SEM review capabilities like high quality imaging in very low FOV, Multi Perspective SEM Imaging (MPSI), tilted column and rotated stage (Tilt&Rotation) imaging and Focused Ion Beam (FIB) cross sectioning. Immersion lithography material has been mainly used to generate the set of data presented in this work even though, in the last part of the results, some EUV lithography data will be presented as part of the continuing effort to extend the micro-bridge defect characterization to the EUV technology on 40 nm technology node and beyond.
NASA Astrophysics Data System (ADS)
Ramanathan, Karthik Narayan
Quantitative and qualitative assessment of the seismic risk to highway bridges is crucial in pre-earthquake planning, and post-earthquake response of transportation systems. Such assessments provide valuable knowledge about a number of principal effects of earthquakes such as traffic disruption of the overall highway system, impact on the regions’ economy and post-earthquake response and recovery, and more recently serve as measures to quantify resilience. Unlike previous work, this study captures unique bridge design attributes specific to California bridge classes along with their evolution over three significant design eras, separated by the historic 1971 San Fernando and 1989 Loma Prieta earthquakes (these events affected changes in bridge seismic design philosophy). This research developed next-generation fragility curves for four multispan concrete bridge classes by synthesizing new knowledge and emerging modeling capabilities, and by closely coordinating new and ongoing national research initiatives with expertise from bridge designers. A multi-phase framework was developed for generating fragility curves, which provides decision makers with essential tools for emergency response, design, planning, policy support, and maximizing investments in bridge retrofit. This framework encompasses generational changes in bridge design and construction details. Parameterized high-fidelity three-dimensional nonlinear analytical models are developed for the portfolios of bridge classes within different design eras. These models incorporate a wide range of geometric and material uncertainties, and their responses are characterized under seismic loadings. Fragility curves were then developed considering the vulnerability of multiple components and thereby help to quantify the performance of highway bridge networks and to study the impact of seismic design principles on the performance within a bridge class. This not only leads to the development of fragility relations that are unique and better suited for bridges in California, but also leads to the creation of better bridge classes and sub-bins that have more consistent performance characteristics than those currently provided by the National Bridge Inventory. Another important feature of this research is associated with the development of damage state definitions and grouping of bridge components in a way that they have similar consequences in terms of repair and traffic implications following a seismic event. These definitions are in alignment with the California Department of Transportation’s design and operational experience, thereby enabling better performance assessment, emergency response, and management in the aftermath of a seismic event. The fragility curves developed as a part of this research will be employed in ShakeCast, a web-based post-earthquake situational awareness application that automatically retrieves earthquake shaking data and generates potential damage assessment notifications for emergency managers and responders.
Building bridges: marketing managed care to ethnically diverse populations.
Rosen, M B
1996-12-01
America's population "stew" creates specific challenges to health plans attempting to reach ethnically differentiated enrollee groups. In this article, the author provides snapshots of four ethnic groups, suggests some marketing considerations when preparing communications to these groups, and helps draw some conclusions about marketing managed care products to a culturally diverse population.
Pauly, Stephan; Fiebig, David; Kieser, Bettina; Albrecht, Bjoern; Schill, Alexander; Scheibel, Markus
2011-12-01
Biomechanical comparison of four different Speed-Bridge configurations with or without medial or lateral row reinforcement. Reinforcement of the knotless Speed-Bridge double-row repair technique with additional medial mattress- or lateral single-stitches was hypothesized to improve biomechanical repair stability at time zero. Controlled laboratory study: In 36 porcine fresh-frozen shoulders, the infraspinatus tendons were dissected and shoulders were randomized to four groups: (1) Speed-Bridge technique with single tendon perforation per anchor (STP); (2) Speed-Bridge technique with double tendon perforation per anchor (DTP); (3) Speed-Bridge technique with medial mattress-stitch reinforcement (MMS); (4) Speed-Bridge technique with lateral single-stitch reinforcement (LSS). All repairs were cyclically loaded from 10-60 N up to 10-200 N (20 N stepwise increase) using a material testing device. Forces at 3 and 5 mm gap formation, mode of failure and maximum load to failure were recorded. The MMS-technique with double tendon perforation showed significantly higher ultimate tensile strength (338.9 ± 90.0 N) than DTP (228.3 ± 99.9 N), LSS (188.9 ± 62.5 N) and STP-technique (122.2 ± 33.8 N). Furthermore, the MMS-technique provided increased maximal force resistance until 3 and 5 mm gap formation (3 mm: 77.8 ± 18.6 N; 5 mm: 113.3 ± 36.1 N) compared with LSS, DTP and STP (P < 0.05 for each 3 and 5 mm gap formation). Failure mode was medial row defect by tendon sawing first, then laterally. No anchor pullout occurred. Double tendon perforation per anchor and additional medial mattress stitches significantly enhance biomechanical construct stability at time zero in this ex vivo model when compared with the all-knotless Speed-Bridge rotator cuff repair.
Xu, Huajun; Yang, Dan; Liu, Fenggang; Fu, Mingkai; Bo, Shuhui; Liu, Xinhou; Cao, Yuan
2015-11-28
In this work, we investigated the enhancement of the electro-optic response by introducing electron-rich heteroatoms as additional donors into the donor or bridge of a conventional second-order nonlinear optical chromophore. A series of chromophores C2-C4 based on the same tricyanofuran acceptor (TCF) but with different heteroatoms in the alkylamino phenyl donor (C2 or C3) or thiophene bridge (C4) have been synthesized and systematically investigated. Density functional theory calculations suggested that chromophores C2-C4 had a smaller energy gap and larger first-order hyperpolarizability (β) than traditional chromophore C1 due to the additional heteroatoms. Single crystal structure analyses and optimized configurations indicate that the rationally introduced heteroatom group would bring larger β and weaker intermolecular interactions which were beneficial for translating molecular β into macro-electro-optic activity in electric field poled films. The electro-optic coefficient of poled films containing 25 wt% of these new chromophores doped in amorphous poly-carbonate afforded values of 83 and 91 pm V(-1) at 1310 nm for chromophores C3 and C4, respectively, which are two times higher than that of the traditional chromophore C1 (39 pm V(-1)). High r33 values indicated that introducing heteroatoms to the donor and bridge of a conventional molecular structure can efficiently improve the electron-donating ability, which improves the β. The long-chain on the donor or bridge part, acting as the isolation group, may reduce inter-molecular electrostatic interactions, thus enhancing the macroscopic EO activity. These results, together with good solubility and compatibility with the polymer, show the new chromophore's potential application in electro-optic devices.
Cho, Byung-Ki; Kim, Yong-Min; Park, Kyoung-Jin; Park, Ji-Kang; Kim, Do-Kyoon
2015-02-01
There are various ligament reattachment techniques for the modified Brostrom procedure. There have been few comparative studies on recently developed techniques. This prospective study was performed to compare the functional outcomes of 2 different ligament reattachment techniques using suture anchors. We furthermore evaluated the cost-effectiveness of the suture bridge technique. Forty-five amateur athletes under 30 years of age were followed for more than 2 years. Twenty-four procedures with the suture anchor technique and 21 procedures with the suture bridge technique were performed by one surgeon. The functional evaluation consisted of the American Orthopaedic Foot & Ankle Society (AOFAS) score, Foot and Ankle Outcome Score (FAOS), Karlsson score, Sefton grading system, and the period to return to various forms of exercise (jogging, spurt running, jumping, one leg standing for >1 minute, walking on uneven ground, and going down stairs). Measurement of talar tilt angle and anterior talar translation was obtained from stress radiographs to evaluate mechanical stability. There were no significant differences on AOFAS score, FAOS, Karlsson score, Sefton grade, and stress radiographs. There were no significant differences on the return to exercises, except for jumping. As the most common complication, there were 3 cases of skin irritation by suture materials in the suture anchor group and 2 cases of intraoperative breakage of the suture anchor in suture bridge group. Both ligament reattachment techniques using suture anchors showed similar functional outcomes. Considering the additional medical expenses incurred by more suture anchors, the modified Brostrom procedure using the suture bridge technique had low cost-effectiveness. Proper indication and clinical usefulness of suture bridge technique for chronic ankle instability will be addressed in further studies. Level II, prospective comparative study. © The Author(s) 2014.
Load response and gap formation in a single-row cruciate suture rotator cuff repair.
Huntington, Lachlan; Richardson, Martin; Sobol, Tony; Caldow, Jonathon; Ackland, David C
2017-06-01
Double-row rotator cuff tendon repair techniques may provide superior contact area and strength compared with single-row repairs, but are associated with higher material expenses and prolonged operating time. The purpose of this study was to evaluate gap formation, ultimate tensile strength and stiffness of a single-row cruciate suture rotator cuff repair construct, and to compare these results with those of the Mason-Allen and SutureBridge repair constructs. Infraspinatus tendons from 24 spring lamb shoulders were harvested and allocated to cruciate suture, Mason-Allen and SutureBridge repair groups. Specimens were loaded cyclically between 10 and 62 N for 200 cycles, and gap formation simultaneously measured using a high-speed digital camera. Specimens were then loaded in uniaxial tension to failure, and construct stiffness and repair strength were evaluated. Gap formation in the cruciate suture repair was significantly lower than that of the Mason-Allen repair (mean difference = 0.6 mm, P = 0.009) and no different from that of the SutureBridge repair (P > 0.05). Both the cruciate suture repair (mean difference = 15.7 N/mm, P = 0.002) and SutureBridge repair (mean difference = 15.8 N/mm, P = 0.034) were significantly stiffer than that of the Mason-Allen repair; however, no significant differences in ultimate tensile strength between repair groups were discerned (P > 0.05). The cruciate suture repair construct, which may represent a simple and cost-effective alternative to double-row and double-row equivalent rotator cuff repairs, has comparable biomechanical strength and integrity with that of the SutureBridge repair, and may result in improved construct longevity and tendon healing compared with the Mason-Allen repair. © 2017 Royal Australasian College of Surgeons.
Kjaer, D W; Nassar, M; Jensen, L S; Svendsen, L B; Mortensen, F V
2017-02-01
This study aimed to assess the impact of esophageal stenting on postoperative complications and survival in patients with obstructing esophageal and gastroesophageal junction (GEJ) cancer. All patients treated without neoadjuvant therapy that had an R0-resection performed for esophageal and GEJ cancer between January 2003 and December 2010 were identified from a prospectively maintained database. Data on stenting, postoperative mortality, morbidity, recurrence-free survival, complications, and length of hospital stay were collected. Kaplan-Meier plots for survival and recurrence-free survival curves were constructed for R0 resected patients. Data were compared between the stent and no-stent group by nonparametric tests. Two hundred seventy three consecutive R0 resected patients with esophageal or GEJ cancer were identified. Of these patients, 63 had a stent as a bridge to surgery. The male/female ratio was 2.64 (198/75) with a median age in the stent group (SG) of 65.1 versus 64.3 in the no stent group (NSG). Patients were comparable with respect to gender, age, smoking, TNM-classification, oncological treatment, hospital stay, tumor location, and histology. The median survival in the SG was 11.6 months compared with 21.3 months for patients treated without a bridging stent (P < 0.001). There were no statistically significant differences in 30-day mortality between the two groups, but NSG patients exhibited a significantly better two-year survival (P = 0.017). The median recurrence-free survival was 9.1 months for the SG compared with 15.2 months for the NSG. The use of a stent as a bridging procedure to surgery in patients treated without neaoadjuvant therapy for an esophageal or GEJ cancer that later underwent R0 resection decreased the two year survival and the recurrence-free survival. © 2016 International Society for Diseases of the Esophagus.
Load and resistance factor design of bridge foundations accounting for pile group-soil interaction.
DOT National Transportation Integrated Search
2015-11-01
Pile group foundations are used in most foundation solutions for transportation structures. Rigorous and reliable pile design methods are : required to produce designs whose level of safety (probability of failure) is known. By utilizing recently dev...
NASA Astrophysics Data System (ADS)
Golbedaghi, Reza; Azimi, Saeid; Molaei, Atefeh; Hatami, Masoud; Notash, Behrouz
2017-10-01
A new Schiff base ligand HL, 1,3-bis(2-((Z)-(2-aminoethylimino)methyl)phenoxy)ethylene di amine, has been synthesized from the reaction of a new aldehyde and ethylenediamine. After preparation the Schiff base, a new dinuclear Cu(II) complex with two different geometry for each metal ion was synthesized. Single crystal X-ray structure analysis of the complex Cu(II) showed that the complex is binuclear and all nitrogen and oxygen atoms of ligand (N4O3) are coordinated to two Cu(II) center ions. The crystal structure studying shows, a perchlorate ion has been coordinated to the two Cu(II) metal centers as bridged and another perchlorate coordinated to the one of Cu(II) ion as terminal. However, two interesting structures square pyramidal and distorted octahedral Cu(II) ions are bridged asymmetrically by a perchlorate ion and oxygen of hydroxyl group of Schiff base ligand. In addition, we had a theoretical study to have a comparison of experimental and theoretical results we determined the HOMO and LUMO orbitals.
Pike, Meredith; Swank, Paul; Taylor, Heather; Landry, Susan; Barnes, Marcia A.
2014-01-01
Children with spina bifida myelomeningocele (SBM) are more likely to display a pattern of good-decoding/poor comprehension than their neurologically intact peers. The goals of the current study were to (1) examine the cognitive origins of one of the component skills of comprehension, bridging inferences, from a developmental perspective and (2) to test the effects of those relations on reading comprehension achievement. Data from a sample of children with SBM and a control group (n = 78) who participated in a longitudinal study were taken from age 36-month and 9.5-year time points. A multiple mediation model provided evidence that three preschool cognitive abilities (working memory/inhibitory control, oral comprehension, narrative recall), could partially explain the relation between group and bridging inference skill. A second mediation model supported that each of the 36-month abilities had an indirect effect on reading comprehension through bridging inference skill. Findings contribute to an understanding of both typical and atypical comprehension development, blending theories from the developmental, cognitive, and neuropsychological literature. PMID:23388065
Pike, Meredith; Swank, Paul; Taylor, Heather; Landry, Susan; Barnes, Marcia A
2013-04-01
Children with spina bifida myelomeningocele (SBM) are more likely to display a pattern of good-decoding/poor comprehension than their neurologically intact peers. The goals of the current study were to (1) examine the cognitive origins of one of the component skills of comprehension, bridging inferences, from a developmental perspective and (2) to test the effects of those relations on reading comprehension achievement. Data from a sample of children with SBM and a control group (n = 78) who participated in a longitudinal study were taken from age 36-month and 9.5-year time points. A multiple mediation model provided evidence that three preschool cognitive abilities (working memory/inhibitory control, oral comprehension, narrative recall), could partially explain the relation between group and bridging inference skill. A second mediation model supported that each of the 36-month abilities had an indirect effect on reading comprehension through bridging inference skill. Findings contribute to an understanding of both typical and atypical comprehension development, blending theories from the developmental, cognitive, and neuropsychological literature.
NASA Astrophysics Data System (ADS)
Golbedaghi, Reza; Alavipour, Ehsan
2015-11-01
Three new binuclear Cu(II), Mn(II), Co(II) complexes [Cu2(L) (ClO4)](ClO4)2 (1), [Mn2(L) (ClO4)](ClO4)2 (2), and [Co2(L) (ClO4)](ClO4)2 (3), {L = 1,3-bis(2-((Z)-(2-aminopropylimino)methyl)phenoxy)propan-2-ol} have been synthesized. Single crystal X-ray structure analysis of complex 1 showed that the complex is binuclear and all nitrogen and oxygen atoms of ligand (N4O3) are coordinated to two Cu(II) center ions. In addition, the crystal structure studying shows, a perchlorate ion has been bridged to the Cu(II) metal centers. However, two distorted square pyramidal Cu(II) ions are bridged asymmetrically by a perchlorate ion and oxygen of hydroxyl group of Schiff base ligand. In addition, the conductometry behaviors of all complexes were studied in acetonitrile solution.
Ravald, Nils; Dahlgren, Simon; Teiwik, Anders; Gröndahl, Kerstin
2013-10-01
To study the long-term outcome of implant survival rate, soft and hard tissue conditions and prosthetic status in a group of individuals treated with either Astra Tech TiOblast or Brånemark turned implants supporting a full-arch bridge. Edentulous patients treated with either Astra Tech TiOblast surface or Brånemark turned implants were recalled for examination after 12-15 years. Out of initially 66 patients 46 were available for examination. Intra-oral radiographs were taken for bone level assessments. Clinical prosthetic conditions, number of surviving implants, implant stability, plaque scores, probing pocket depths, bleeding and pus after probing were recorded. Analyses of bone level changes during the total observation period were performed. Three patients in the Astra Tech group lost totally eight implants and five patients in the Brånemark group lost 10 implants during the total observation period. No statistically significant difference in implant loss or bone level change was found. Sixteen per cent of Astra Tech and 29% of Brånemark patients showed at least one implant with ≥2 mm bone loss after the first year in function. The corresponding prevalence on implant level was 6% and 5% respectively. No significant differences were found between the other examined variables. Two patients showed prosthetic complications of the supra construction in need of repair. Seven bridges had minor ceramic chippings. Treatment with Astra Tech TiOblast implants and Brånemark turned implants supporting full-arch bridges showed generally good clinical results with low numbers of implants with marginal bone loss indicative of peri-implantitis. No significant differences were found between the implant systems after 12-15 years in function. © 2012 John Wiley & Sons A/S.
Longevity of anterior resin-bonded bridges: survival rates of two tooth preparation designs.
Abuzar, M; Locke, J; Burt, G; Clausen, G; Escobar, K
2018-04-16
Significant developments have occurred in the design of resin-bonded bridges (RBB) over the past two decades. They are commonly used as an alternative treatment option for a single missing tooth. The longevity of these bridges needs to be further investigated to evaluate long-term outcomes for this option to remain relevant. A cohort of patients who received anterior resin-bonded bridges (ARBB) over two decades was studied retrospectively. Longevity of 206 ARBB was assessed using Kaplan-Meier probability estimates. The two modified tooth preparation designs investigated were: (A) mesial and distal vertical grooves only; and (B) one proximal groove adjacent to the pontic and two palatal grooves. Age and gender of the patient cohort were also recorded. Overall survival rate of ARBB was 98% at 5 years, 97.2% at 10 years, and 95.1% from 12 years till 21 years. Survival curves showed minor differences when compared for the two designs, age groups and gender of ARBB recipients. Differences in the proportion of surviving bridges for design A (95.96%) and design B (98.13%) were not statistically significant (Fisher's exact test). Anterior RBB with described tooth preparation designs demonstrate a high survival rate. © 2018 Australian Dental Association.
Kurimura, Muneaki; Liu, Hehua; Sulima, Agnieszka; Hashimoto, Akihiro; Przybyl, Anna K.; Ohshima, Etsuo; Kodato, Shinichi; Deschamps, Jeffrey R.; Dersch, Christina M.; Rothman, Richard B.; Lee, Yong Sok; Jacobson, Arthur E.; Rice, Kenner C.
2008-01-01
In the isomeric series of 12 racemic topologically rigid N-methyl analogues of oxide-bridged phenylmorphans, all but two of the racemates, the ortho- and para-b-oxide-bridged phenylmorphansa 20 and 12, have remained to be synthesized. The b-isomers were very difficult to synthesize because of the highly strained 5,6-trans-fused ring junction that had to be formed. Our successful strategy required functionalization of the position para (or ortho) to a fluorine atom on the aromatic ring using an electron-withdrawing nitro group to activate that fluorine. The racemic N-phenethyl analogues 24 and 16 were moderately potent κ-receptor antagonists in the [35S]GTPγS assay. We synthesized the N-phenethyl-substituted oxide-bridged phenylmorphans in the ortho- and para-d oxide-bridged phenylmorphana series (51 and 52) which had not been previously evaluated using contemporary receptor binding assays to see whether they also have higher affinity for opioid receptors than their N-methyl relatives 46 and 47. PMID:19053757
Li, Zhi-Xiong; Wu, Xiao-Hua; Wu, Hai-yan; Chang, Wen-Ju; Chang, Xiu-juan; Yi, Tuo; Shi, Qiang; Chen, Jing-Wen; Feng, Qing-Yang; Zhu, De-Xiang; Wei, Ye; Zhong, Yun-Shi; Xu, Jian-Min
2016-03-01
The efficacy and safety of self-expandable metallic stents (SEMSs) as a bridge for patients with acute malignant colorectal obstructions (AMCOs) are still controversial. We conducted this study to evaluate the outcomes of patients with AMCOs treated by different strategies. From January 2010 to March 2014, a total of 171 patients with AMCOs from Zhongshan Hospital were retrospectively enrolled in this study. One hundred twenty patients successfully received stent placement followed by one-stage laparoscopic or open resection in the stent group, and 51 patients received emergency operations in the emergency group. The operation duration and postoperative hospital stay were significantly shorter in the stent group (114.51 ± 28.65 vs. 160.39 ± 58.94 min, P < 0.001; 8.00 ± 3.97 vs. 12.59 ± 9.07 days, P = 0.001). The stent group also had significantly reduced intraoperative blood loss and the incidence of postoperative complications compared with the emergency group (61.00 ± 43.70 vs. 121.18 ± 85.90 ml, P < 0.001; 16.7 vs. 37.3%, P = 0.003). Kaplan-Meier survival curves showed that the median survival time in the stent group was significantly longer than that in the emergency group (53 vs. 41 months, P = 0.034). In subgroup analysis of stent group, the stent laparoscopy group had significantly decreased postoperative complications (P = 0.025), and similar long-term survival (P = 0.81). Stent placement as a bridge to surgery is a safe and feasible procedure and provides significant advantages in terms of short-term outcomes and favorable prognoses for patients with AMCOs. Laparoscopic surgery could be considered as an optimal treatment after stent placement.
NASA Astrophysics Data System (ADS)
Ambati, Jyothirmai
This dissertation presents studies of the synthetic processes and applications of siloxane-based materials. Kinetic investigations of bridged organoalkoxysilanes that are precursors to organic-inorganic hybrid polysilsesquioxanes are a primary focus. Quick gelation despite extensive cyclization is found during the polymerization of bridged silane precursors except for silanes with certain short bridges. This work is an attempt to characterize and understand some of the distinct features of bridged silanes using experimental characterization, kinetic modeling and simulation. In addition to this, the dissertation shows how the properties of siloxane-materials can be engineered for drug delivery and adsorption. The phase behavior of polymerizing mixtures is first investigated to identify the solutions that favor kinetic characterization. Microphase separation is found to cause gradual loss of NMR signal for certain initial compositions. Distortionless Enhancement by Polarization Transfer 29Si NMR is employed to identify the products of polymerization of some short-bridged silanes under no signal loss conditions. This technique requires knowing indirect 29Si-1H scalar coupling constants which sometimes cannot be measured due to second-order effects. However, the B3LYP density functional method with 6-31G basis set is found to predict accurate 29Si- 1H coupling constants of organoalkoxysilanes and siloxanes. The scalar coupling constants thus estimated are employed to resolve non-trivial coupled NMR spectra and quantitative kinetic modeling is performed using the DEPT Si NMR transients. In order to investigate the role of the organic bridging group, the structural evolution of bridged and non-bridged silanes are compared using Monte Carlo simulations. Kinetic and simulation models suggest that cyclization plays a key role right from the onset of polymerization for bridged silanes even more than in non-bridged silanes. The simulations indicate that the carbosiloxane rings formed from short-bridged precursors slow down but do not prevent gelation. The tuning of siloxane-based materials for adsorption technologies are also discussed here. In the first example, antioxidant enzyme loading is investigated as a means to reduce oxidative stress generated by silica nanoparticle drug carriers. Materials are engineered for promising enzyme loading and protection from proteolysis. Second, the potential of copper sulfate impregnation to enhance adsorption of ammonia by silica is explored by molecular simulation. KEYWORDS: Sol-gel Polymerization, Kinetic Investigation, Si NMR, Bridged Silanes, DFT Calculations.
Structural characterization of thioether-bridged bacteriocins.
Lohans, Christopher T; Vederas, John C
2014-01-01
Bacteriocins are a group of ribosomally synthesized antimicrobial peptides produced by bacteria, some of which are extensively post-translationally modified. Some bacteriocins, namely the lantibiotics and sactibiotics, contain one or more thioether bridges. However, these modifications complicate the structural elucidation of these bacteriocins using conventional techniques. This review will discuss the techniques and strategies that have been applied to determine the primary structures of lantibiotics and sactibiotics. A major challenge is to identify the topology of thioether bridges in these peptides (i.e., which amino-acid residues are involved in which bridges). Edman degradation, NMR spectroscopy and tandem MS have all been commonly applied to characterize these bacteriocins, but can be incompatible with the post-translational modifications present. Chemical modifications to the modified residues, such as desulfurization and reduction, make the treated bacteriocins more compatible to analysis by these standard peptide analytical techniques. Despite their differences in structure, similar strategies have proved useful to study the structures of both lantibiotics and sactibiotics.
Implementation of Teacher Consultation and Coaching in Urban Schools: A Mixed Method Study
Cappella, Elise; Jackson, Daisy R.; Kim, Ha Yeon; Bilal, Caroline; Holland, Sibyl; Atkins, Marc S.
2015-01-01
Guided by implementation science scholarship and school mental health research, the current study uses qualitative and quantitative data to illuminate the barriers, opportunities, and processes underlying the implementation of a teacher consultation and coaching model (BRIDGE) in urban elementary schools. Data come from five public elementary schools, 12 school mental health staff (BRIDGE consultants), and 18 teachers participating in a classroom-randomized trial of BRIDGE. Findings from directed content analysis of teacher focus group and interview data suggest that aspects of the BRIDGE intervention model, school organization and classroom contexts, and teachers/consultants and their relationship were relevant as implementation facilitators or barriers. In addition, case study analysis of intervention materials and fidelity tools from classrooms with moderate-to-high dosage and adherence suggest variation in consultation and coaching by initial level of observed classroom need. Results illuminate the need for implementation research to extend beyond simple indicators of fidelity to the multiple systems and variation in processes at play across levels of the implementation context. PMID:27293490
Lee, Li-Wan; Hsiao, Sheng-Huang; Hung, Wei-Chiang; Lin, Yun-Ho; Chen, Po-Yu; Chiang, Chun-Pin
2015-05-01
Mineral trioxide aggregate (MTA) is a biocompatible material for direct pulp capping. This study was designed to compare the clinical outcomes of pulp-exposed teeth treated with either poly(ε-caprolactone) fiber mesh (PCL-FM) as a barrier for MTA (so-called PCL-FM/MTA) or MTA direct pulp capping. Sixty human vital teeth were evenly divided into 4 groups (n = 15 in each group). Teeth in groups 1 and 3 had pulp exposure <1 mm in diameter, whereas teeth in groups 2 and 4 had pulp exposure of 1-1.5 mm in diameter. Teeth in groups 1 and 2 were treated with PCL-FM/MTA direct pulp capping, and those in groups 3 and 4 were treated with MTA direct pulp capping. Teeth treated with PCL-FM/MTA direct pulp capping needed a significantly shorter mean duration for dentin bridge formation than teeth treated with MTA direct pulp capping. Moreover, teeth with pulp exposure <1.0 mm in diameter needed a significantly shorter mean duration for dentin bridge formation than teeth with pulp exposure of 1-1.5 mm in diameter after either PCL-FM/MTA or MTA direct pulp capping treatment. In addition, teeth treated with PCL-FM/MTA direct pulp capping formed an approximately 3-fold thicker dentin bridge than teeth treated with MTA direct pulp capping 8 weeks or 3 months later. Furthermore, none of the teeth treated with PCL-FM/MTA direct pulp capping showed tooth discoloration after treatment for 3 months. PCL-FM/MTA is a better combination material than MTA alone for direct pulp capping of human permanent teeth. Copyright © 2015 American Association of Endodontists. Published by Elsevier Inc. All rights reserved.
Paris, Guillaume; Kraszewski, Sebastian; Ramseyer, Christophe; Enescu, Mironel
2012-11-01
The role of the 17 disulfide (S-S) bridges in preserving the native conformation of human serum albumin (HSA) is investigated by performing classical molecular dynamics (MD) simulations on protein structures with intact and, respectively, reduced S-S bridges. The thermal unfolding simulations predict a clear destabilization of the protein secondary structure upon reduction of the S-S bridges as well as a significant distortion of the tertiary structure that is revealed by the changes in the protein native contacts fraction. The effect of the S-S bridges reduction on the protein compactness was tested by calculating Gibbs free energy profiles with respect to the protein gyration radius. The theoretical results obtained using the OPLS-AA and the AMBER ff03 force fields are in agreement with the available experimental data. Beyond the validation of the simulation method, the results here reported provide new insights into the mechanism of the protein reductive/oxidative unfolding/folding processes. It is predicted that in the native conformation of the protein, the thiol (-SH) groups belonging to the same reduced S-S bridge are located in potential wells that maintain them in contact. The -SH pairs can be dispatched by specific conformational transitions of the peptide chain located in the neighborhood of the cysteine residues. Copyright © 2012 Wiley Periodicals, Inc.
Effects of acute respiratory and metabolic acidosis on diaphragm muscle obtained from rats.
Michelet, Pierre; Carreira, Serge; Demoule, Alexandre; Amour, Julien; Langeron, Olivier; Riou, Bruno; Coirault, Catherine
2015-04-01
Acute respiratory acidosis is associated with alterations in diaphragm performance. The authors compared the effects of respiratory acidosis and metabolic acidosis in the rat diaphragm in vitro. Diaphragmatic strips were stimulated in vitro, and mechanical and energetic variables were measured, cross-bridge kinetics calculated, and the effects of fatigue evaluated. An extracellular pH of 7.00 was obtained by increasing carbon dioxide tension (from 25 to 104 mmHg) in the respiratory acidosis group (n = 12) or lowering bicarbonate concentration (from 24.5 to 5.5 mM) in the metabolic acidosis group (n = 12) and the results compared with a control group (n = 12, pH = 7.40) after 20-min exposure. Respiratory acidosis induced a significant decrease in maximum shortening velocity (-33%, P < 0.001), active isometric force (-36%, P < 0.001), and peak power output (-59%, P < 0.001), slowed relaxation, and decreased the number of cross-bridges (-35%, P < 0.001) but not the force per cross-bridge, and impaired recovery from fatigue. Respiratory acidosis impaired more relaxation than contraction, as shown by impairment in contraction-relaxation coupling under isotonic (-26%, P < 0.001) or isometric (-44%, P < 0.001) conditions. In contrast, no significant differences in diaphragmatic contraction, relaxation, or contraction-relaxation coupling were observed in the metabolic acidosis group. In rat diaphragm, acute (20 min) respiratory acidosis induced a marked decrease in the diaphragm contractility, which was not observed in metabolic acidosis.
Histological Effects of Enamel Matrix Derivative on Exposed Dental Pulp.
Bajić, Marijana Popović; Danilović, Vesna; Prokić, Branislav; Prokić, Bogomir Bolka; Manojlović, Milica; Živković, Slavoljub
2015-01-01
Direct pulp capping procedure is a therapeutic application of a drug on exposed tooth pulp in order to ensure the closure of the pulp chamber and to allow the healing process to take place. The aim of this study was to examine the histological effects of Emdogain® on exposed tooth pulp of a Vietnamese pig (Sus scrofa verus). The study comprised 20 teeth of a Vietnamese pig. After class V preparation on the buccal surfaces of incisors, canines and first premolars, pulp was exposed. In the experimental group, the perforations were capped with Emdogain® (Straumann, Basel, Switzerland), while in the control group pulp capping was performed with MTA® (Dentsply Tulsa Dental, Johnson City, TN, USA). All cavities were restored with glass-ionomer cement (GC Fuji VIII, GC Corporation, Tokyo, Japan). The observational period was 28 days, after which the animal was sacrificed and histological preparations were made. A light microscope was used to analyze dentin bridge formation, tissue reorganization and inflammation, and the presence of bacteria in the pulp. The formation of dentin bridge was observed in the experimental and control groups. Inflammation of the pulp was mild to moderate in both groups. Angiogenesis and many odontoblast-like cells, responsible for dentin bridge formation, were observed. Necrosis was not observed in any case, nor were bacteria present in the pulp. Histological analysis indicated a favorable therapeutic effect of Emdogain® Gel in direct pulp capping of Vietnamese pigs. Pulp reaction was similar to that of MTA®.
ERIC Educational Resources Information Center
Baillie, Pat; Gedro, Julie
2009-01-01
As early as 1983, a group of lesbian, gay, bisexual, and transgenders (LGBTs) in the San Francisco Bay Area met with the United Way to discuss the needs of the community in the workplace. In 1986, the United Way authorized a board-level task force on LGBT issues, which looked at health and human care concerns. In 1990, Building Bridges was formed…
2013-05-15
many consecutive hours can you walk in your prosthesis before you feel you need to stop and rest? (hr) 6.9 ± 6.15 8.5 ± 7.1 0.34 0.73 NA *Values are...Walter Reed Army Medical Center and National Naval Medical Center, have since been consolidated. Short Form-36, Prosthesis Evaluation Questionnaire...0.005). There were no significant differences between groups with regard to any of the Short Form-36 domains or Prosthesis Evaluation Questionnaire
Army ants dynamically adjust living bridges in response to a cost-benefit trade-off.
Reid, Chris R; Lutz, Matthew J; Powell, Scott; Kao, Albert B; Couzin, Iain D; Garnier, Simon
2015-12-08
The ability of individual animals to create functional structures by joining together is rare and confined to the social insects. Army ants (Eciton) form collective assemblages out of their own bodies to perform a variety of functions that benefit the entire colony. Here we examine ‟bridges" of linked individuals that are constructed to span gaps in the colony's foraging trail. How these living structures adjust themselves to varied and changing conditions remains poorly understood. Our field experiments show that the ants continuously modify their bridges, such that these structures lengthen, widen, and change position in response to traffic levels and environmental geometry. Ants initiate bridges where their path deviates from their incoming direction and move the bridges over time to create shortcuts over large gaps. The final position of the structure depended on the intensity of the traffic and the extent of path deviation and was influenced by a cost-benefit trade-off at the colony level, where the benefit of increased foraging trail efficiency was balanced by the cost of removing workers from the foraging pool to form the structure. To examine this trade-off, we quantified the geometric relationship between costs and benefits revealed by our experiments. We then constructed a model to determine the bridge location that maximized foraging rate, which qualitatively matched the observed movement of bridges. Our results highlight how animal self-assemblages can be dynamically modified in response to a group-level cost-benefit trade-off, without any individual unit's having information on global benefits or costs.
BRIDG: a domain information model for translational and clinical protocol-driven research.
Becnel, Lauren B; Hastak, Smita; Ver Hoef, Wendy; Milius, Robert P; Slack, MaryAnn; Wold, Diane; Glickman, Michael L; Brodsky, Boris; Jaffe, Charles; Kush, Rebecca; Helton, Edward
2017-09-01
It is critical to integrate and analyze data from biological, translational, and clinical studies with data from health systems; however, electronic artifacts are stored in thousands of disparate systems that are often unable to readily exchange data. To facilitate meaningful data exchange, a model that presents a common understanding of biomedical research concepts and their relationships with health care semantics is required. The Biomedical Research Integrated Domain Group (BRIDG) domain information model fulfills this need. Software systems created from BRIDG have shared meaning "baked in," enabling interoperability among disparate systems. For nearly 10 years, the Clinical Data Standards Interchange Consortium, the National Cancer Institute, the US Food and Drug Administration, and Health Level 7 International have been key stakeholders in developing BRIDG. BRIDG is an open-source Unified Modeling Language-class model developed through use cases and harmonization with other models. With its 4+ releases, BRIDG includes clinical and now translational research concepts in its Common, Protocol Representation, Study Conduct, Adverse Events, Regulatory, Statistical Analysis, Experiment, Biospecimen, and Molecular Biology subdomains. The model is a Clinical Data Standards Interchange Consortium, Health Level 7 International, and International Standards Organization standard that has been utilized in national and international standards-based software development projects. It will continue to mature and evolve in the areas of clinical imaging, pathology, ontology, and vocabulary support. BRIDG 4.1.1 and prior releases are freely available at https://bridgmodel.nci.nih.gov . © The Author 2017. Published by Oxford University Press on behalf of the American Medical Informatics Association. All rights reserved. For Permissions, please email: journals.permissions@oup.com
Ostrander, Roger V; McKinney, Bart I
2012-10-01
Studies suggest that arthroscopic repair techniques may have high recurrence rates for larger rotator cuff tears. A more anatomic repair may improve the success rate when performing arthroscopic rotator cuff repair. We hypothesized that a triple-row modification of the suture-bridge technique for rotator cuff repair would result in significantly more footprint contact area and pressure between the rotator cuff and the humeral tuberosity. Eighteen ovine infraspinatus tendons were repaired using 1 of 3 simulated arthroscopic techniques: a double-row repair, the suture-bridge technique, and a triple-row repair. The triple-row repair technique is a modification of the suture-bridge technique that uses an additional reducing anchor between the medial and lateral rows. Six samples were tested per group. Pressure-indicating film was used to measure the footprint contact area and pressure after each repair. The triple-row repair resulted in significantly more rotator cuff footprint contact area and contact pressure compared with the double-row technique and the standard suture-bridge technique. No statistical difference in contact area or contact pressure was found between the double-row technique and the suture-bridge technique. The triple-row technique for rotator cuff repair results in significantly more footprint contact area and contact pressure compared with the double-row and standard suture-bridge techniques. This more anatomic repair may improve the healing rate when performing arthroscopic rotator cuff repair. Copyright © 2012 Journal of Shoulder and Elbow Surgery Board of Trustees. Published by Mosby, Inc. All rights reserved.
Center Director Bridges visits Disability Awareness and Action working Group Technology Fair
NASA Technical Reports Server (NTRS)
1999-01-01
Center Director Roy Bridges (standing, center) poses with members of the Disability Awareness and Action Working Group (DAAWG), which is holding the 1999 Technology Fair Oct. 20-21 at Kennedy Space Center. The Fair is highlighting vendors demonstrating mobility, hearing, vision and silent disability assistive technology. The purpose is to create an awareness of the types of technology currently available to assist people with various disabilities in the workplace. The theme is that of this year's National Disability Employment Awareness Month, 'Opening Doors to Ability.' Some of the vendors participating are Canine Companions for Independence, Goodwill Industries, Accessible Structures, Division of Blind Services, Space Coast Center for Independent Living, KSC Fitness Center and Delaware North Parks Services.
Single and double C-Cl-activation of methylene chloride by P,N-ligand coordinated rhodium complexes.
Blank, Benoît; Glatz, Germund; Kempe, Rhett
2009-02-02
Two in one: The simultaneous formation of bimetallic mu-methylene bridged Rh(III) complexes as well as dimeric Rh(III) complexes with terminal chloromethyl groups is observed for P,N-ligand stabilized Rh(I) complexes by C-Cl bond activation of methylene chloride. A mechanistic proposal for the formation of both activation products is also discussed. The synthesis of Rh(I) complexes with P-functionalized aminopyridine ligands is reported as well as the first simultaneous observation of a single and double activation of C-Cl bonds of methylene chloride affording both a dimeric Rh(III) complex bearing terminal CH(2)Cl groups in addition to a binuclear Rh(III) complex with a bridging mu-CH(2) group. The structures of the oxidative addition products were obtained by X-ray diffraction studies and NMR experiments were performed to elucidate some aspects of the reaction pathway.
NASA Astrophysics Data System (ADS)
Tong, Kefeng; Song, Xingfu; Sun, Shuying; Xu, Yanxia; Yu, Jianguo
2014-08-01
All-atom molecular dynamics simulations were employed to provide microscopic mechanism for the salt tolerance of polyelectrolytes dispersants. The conformational variation of polyelectrolytes and interactions between COO- groups and counterions/water molecules were also studied via radius of gyration and pair correlations functions. Sodium polyacrylate (NaPA) and sodium salts of poly(acrylic acid)-poly(ethylene oxide) (NaPA-PEO) were selected as the representative linear and comb-like polyelectrolyte, respectively. The results show that Ca2+ ions interact with COO- groups much stronger than Na+ ions and can bring ion-bridging interaction between intermolecular COO- groups in the NaPA systems. While in the NaPA-PEO systems, the introduced PEO side chains can prevent backbone chains from ion-bridging interactions and weaken the conformational changes. The present results can help in selecting and designing new-type efficient polyelectrolyte dispersants with good salt tolerance.
Bridging the bonding gap: the transition from primates to humans.
Dunbar, R I M
2012-07-05
Primate societies are characterized by bonded social relationships of a kind that are rare in other mammal taxa. These bonded relationships, which provide the basis for coalitions, are underpinned by an endorphin mechanism mediated by social grooming. However, bonded relationships of this kind impose constraints on the size of social groups that are possible. When ecological pressures have demanded larger groups, primates have had to evolve new mechanisms to facilitate bonding. This has involved increasing the size of vocal and visual communication repertoires, increasing the time devoted to social interaction and developing a capacity to manage two-tier social relationships (strong and weak ties). I consider the implications of these constraints for the evolution of human social communities and argue that laughter was an early evolutionary innovation that helped bridge the bonding gap between the group sizes characteristic of chimpanzees and australopithecines and those in later hominins.
Poon, G K; Raynaud, F I; Mistry, P; Odell, D E; Kelland, L R; Harrap, K R; Barnard, C F; Murrer, B A
1995-09-29
Bis(acetato)amminedichloro(cyclohexylamine) platinum(IV) (JM216) is a new orally administered platinum complex with antitumor properties, and is currently undergoing phase II clinical trials. When JM216 was incubated with human plasma ultrafiltrate, 93% of the platinum species were protein-bound and 7% were unbound. The unbound platinum complexes in the ultrafiltrates of human plasma were analysed using a liquid chromatography-electrospray ionization-mass spectrometry (LC-ESI-MS) method. Apart from the parent drug, four metabolites were identified and characterised. These include JM118 [amminedichloro(cyclohexylamine) platinum(II)], JM383 [bis(acetato)ammine(cyclohexylamine)dihydroxo platinum(IV)] and the two isomers JM559 and JM518 [bis(acetato)amminechloro(cyclohexylamine) hydroxo platinum(IV)]. Their elemental compositions were determined by accurate mass measurement during the LC analysis, to confirm their identities. Quantitation of these metabolites by off-line LC atomic absorption spectroscopy demonstrated that JM118 is the major metabolite in plasma from patients receiving JM216 treatment.
A Janus cobalt-based catalytic material for electro-splitting of water
NASA Astrophysics Data System (ADS)
Cobo, Saioa; Heidkamp, Jonathan; Jacques, Pierre-André; Fize, Jennifer; Fourmond, Vincent; Guetaz, Laure; Jousselme, Bruno; Ivanova, Valentina; Dau, Holger; Palacin, Serge; Fontecave, Marc; Artero, Vincent
2012-09-01
The future of energy supply depends on innovative breakthroughs regarding the design of cheap, sustainable and efficient systems for the conversion and storage of renewable energy sources. The production of hydrogen through water splitting seems a promising and appealing solution. We found that a robust nanoparticulate electrocatalytic material, H2-CoCat, can be electrochemically prepared from cobalt salts in a phosphate buffer. This material consists of metallic cobalt coated with a cobalt-oxo/hydroxo-phosphate layer in contact with the electrolyte and mediates H2 evolution from neutral aqueous buffer at modest overpotentials. Remarkably, it can be converted on anodic equilibration into the previously described amorphous cobalt oxide film (O2-CoCat or CoPi) catalysing O2 evolution. The switch between the two catalytic forms is fully reversible and corresponds to a local interconversion between two morphologies and compositions at the surface of the electrode. After deposition, the noble-metal-free coating thus functions as a robust, bifunctional and switchable catalyst.
Ferritins: dynamic management of biological iron and oxygen chemistry.
Liu, Xiaofeng; Theil, Elizabeth C
2005-03-01
Ferritins are spherical, cage-like proteins with nanocavities formed by multiple polypeptide subunits (four-helix bundles) that manage iron/oxygen chemistry. Catalytic coupling yields diferric oxo/hydroxo complexes at ferroxidase sites in maxi-ferritin subunits (24 subunits, 480 kDa; plants, animals, microorganisms). Oxidation occurs at the cavity surface of mini-ferritins/Dps proteins (12 subunits, 240 kDa; bacteria). Oxidation products are concentrated as minerals in the nanocavity for iron-protein cofactor synthesis (maxi-ferritins) or DNA protection (mini-ferritins). The protein cage and nanocavity characterize all ferritins, although amino acid sequences diverge, especially in bacteria. Catalytic oxidation/di-iron coupling in the protein cage (maxi-ferritins, 480 kDa; plants, bacteria and animal cell-specific isoforms) or on the cavity surface (mini-ferritins/Dps proteins, 280 kDa; bacteria) initiates mineralization. Gated pores (eight or four), symmetrically arranged, control iron flow. The multiple ferritin functions combine pore, channel, and catalytic functions in compact protein structures required for life and disease response.
Mihata, Teruhisa; Watanabe, Chisato; Fukunishi, Kunimoto; Ohue, Mutsumi; Tsujimura, Tomoyuki; Fujiwara, Kenta; Kinoshita, Mitsuo
2011-10-01
Although previous biomechanical research has demonstrated the superiority of the suture-bridge rotator cuff repair over double-row repair from a mechanical point of view, no articles have described the structural and functional outcomes of this type of procedure. The structural and functional outcomes after arthroscopic rotator cuff repair may be different between the single-row, double-row, and combined double-row and suture-bridge (compression double-row) techniques. Cohort study; Level of evidence, 3. There were 206 shoulders in 201 patients with full-thickness rotator cuff tears that underwent arthroscopic rotator cuff repair. Eleven patients were lost to follow-up. Sixty-five shoulders were repaired using the single-row, 23 shoulders using the double-row, and 107 shoulders using the compression double-row techniques. Clinical outcomes were evaluated at an average of 38.5 months (range, 24-74 months) after rotator cuff repair. Postoperative cuff integrity was determined using Sugaya's classification of magnetic resonance imaging (MRI). The retear rates after arthroscopic rotator cuff repair were 10.8%, 26.1%, and 4.7%, respectively, for the single-row, double-row, and compression double-row techniques. In the subcategory of large and massive rotator cuff tears, the retear rate in the compression double-row group (3 of 40 shoulders, 7.5%) was significantly less than those in the single-row group (5 of 8 shoulders, 62.5%, P < .001) and the double-row group (5 of 12 shoulders, 41.7%, P < .01). Postoperative clinical outcomes in patients with a retear were significantly lower than those in patients without a retear for all 3 techniques. The additional suture bridges decreased the retear rate for large and massive tears. The combination of the double-row and suture-bridge techniques, which had the lowest rate of postoperative retear, is an effective option for arthroscopic repair of the rotator cuff tendons because the postoperative functional outcome in patients with a retear is inferior to that without retear.
Murphy, Terrence E; Gaughan, Monica; Hume, Robert; Moore, S Gordon
2010-03-01
There are many approaches to solving the problem of underrepresentation of some racial and ethnic groups and women in scientific and technical disciplines. Here, the authors evaluate the association of a summer bridge program with the graduation rate of underrepresented minority (URM) students at a selective technical university. They demonstrate that this 5-week program prior to the fall of the 1st year contains elements reported as vital for successful student retention. Using multivariable survival analysis, they show that for URM students entering as fall-semester freshmen, relative to their nonparticipating peers, participation in this accelerated summer bridge program is associated with higher likelihood of graduation. The longitudinal panel data include more than 2,200 URM students.
Murphy, Terrence E.; Gaughan, Monica; Hume, Robert; Moore, S. Gordon
2012-01-01
There are many approaches to solving the problem of underrepresentation of some racial and ethnic groups and women in scientific and technical disciplines. Here, the authors evaluate the association of a summer bridge program with the graduation rate of underrepresented minority (URM) students at a selective technical university. They demonstrate that this 5-week program prior to the fall of the 1st year contains elements reported as vital for successful student retention. Using multivariable survival analysis, they show that for URM students entering as fall-semester freshmen, relative to their nonparticipating peers, participation in this accelerated summer bridge program is associated with higher likelihood of graduation. The longitudinal panel data include more than 2,200 URM students. PMID:23136456
Efficient method for assessing channel instability near bridges
Robinson, Bret A.; Thompson, R.E.
1993-01-01
Efficient methods for data collection and processing are required to complete channel-instability assessments at 5,600 bridge sites in Indiana at an affordable cost and within a reasonable time frame while maintaining the quality of the assessments. To provide this needed efficiency and quality control, a data-collection form was developed that specifies the data to be collected and the order of data collection. This form represents a modification of previous forms that grouped variables according to type rather than by order of collection. Assessments completed during two field seasons showed that greater efficiency was achieved by using a fill-in-the-blank form that organizes the data to be recorded in a specified order: in the vehicle, from the roadway, in the upstream channel, under the bridge, and in the downstream channel.
NASA Astrophysics Data System (ADS)
Jian, Fang-Fang; Xiao, Hai-Lian; Liu, Fa Qian
2006-12-01
Three new M/Hg bimetallic thiocyanato-bridged coordination polymers; [Hg(SCN) 4Ni(Im) 3] ∞1, [Hg(SCN) 4Mn(Im) 2] ∞2, and [Hg(SCN) 4Cu(Me-Im) 2 Hg(SCN) 4Cu(Me-Im) 4] ∞3, (Im=imidazole, Me-Im= N-methyl-imidazole), have been synthesized and characterized by means of elemental analysis, ESR, and single-crystal X-ray. X-ray diffraction analysis reveals that these three complexes all form 3D network structure, and their structures all contain a thiocyanato-bridged Hg⋯M⋯Hg chain ( M=Mn, Ni, Cu) in which the metal and mercury centers exhibit different coordination environments. In complex 1, the [Hg(SCN) 4] 2- anion connects three [Ni(Im) 3] 2+ using three SCN ligands giving rise to a 3D structure, and in complex 2, four SCN ligands bridge [Hg(SCN) 4] 2- and [Mn(Im) 2] 2+ to form a 3D structure. The structure of 3 contains two copper atoms with distinct coordination environment; one is coordinated by four N-methyl-imidazole ligands and two axially elongated SCN groups, and another by four SCN groups (two elongated) and two N-methyl-imidazole ligands. The magnetic property of complex 1 has been investigated. The spin state structure in hetermetallic NiHgNi systems of complex 1 is irregular. The ESR spectra results of complex 3 demonstrate Cu 2+ ion lie on octahedral environment.
de Villiers, Katherine A; Marques, Helder M; Egan, Timothy J
2008-08-01
The crystal structure of the complex formed between the antimalarial drug halofantrine and ferriprotoporphyrin IX (Fe(III)PPIX) has been determined by single crystal X-ray diffraction. The structure shows that halofantrine coordinates to the Fe(III) center through its alcohol functionality in addition to pi-stacking of the phenanthrene ring over the porphyrin. The length of the Fe(III)-O bond is consistent with an alkoxide and not an alcohol coordinating group. The iron porphyrin is five coordinate and monomeric. Changes in the electronic spectrum of Fe(III)PPIX upon addition of halofantrine base in acetonitrile solution are almost identical to those observed upon addition of quinidine free base in the same solvent. This suggests homologous binding. Molecular mechanics modeling of Fe(III)PPIX complexes of quinidine, quinine, 9-epiquinine and 9-epiquinidine based on this homology suggests that the antimalarially active quinidine and quinine can readily adopt conformations that permit formation of an intramolecular salt bridge between the protonated quinuclidine tertiary amino group and unprotonated heme propionate group, while the inactive epimers 9-epiquinidine and 9-epiquinine have to adopt high energy conformations in order to accommodate such salt bridge formation. We propose that salt bridge formation may interrupt formation of the hemozoin precursor dimer formed during the heme detoxification pathway and so account for the strong activity of the two active isomers.
Heimann, Sebastian M; Vehreschild, Maria J G T; Cornely, Oliver A; Franke, Bernd; von Bergwelt-Baildon, Michael; Wisplinghoff, Hilmar; Kron, Florian; Scheid, Christoph; Vehreschild, Jörg J
2015-06-01
Intravenous bridging strategies increase exposure of antifungal prophylaxis in high-risk hematological patients. The cost-effectiveness of such strategies has not been analyzed. A recent study compared the impact of oral posaconazole (POS) and oral posaconazole with intravenous micafungin bridging (POS-MIC) as prophylactic antifungal regimens in patients undergoing allogeneic stem cell transplantation (aSCT). Based on data from the Cologne Cohort of Neutropenic Patients (CoCoNut), a health economic evaluation of direct treatment costs was performed to analyze the economic impact of micafungin bridging. Analysis was undertaken based on current guidelines for the German societal perspective with an annual discount rate of 5%, whereby indirect costs were disregarded due to the severity of the underlying disease. Sensitivity analysis of cost calculation with different discount rates was performed to improve robustness of our health economic evaluation. A retrospective case-control analysis of patients undergoing aSCT between 05/2006 and 07/2011 was performed; 106 patients each in the POS and POS-MIC group were included. In the POS and POS-MIC group, mean costs per patient for the treatment on bone marrow transplant ward were €27,228 (95% CI: €24,932-€29,525) vs. €27,894 (95% CI: €26,414-€29,375; P = 0.629), for diagnostic measures €2124 (95% CI: €1823-€2425) vs. €1269 (95% CI: €1168-€1370; P ≤ 0.001), for laboratory findings €10,612 (95% CI: €9681-€11,544) vs. €8836 (95% CI: €8198-€9475; P = 0.002), and for overall antifungal treatment €6105 (95% CI: €4703-€7508) vs. €6943 (95% CI: €5393-€8493; P = 0.428), resulting in mean overall costs per patient of €60,304 (95% CI: €53,969-€66,639) vs. €58,089 (95% CI: €51,736-64,442; P = 0.625). Our health economic evaluation shows micafungin bridging in aSCT patients did not result in excess cost. Higher acquisition costs of antifungal prophylaxis were balanced by a reduced incidence of possible IFD and lower costs for empirical, preemptive, and targeted antifungal therapy as well as lower costs for diagnostic measures and laboratory tests in the micafungin bridging group. © 2014 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.
Advocacy Groups Deliver Guidelines for Schools Facing Sexual-Orientation Issues
ERIC Educational Resources Information Center
Curriculum Review, 2006
2006-01-01
Groups that often find themselves on opposing sides of the cultural war over gay rights have bridged their divide to draft consensus guidelines designed to help public schools address sexual-orientation issues with sensitivity and respect. Representatives from the Christian Educators Association International and the Gay, Lesbian and Straight…
A Personal Development File: Self-Development among Business Studies Students.
ERIC Educational Resources Information Center
Estienne, Marion
1991-01-01
The Personal Development File involved undergraduate business students in exploring the present, envisioning the future, and bridging the gap within the framework of a support group. However, many students opposed the behavioral and attitudinal objectives involved, and negative group interaction caused some students to withdraw from the project.…
CAMPARE and Cal-Bridge: Two Institutional Networks Increasing Diversity in Astronomy
NASA Astrophysics Data System (ADS)
Rudolph, Alexander L.; Impey, Chris David; Phillips, Cynthia B.; Povich, Matthew S.; Prather, Edward E.; Smecker-Hane, Tammy A.
2015-01-01
We describe two programs, CAMPARE and Cal-Bridge, with the common mission of increasing participation of groups traditionally underrepresented in astronomy, particularly underrepresented minorities and women, through summer research opportunities, in the case of CAMPARE, scholarships in the case of Cal-Bridge, and significant mentoring in both programs, leading to an increase in their numbers successfully pursuing a PhD in the field.CAMPARE is an innovative REU-like summer research program, currently in its sixth year, comprising a network of comprehensive universities and community colleges in Southern California and Arizona (most of which are minority serving institutions), and ten major research institutions (University of Arizona Steward Observatory, the SETI Institute, JPL, Caltech, and the five Southern California UC campuses, UCLA, UCI, UCSD, UCR, and UCSB).In its first five summers, CAMPARE sent a total of 49 students from 10 different CSU and community college campuses to 5 research sites of the program. Of these 49 participants, 25 are women and 24 are men; 22 are Hispanic, 4 are African American, and 1 is Native American, including 6 female Hispanic and 2 female African-American participants. Twenty-one (21) CAMPARE participants have graduated from college, and more than half (11) have attended or are attending a graduate program, including 8 enrolled in PhD or Master's-to-PhD programs. Over twenty CAMPARE students have presented at the AAS and other national meetings.The Cal-Bridge program is a diverse network of higher education institutions in Southern California, including 5 UC campuses, 8 CSU campuses, and 7 community colleges dedicated to the goal of increasing the number of underrepresented minority and female students attending graduate school in astronomy or related fields. We have recently selected our inaugural group of five 2014 Cal-Bridge Scholars, including four women (two Hispanic and one part Native American), and one Hispanic man.Once selected, the Cal-Bridge Scholars benefit from three years of financial support, intensive, joint mentoring by CSU and UC faculty, professional development workshops, and exposure to research opportunities at the participating UC campuses.
CAMPARE and Cal-Bridge: Two Institutional Networks Increasing Diversity in Astronomy
NASA Astrophysics Data System (ADS)
Rudolph, Alexander L.; Impey, Chris David; Phillips, Cynthia B.; Povich, Matthew S.; Prather, Edward E.; Smecker-Hane, Tammy A.
2015-01-01
We describe two programs, CAMPARE and Cal-Bridge, with the common mission of increasing participation of groups traditionally underrepresented in astronomy, particularly underrepresented minorities and women, through summer research opportunities, in the case of CAMPARE, scholarships in the case of Cal-Bridge, and significant mentoring in both programs, leading to an increase in their numbers successfully pursuing a PhD in the field.CAMPARE is an innovative REU-like summer research program, currently in its sixth year, comprising a network of comprehensive universities and community colleges in Southern California and Arizona (most of which are minority serving institutions), and ten major research institutions (University of Arizona Steward Observatory, the SETI Institute, JPL, Caltech, and the five Southern California UC campuses, UCLA, UCI, UCSD, UCR, and UCSB).In its first five summers, CAMPARE sent a total of 49 students from 10 different CSU and community college campuses to 5 research sites of the program. Of these 49 participants, 25 are women and 24 are men; 22 are Hispanic, 4 are African American, and 1 is Native American, including 6 female Hispanic and 2 female African-American participants. Twenty-one (21) CAMPARE participants have graduated from college, and more than half (11) have attended or are attending a graduate program, including 8 enrolled in PhD or Master's-to-PhD programs. Over twenty CAMPARE students have presented at the AAS and other national meetings.The Cal-Bridge program is a diverse network of higher education institutions in Southern California, including 5 UC campuses, 8 CSU campuses, and 7 community colleges dedicated to the goal of increasing the number of underrepresented minority and female students attending graduate school in astronomy or related fields. We have recently selected our inaugural group of five 2014 Cal-Bridge Scholars, including four women (two Hispanic and one part Native American), and one Hispanic man.Once selected, Cal-Bridge Scholars benefit from financial support, intensive, joint mentoring by CSU and UC faculty, professional development workshops, and exposure to research opportunities at the participating UC campuses.
Quantum Calculations on Salt Bridges with Water: Potentials, Structure, and Properties
DOE Office of Scientific and Technical Information (OSTI.GOV)
Liao, Sing; Green, Michael E.
2011-01-01
Salt bridges are electrostatic links between acidic and basic amino acids in a protein; quantum calculations are used here to determine the energetics and other properties of one form of these species, in the presence of water molecules. The acidic groups are carboxylic acids (aspartic and glutamic acids); proteins have two bases with pK above physiological pH: one, arginine, with a guanidinium basic group, the other lysine, which is a primary amine. Only arginine is modeled here, by ethyl guanidinium, while propionic acid is used as a model for either carboxylic acid. The salt bridges are accompanied by 0-12 watermore » molecules; for each of the 13 systems, the energy-bond distance relation, natural bond orbitals (NBO), frequency calculations allowing thermodynamic corrections to room temperature, and dielectric constant dependence, were all calculated. The water molecules were found to arrange themselves in hydrogen bonded rings anchored to the oxygens of the salt bridge components. This was not surprising in itself, but it was found that the rings lead to a periodicity in the energy, and to a 'water addition' rule. The latter shows that the initial rings, with four oxygen atoms, become five member rings when an additional water molecule becomes available, with the additional water filling in at the bond with the lowest Wiberg index, as calculated using NBO. The dielectric constant dependence is the expected hyperbola, and the fit of the energy to the inverse dielectric constant is determined. There is an energy periodicity related to ring formation upon addition of water molecules. When 10 water molecules have been added, all spaces near the salt bridge are filled, completing the first hydration shell, and a second shell starts to form. The potentials associated with salt bridges depend on their hydration, and potentials assigned without regard to local hydration are likely to cause errors as large as or larger than kBT, thus suggesting a serious problem if these potentials are used in Molecular Dynamics simulations.« less
Kersten, Paula; McPherson, Kathryn M; Kayes, Nicola M; Theadom, Alice; McCambridge, Alana
2015-01-01
To test the feasibility and acceptability of an implementation intention strategy (if-then plans) increasingly used in health psychology to bridge the goal intention-action gap in rehabilitation with people with neurological conditions who are experiencing difficulties with mobility. Twenty people with multiple sclerosis (MS) and stroke, randomised to an experimental and control group, set up to three mobility related goals with a physiotherapist. The experimental group also formulated if-then plans for every goal. Focus groups and interviews with participants and therapists; Patient Activation Measure (PAM), 10-m walk test, Rivermead Mobility Index, self-efficacy, subjective health status, quality of life. Qualitative data highlighted one main theme: Rehabilitation in context, encapsulating the usefulness of the if-then strategy in thinking about the patient in the context of complexity, the usefulness of home-based rehabilitation, and the perceived need for a few more sessions. Changes in walking speed were in the expected direction for both groups; PAM scores improved over 3 months in both groups. If-then plans were feasible and acceptable in bridging the goal intention-action gap in rehabilitation with people with MS and stroke, who are experiencing difficulties with mobility. This approach can now be adapted and trialled further in a definitive study. Goal planning in rehabilitation necessitates specific strategies that help people engage in goal-related tasks. If-then plans aim to support people to deal more effectively with self-regulatory problems that might undermine goal striving and have been found to be effective in health promotion and health behaviour change. This feasibility study with people with a stroke and multiple sclerosis has demonstrated that if-then plans are feasible and acceptable to patients and physiotherapists in supporting goal-directed behaviour.
Lee, Tai-Sung; López, Carlos Silva; Martick, Monika; Scott, William G.; York, Darrin M.
2008-01-01
Results of a series of 12 ns molecular dynamics (MD) simulations of the reactant state (with and without a Mg2+ ion), early and late transition state mimics are presented based on a recently reported crystal structure of a full-length hammerhead RNA. The simulation results support a catalytically active conformation with a Mg2+ ion bridging the A9 and scissile phosphates. In the reactant state, the Mg2+ spends significant time closely associated with the 2′OH of G8, but remains fairly distant from the leaving group O5′ position. In the early TS mimic simulation, where the nucleophilic O2′ and leaving group O5′ are equidistant from the phosphorus, the Mg2+ ion remains tightly coordinated to the 2′OH of G8, but is positioned closer to the O5′ leaving group, stabilizing the accumulating charge. In the late TS mimic simulation, the coordination around the bridging Mg2+ ion undergoes a transition whereby the coordination with the 2′OH of G8 is replace by the leaving group O5′ that has developed significant charge. At the same time, the 2′OH of G8 forms a hydrogen bond with the leaving group O5′ and is positioned to act as a general acid catalyst. This work represents the first reported simulations of the full-length hammerhead structure and TS mimics, and provides direct evidence for the possible role of a bridging Mg2+ ion in catalysis that is consistent with both crystallographic and biochemical data. PMID:19079784
Use of the film The Bridge to augment the suicide curriculum in undergraduate medical education.
Retamero, Carolina; Walsh, Leorah; Otero-Perez, Guillermo
2014-10-01
The purpose of this study was to evaluate the use and reception of the movie The Bridge as complementary to the suicide curriculum of medical students. One hundred eighty second-year medical students watched The Bridge as a part of the neuroscience curriculum in understanding suicide. They completed a pre- and post-movie survey regarding the understanding of suicide risk, reasons for suicide, prevention of suicide, and impact of suicide on surviving families. The percentage of answers in categories agree, strongly agree, disagree, and strongly disagree were calculated. The significance of results was calculated using paired t tests. Students were also asked to comment on the movie. The comments were grouped according to themes, and the percentages of comments on each theme were calculated. Students consistently reported they found watching the movie The Bridge to be valuable. Students were very receptive to the idea of using a movie to augment instruction on suicide and agreed that it reinforced concepts used in lecture. They also believed that The Bridge should be shown to people in the medical field, and more than 80 % of students had detailed comments to make about one or more people in the story or about the story in general. The Bridge represents a useful method for instructing students and residents on suicide and has utility in medical education. It can and should be used alongside lectures for assisting in education about suicide.
Wang, Jin-Liang; Liu, Kai-Kai; Liu, Sha; Liu, Feng; Wu, Hong-Bin; Cao, Yong; Russell, Thomas P
2017-06-14
A pair of linear tetrafluorinated small molecular donors, named as ThIDTTh4F and ThIDTSe4F, which are with tetrathienyl-substituted IDT as electron-rich central core, electron-deficient difluorobenzothiadiazole as acceptor units, and donor end-capping groups, but having differences in the π-bridge (thiophene and selenophene), were successfully synthesized and evaluated as donor materials in organic solar cells. Such π-bridge and core units in these small molecules play a decisive role in the formation of the nanoscale separation of the blend films, which were systematically investigated through absorption spectra, grazing incidence X-ray diffraction pattern, transmission electron microscopy images, resonant soft X-ray scattering profiles, and charge mobility measurement. The ThIDTSe4F (with selenophene π-bridge)-based device exhibited superior performance than devices based on ThIDTh4F (with thiophene π-bridge) after post annealing treatment owing to optimized film morphology and improved charge transport. Power conversion efficiency of 7.31% and fill factor of ∼0.70 were obtained by using a blend of ThIDTSe4F and PC 71 BM with thermal annealing and solvent vapor annealing treatments, which is the highest PCE from aromatic side-chain substituted IDT-based small molecular solar cells. The scope of this study is to reveal the structure-property relationship of the aromatic side-chain substituted IDT-based donor materials as a function of π-bridge and the post annealing conditions.
ERIC Educational Resources Information Center
Williams, Conor P.
2015-01-01
On December 11, 2014, "New America" convened a group of leading experts on dual language learners (DLLs) to launch its new Dual Language Learners National Work Group. The group aimed to address three questions: (1) What are the key best practices for dual language learner instruction, policy, and research?; (2) What are the areas of…
Shah, Nirav S; Iveniuk, James; Muth, Stephen Q; Michaels, Stuart; Jose, Jo-Anne; Laumann, Edward O; Schneider, John A
2014-02-01
Younger Black men who have sex with men (BMSM) ages 16-29 have the highest rates of HIV in the United States. Despite increased attention to social and sexual networks as a framework for biomedical intervention, the role of measured network positions, such as bridging and their relationship to HIV risk has received limited attention. A network sample (N = 620) of BMSM respondents (N = 154) and their MSM and transgendered person network members (N = 466) was generated through respondent driven sampling of BMSM and elicitation of their personal networks. Bridging status of each network member was determined by a constraint measure and was used to assess the relationship between this bridging and unprotected anal intercourse (UAI), sex-drug use (SDU), group sex (GS) and HIV status within the network in South Chicago. Low, moderate and high bridging was observed in 411 (66.8 %), 81 (13.2 %) and 123 (20.0 %) of the network. In addition to age and having sex with men only, moderate and high levels of bridging were associated with HIV status (aOR 3.19; 95 % CI 1.58-6.45 and aOR 3.83; 95 % CI 1.23-11.95, respectively). Risk behaviors observed including UAS, GS, and SDU were not associated with HIV status, however, they clustered together in their associations with one another. Bridging network position but not risk behavior was associated with HIV status in this network sample of younger BMSM. Socio-structural features such as position within the network may be important when implementing effective HIV prevention interventions in younger BMSM populations.
Stensby, J Derek; Kaliney, Ryan W; Alford, Bennett; Shen, Francis H; Patrie, James T; Fox, Michael G
2016-03-01
The purpose of this study is to determine whether recombinant human morphogenetic protein-2 (rhBMP-2) alters the findings on routine radiographs performed after transforaminal lumbar interbody fusion (TLIF). A retrospective review of 256 TLIF procedures in 200 patients was performed over a 4-year period. The rhBMP-2 group included 204 TLIFs in 160 patients, and the control group included 52 TLIFs in 40 patients. Two musculoskeletal radiologists reviewed the postoperative radiographs for endplate resorption, resorption resolution, new bone formation, bridging bone, and allograft migration. Statistical analysis was performed using logistic regression. The median age was 53 years in the rhBMP-2 group and 54 years in the control group (p = 0.182). The groups were similar with regard to sex (p = 0.517), single or multilevel TLIF (p = 0.921), specific TLIF levels (p = 0.53), and median radiographic follow-up (373 vs 366 days; p = 0.34). Findings that were more common in the rhBMP-2 group than in the control group included endplate resorption (38% [78/204] vs 12% [6/52]; odds ratio [OR], 4.67; 95% CI, 1.99-12.54; p < 0.001), resorption resolution (59% [46/78] vs 0% [0/6]; OR, 8.09; 95% CI, 1.41 to ∞; p = 0.022), new bone formation (84% [171/204] vs 67% [35/52]; OR, 2.51; 95% CI, 1.24-4.99; p = 0.011), bridging bone (55% [112/204] vs 31% [16/52]; OR, 2.73; 95% CI, 1.43-5.34; p = 0.002), and allograft migration (17% [35/204] vs 2% [1/52]; OR, 6.30; 95% CI, 0.91-151.41; p = 0.065). A statistically significant higher frequency of endplate resorption, new bone formation, and bone bridging is present in TLIF augmented by rhBMP-2 compared with TLIF performed without rhBMP-2. Endplate resorption resolves without treatment in most cases after rhBMP-2 use.
Tornow, Sabine; Tong, Ning-Hua; Bulla, Ralf
2006-07-05
We present a detailed model study of exciton transfer processes in donor-bridge-acceptor (DBA) systems. Using a model which includes the intermolecular Coulomb interaction and the coupling to a dissipative environment we calculate the phase diagram, the absorption spectrum as well as dynamic equilibrium properties with the numerical renormalization group. This method is non-perturbative and therefore allows one to cover the full parameter space, especially the case when the intermolecular Coulomb interaction is of the same order as the coupling to the environment and perturbation theory cannot be applied. For DBA systems with up to six sites we found a transition to the localized phase (self-trapping) depending on the coupling to the dissipative environment. We discuss various criteria which favour delocalized exciton transfer.
NASA Astrophysics Data System (ADS)
Kekelis, Linda S.; Ancheta, Rebecca Wepsic; Heber, Etta; Countryman, Jeri
In this article, we explore an understudied dimension of girls' single-sex education - how social relationships and racial diversity impact the educational environment for girls, and how teachers may best address these concerns. Findings are presented from a 3-year qualitative study of girls' experiences in a single-sex technology program. Girls valued the all-girls aspect of the programs, and friendships formed the foundation of their social experiences. Girls' friendship groups influenced their experiences and eventually their success in the after school technology programs. When friendship groups were observed to be racially homogeneous, they created challenges for including and supporting a racially diverse student membership. Our responses to the challenges that cultural differences and tensions present are outlined, along with recommendations for helping girls bridge these differences.
Pichon, Céline; Mialane, Pierre; Dolbecq, Anne; Marrot, Jérôme; Rivière, Eric; Bassil, Bassem S; Kortz, Ulrich; Keita, Bineta; Nadjo, Louis; Sécheresse, Francis
2008-12-01
Three high-nuclearity NiII-substituted polyoxometalate compounds functionalized by exogenous ligands have been synthesized and characterized. The octanuclear complexes in Na15[Na{(A-R-SiW9O34)Ni4(CH3COO)3(OH)3}2] . 4NaCl . 36H2O (1) and Na15[Na{(A-R-SiW9O34)Ni4(CH3COO)3(OH)2(N3)}2] . 32H2O (2) can be described as two {Ni4} subunits connected via a {Na(CH3COO)6} group, with the acetato ligands also ensuring in each subunit the connection between the paramagnetic centers. In 2, two azido groups replace two of the six mu-hydroxo ligands present in 1. The nonanuclear complex K7Na7[(A-R-SiW9O34)2Ni9(OH)6(H2O)6(CO3)3] . 42H2O (3) exhibits a double cubanestructure with two [(A-R-SiW9O34)Ni4(OH)3]5- subunits linked by three carbonato ligands. A ninth NiII center connected to one subunit via a carbonato ligand and a O=W group completes this asymmetric polyoxometalate.Electronic spectroscopy and electrochemical studies indicate that, while compounds 1-3 decompose in a pure aqueous medium, these complexes are very stable in a pH 6 acetate medium. The cyclic voltammetry pattern of each complex is constituted by a first eight-electron reduction wave followed by a second large-current intensity wave. The characteristics of the first waves of the complexes are clearly distinct from those obtained for their lacunary precursor [A-R-SiW9O34]10-, a feature that is due to the Ni centers in the complexes. Such observations of electroactive, stable, and highly nickel-rich polyoxometalates are not common. Measurements of the magnetic susceptibility revealed the occurrence of concomitant ferromagnetic and antiferromagnetic interactions in 1 and 3.For both of these compounds, the extension of the magnetic exchange has been determined by means of a spin Hamiltonian with three and four J constants, respectively.
Nadyrov, Eldar; Rozhko, Alexander; Kravtsov, Viacheslav; Mabuchi, Kiyohiko; Hatch, Maureen; Nakamura, Nori; Nikonovich, Sergey; Aleksanin, Sergey
2012-05-01
The Belarus-American (BelAm) thyroid study cohort consists of persons who were 0-18 years of age at the time of exposure to radioactive iodine fallout from the 1986 Chernobyl nuclear power plant accident and who have undergone serial thyroid screenings with referral for fine-needle aspiration biopsy (FNAB) using standardized criteria. We investigated thyrocyte nuclear abnormalities in cytological samples from FNABs in 75 BelAm subjects with single and multiple thyroid nodules and 47 nodular goiter patients from Leningrad, Russia, unexposed to Chernobyl fallout. Nuclear abnormalities examined included internuclear chromosome bridges and derivative nuclei with broken bridges (i.e., "tailed" nuclei), which are formed from dicentric and ring chromosomes and thus may be cellular markers of radiation exposure. Among subjects with single-nodular goiter, thyrocytes with bridges were present in 86.8% of the exposed BelAm cohort compared with 27.0% of unexposed controls. The average frequency of thyrocytes with bridges and with tailed nuclei was also significantly higher in the BelAm subjects than in controls. Among subjects with multinodular goiters, thyrocytes with bridges were present in 75.7% of exposed BelAm patients compared with 16.7% of unexposed controls; thyrocytes with tailed nuclei were observed in all of the BelAm subjects but in only 40% of controls, and the mean frequencies of bridges and tailed nuclei were significantly higher in the exposed group. Unusually, long bridges were detected in 29% of BelAm patients with single-nodular goiters and 35% of those with multinodular goiters, while no such abnormalities were observed among patients from the Leningrad region. In the exposed subjects from BelAm, we also found positive correlations between their estimated dose of Iodine-131 from Chernobyl fallout and the frequency of tailed nuclei (p = 0.008) and bridges (p = 0.09). Further study is needed to confirm that these phenomena represent consequences of radiation exposure in the human organism.
Diethyl 4,4'-(3,6-dioxaoctane-1,8-diyl-dioxy)dibenzoate.
Ma, Zhen; Qin, Haisha; Lai, Gang; Fan, Jingjie
2012-03-01
The title compound, C(24)H(30)O(8), was obtained by reaction of ethyl 4-hy-droxy-benzoate with 1,2-dichloro-ethane. The mol-ecule occupies a crystallographic inversion center, with its central ethyl-ene bridge in an anti conformation. The other ethyl-ene bridge has a gauche conformation, with the corresponding O-C-C-O torsion angle being 74.2 (1)°. The benzene rings are almost coplanar with the adjacent eth-oxy-carbonyl groups, with an r.m.s. deviation of 0.078 Å.
Park, Ji Soon; McGarry, Michelle H; Campbell, Sean T; Seo, Hyuk Jun; Lee, Yeon Soo; Kim, Sae Hoon; Lee, Thay Q; Oh, Joo Han
2015-09-01
Transosseous-equivalent (TOE) rotator cuff repair can increase contact area and contact pressure between the repaired cuff tendon and bony footprint and can show higher ultimate loads to failure and smaller gap formation compared with other repair techniques. However, it has been suggested that medial rotator cuff failure after TOE repair may result from increased bridging suture tension. To determine optimum bridging suture tension in TOE repair by evaluating footprint contact and construct failure characteristics at different tensions. Controlled laboratory study. A total of 18 fresh-frozen cadaveric shoulders, randomly divided into 3 groups, were constructed with a TOE configuration using the same medial suture anchor and placing a Tekscan sensing pad between the repaired rotator cuff tendon and footprint. Nine of the 18 shoulders were used to measure footprint contact characteristics. With use of the Tekscan measurement system, the contact pressure and area between the rotator cuff tendon and greater tuberosity were quantified for bridging suture tensions of 60, 90, and 120 N with glenohumeral abduction angles of 0° and 30° and humeral rotation angles of 30° (internal), 0°, and 30° (external). TOE constructs of all 18 shoulders then underwent construct failure testing (cyclic loading and load to failure) to determine the yield load, ultimate load, stiffness, hysteresis, strain, and failure mode at 60 and 120 N of tension. As bridging suture tension increased, contact force, contact pressure, and peak pressure increased significantly at all positions (P < .05 for all). Regarding contact area, no significant differences were found between 90 and 120 N at all positions, although there were significant differences between 60 and 90 N. The construct failure test demonstrated no significant differences in any parameters according to various tensions (P > .05 for all). Increasing bridging suture tension to over 90 N did not improve contact area but did increase contact force and pressure. Bridging suture tension did not significantly affect ultimate failure loads. Considering the risks of overtensioning bridging sutures, it may be clinically more beneficial to keep bridging suture tension below 90 N. © 2015 The Author(s).
Banded electromagnetic stator core
Fanning, Alan W.; Gonzales, Aaron A.; Patel, Mahadeo R.; Olich, Eugene E.
1994-01-01
A stator core for an electromagnetic pump includes a plurality of circumferentially adjoining groups of flat laminations disposed about a common centerline axis and collectively defining a central bore and a discontinuous outer perimeter, with adjacent groups diverging radially outwardly to form V-shaped gaps. An annular band surrounds the groups and is predeterminedly tensioned to clamp together the laminations, and has a predetermined flexibility in a radial direction to form substantially straight bridge sections between the adjacent groups.
Banded electromagnetic stator core
Fanning, Alan W.; Gonzales, Aaron A.; Patel, Mahadeo R.; Olich, Eugene E.
1996-01-01
A stator core for an electromagnetic pump includes a plurality of circumferentially adjoining groups of flat laminations disposed about a common centerline axis and collectively defining a central bore and a discontinuous outer perimeter, with adjacent groups diverging radially outwardly to form V-shaped gaps. An annular band surrounds the groups and is predeterminedly tensioned to clamp together the laminations, and has a predetermined flexibility in a radial direction to form substantially straight bridge sections between the adjacent groups.
Bridging Gender Gap in the Physics Classroom: The Instructional Method Perspective
ERIC Educational Resources Information Center
Obafemi, Deborah T. A.
2015-01-01
The study investigated the influence of students' gender on their understanding, application and analysis of Light waves concept in physics in Ikwerre Local Government Area of Rivers State, Nigeria. A quasi-experimental pretest-posttest design comprising of three experimental and one control group was used, each group was taught with a different…
Appreciating Diversity: A Tool for Building Bridges.
ERIC Educational Resources Information Center
American Association of Retired Persons, Washington, DC.
By the year 2000, one in three persons in the United States will belong to a minority group. This booklet aims to help adult educators promote awareness, understanding, acceptance, and appreciation of the cultural diversity of the five major cultural groups in the United States: American Indians/Alaska Natives, Asians and Pacific Americans,…
Creating a Bridge between Industry and Higher Education through an Operations Consultancy Module
ERIC Educational Resources Information Center
Bak, Ozlem
2011-01-01
This paper explores the challenges and use of a postgraduate consultancy module in teaching operations management. The consultancy module extends the traditional learning boundaries between students and lecturers to a tripartite grouping of students, university and industry. The interaction within this group may be influenced by students' skills…
DOT National Transportation Integrated Search
2016-04-01
The objectives of this research study are to develop a three-dimensional FE : model for simulating the behavior of a battered pile group foundation subjected : to lateral loading, and to verify the model using results from a unique static : lateral l...
Group, Team, or Something in Between? Conceptualising and Measuring Team Entitativity
ERIC Educational Resources Information Center
Vangrieken, Katrien; Boon, Anne; Dochy, Filip; Kyndt, Eva
2017-01-01
The current gap between traditional team research and research focusing on non-strict teams or groups such as teacher teams hampers boundary-crossing investigations of and theorising on teamwork and collaboration. The main aim of this study includes bridging this gap by proposing a continuum-based team concept, describing the distinction between…
Information and Communication Technology (ICT) in the Service of Multiculturalism
ERIC Educational Resources Information Center
Hoter, Elaine; Shonfeld, Miri; Ganayim, Asmaa
2009-01-01
This paper presents an online inter-group contact hypothesis (OICH) model, developed within the Israel education system, whereby online and distance learning (ODL) is used in the service of multiculturalism. The goal is to build bridges among secular and religious Arabs and Jews in Israel based on small multicultural groups and collaborative…
Bridging the Gap: Counselling Strategies in a Cross-Cultural Context.
ERIC Educational Resources Information Center
Wierzba, Joan D.
Cultural awareness enlarges the world view of traditional counseling methodologies that teach that the dominant society's values are the healthy norms to use in assessing and assisting ethnic groups. A dominant society counselor or therapist can be more effective in helping members of other groups by utilizing self-awareness and developing a…
Sorption mechanism of enrofloxacin on humic acids extracted from Brazilian soils.
Martínez-Mejía, Mónica J; Sato, Isabela; Rath, Susanne
2017-07-01
Veterinary antimicrobials are emerging environmental contaminants of concern. In this study, the sorption of enrofloxacin (ENR) onto humic acids (HAs) extracted from three Brazilian soils was evaluated. HAs were characterized by elemental analysis and solid 13 C nuclear magnetic resonance spectroscopy. The sorption of ENR onto HAs was at least 20-fold higher than onto the soils from which they were separated. Ionic and cation bridging are the primary interactions involved. The interactions driven by cation exchange are predominant on HAs, which appear to have abundant carboxylic groups and a relatively high proportion of H-bond donor moieties with carbohydrate-like structures. Interactions explained by cation bridging and/or surface complexation on HAs are facilitated by moieties containing conjugated ligands, significant content of oxygen-containing functional groups, such as phenolic-OH or lignin-like structures. HAs containing electron-donating phenolic moieties and carboxylic acid ligand groups exhibit a sorption mechanism that is primarily driven by strong metal binding, favoring the formation of ternary complexes between functional groups of the organic matter and drugs.
Van Weehaeghe, Manú; De Bruyn, Hugo; Vandeweghe, Stefan
2017-12-01
An angulation of the implant connection could overcome the problems related to angulated abutments. This study compares conventional implants with angulated abutment to tilted implants with an angulated connection. Twenty patients were treated in the edentulous mandible. In the posterior jaw locations, one conventional tilted implant with angulated abutment and one angulated implant without abutment were placed. In the anterior jaw, two conventional implants were placed, one with and one without abutment. Implants were immediately loaded and 3 months later, the final bridge (PFM or monolithic zirconia) was placed. After a follow-up of 48 months, 17 patients were available for clinical examination. The mean overall marginal bone loss (MBL) was 1.26 mm. No significant differences in implant survival, MBL, periodontal indices, patients' satisfaction, or complications was found between implants restored on abutment or implant level, between the posteriorly located angulated implant nor angulated abutment, and between both anterior implants with or without abutment. The posterior implants demonstrated less MBL compared to the anterior implants (P < .001). There was no significant difference in MBL between the implants restored with zirconia or PFM bridges (P = .294). Overall mean pocket depth was 2.83 mm. More plaque was found in the PFM group compared to the full-zirconia group, at the bridge (P = .042) and the implants (P = .029). There was no difference between both materials in pocket depth (P = .635) or bleeding (P = .821). One zirconia bridge fractured, two angulated abutment were replaced and four loose bridge screws connected to the angulated abutments had to be tightened. Patients were overall satisfied (4.74/5). An implant with angulated connection may results in a stronger connection but does not affect the marginal bone loss. No difference in MBL was seen between implants restored on abutment or implant level. Zirconia seems to reduce the amount of plaque. © 2017 Wiley Periodicals, Inc.
Kolaitis, Nicholas A; Soong, Allison; Shrestha, Pavan; Zhuo, Hanjing; Neuhaus, John; Katz, Patti P; Greenland, John R; Golden, Jeffrey; Leard, Lorriana E; Shah, Rupal J; Hays, Steven R; Kukreja, Jasleen; Kleinhenz, Mary Ellen; Blanc, Paul D; Singer, Jonathan P
2018-02-22
Extracorporeal membrane oxygenation (ECMO) is increasingly used as a bridge to lung transplantation. The impact of preoperative ECMO on health-related quality of life (HRQL) and depressive symptoms after lung transplantation remains unknown, however. In a single-center prospective cohort study, we assessed HRQL and depressive symptoms before and at 3, 6, and 12 months after lung transplantation using the Short Form 12 Physical and Mental Component Scores (SF12-PCS and SF12-MCS), Airway Questionnaire 20-Revised (AQ20R), EuroQol 5D (EQ5D), and Geriatric Depression Scale (GDS). Changes in HRQL were quantified by segmented linear mixed-effects models controlling for age, sex, diagnosis, preoperative forced expiratory volume in 1 second, 6-minute walk distance, and Lung Allocation Score. We compared changes in HRQL among subjects bridged with ECMO, subjects hospitalized but not on ECMO, and subjects called in for transplantation as outpatients. Out of 189 subjects, 17 were bridged to transplantation with ECMO. In all groups, improvements in HRQL following lung transplantation exceeded the minimally clinically important difference using the SF12-PCS, AQ20R, EQ5D, and GDS. HRQL defined by SF12-MCS did not change after transplantation. Improvements were generally similar among the groups, except for EQ5D, which showed a trend toward less benefit in the outpatients, possibly due to their better HRQL before lung transplantation. Subjects ill enough to require ECMO as a bridge to lung transplantation appear to achieve similar improvements in HRQL and depressive symptoms as those who do not. It is reassuring to both providers and patients that lung transplantation provides substantial improvements in HRQL, even for those patients who are critically ill in the run up to transplantation. Copyright © 2018 The American Association for Thoracic Surgery. All rights reserved.
Lu, Xiaoying; Tobacman, Larry S; Kawai, Masataka
2006-12-01
The effect of temperature on isometric tension and cross-bridge kinetics was studied with a tropomyosin (Tm) internal deletion mutant AS-Delta23Tm (Ala-Ser-Tm Delta(47-123)) in bovine cardiac muscle fibers by using the thin filament extraction and reconstitution technique. The results are compared with those from actin reconstituted alone, cardiac muscle-derived control acetyl-Tm, and recombinant control AS-Tm. In all four reconstituted muscle groups, isometric tension and stiffness increased linearly with temperature in the range 5-40 degrees C for fibers activated in the presence of saturating ATP and Ca(2+). The slopes of the temperature-tension plots of the two controls were very similar, whereas the slope derived from fibers with actin alone had approximately 40% the control value, and the slope from mutant Tm had approximately 36% the control value. Sinusoidal analysis was performed to study the temperature dependence of cross-bridge kinetics. All three exponential processes A, B, and C were identified in the high temperature range (30-40 degrees C); only processes B and C were identified in the mid-temperature range (15-25 degrees C), and only process C was identified in the low temperature range (5-10 degrees C). At a given temperature, similar apparent rate constants (2pia, 2pib, 2pic) were observed in all four muscle groups, whereas their magnitudes were markedly less in the order of AS-Delta23Tm < Actin < AS-Tm approximately Acetyl-Tm groups. Our observations are consistent with the hypothesis that Tm enhances hydrophobic and stereospecific interactions (positive allosteric effect) between actin and myosin, but Delta23Tm decreases these interactions (negative allosteric effect). Our observations further indicate that tension/cross-bridge is increased by Tm, but is diminished by Delta23Tm. We conclude that Tm affects the conformation of actin so as to increase the area of hydrophobic interaction between actin and myosin molecules.
Barber, F Alan
2016-05-01
To compare the structural healing and clinical outcomes of triple-loaded single-row with suture-bridging double-row repairs of full-thickness rotator cuff tendons when both repair constructs are augmented with platelet-rich plasma fibrin membrane. A prospective, randomized, consecutive series of patients diagnosed with full-thickness rotator cuff tears no greater than 3 cm in anteroposterior length were treated with a triple-loaded single-row (20) or suture-bridging double-row (20) repair augmented with platelet-rich plasma fibrin membrane. The primary outcome measure was cuff integrity by magnetic resonance imaging (MRI) at 12 months postoperatively. Secondary clinical outcome measures were American Shoulder and Elbow Surgeons, Rowe, Simple Shoulder Test, Constant, and Single Assessment Numeric Evaluation scores. The mean MRI interval was 12.6 months (range, 12-17 months). A total of 3 of 20 single-row repairs and 3 of 20 double-row repairs (15%) had tears at follow-up MRI. The single-row group had re-tears in 1 single tendon repair and 2 double tendon repairs. All 3 tears failed at the original attachment site (Cho type 1). In the double-row group, re-tears were found in 3 double tendon repairs. All 3 tears failed medial to the medial row near the musculotendinous junction (Cho type 2). All clinical outcome measures were significantly improved from the preoperative level (P < .0001), but there was no statistical difference between groups postoperatively. There is no MRI difference in rotator cuff tendon re-tear rate at 12 months postsurgery between a triple-loaded single-row repair or a suture-bridging double-row repair when both are augmented with platelet-rich plasma fibrin membrane. No difference could be demonstrated between these repairs on clinical outcome scores. I, Prospective randomized study. Copyright © 2016 Arthroscopy Association of North America. All rights reserved.
Exploration Science Opportunities for Students within Higher Education
NASA Astrophysics Data System (ADS)
Bailey, Brad; Minafra, Joseph; Schmidt, Gregory
2016-10-01
The NASA Solar System Exploration Research Virtual Institute (SSERVI) is a virtual institute focused on exploration science related to near-term human exploration targets, training the next generation of lunar scientists, and education and public outreach. As part of the SSERVI mission, we act as a hub for opportunities that engage the public through education and outreach efforts in addition to forming new interdisciplinary, scientific collaborations.SSERVI provides opportunities for students to bridge the scientific and generational gap currently existing in the planetary exploration field. This bridge is essential to the continued international success of scientific, as well as human and robotic, exploration.The decline in funding opportunities after the termination of the Apollo missions to the Moon in the early 1970's produced a large gap in both the scientific knowledge and experience of the original lunar Apollo researchers and the resurgent group of young lunar/NEA researchers that have emerged within the last 15 years. One of SSERVI's many goals is to bridge this gap through the many networking and scientific connections made between young researchers and established planetary principle investigators. To this end, SSERVI has supported the establishment of NextGen Lunar Scientists and Engineers group (NGLSE), a group of students and early-career professionals designed to build experience and provide networking opportunities to its members. SSERVI has also created the LunarGradCon, a scientific conference dedicated solely to graduate and undergraduate students working in the lunar field. Additionally, SSERVI produces monthly seminars and bi-yearly virtual workshops that introduce students to the wide variety of exploration science being performed in today's research labs. SSERVI also brokers opportunities for domestic and international student exchange between collaborating laboratories as well as internships at our member institutions. SSERVI provides a bridge that is essential to the continued international success of scientific, as well as human and robotic, exploration.
Ceresoli, Marco; Fugazzola, Paola; Ansaloni, Luca
2017-01-01
Introduction Emergency resection represents the traditional treatment for left-sided malignant obstruction. However, the placement of self-expanding metallic stents and delayed surgery has been proposed as an alternative approach. The aim of the current meta-analysis was to review the available evidence, with particular interest for the short-term outcomes, including a recent multicentre RCT. Methods We considered randomized controlled trials comparing stenting as a bridge to surgery and emergency surgery for the management of left-sided malignant large bowel obstruction, performing a systematic review in MEDLINE, PubMed database, and the Cochrane libraries. Results We initially identified a total of 2543 studies. After the elimination of duplicates and the screening of titles and abstracts, seven studies, for a total of 448 patients, were considered. The current meta-analysis revealed no difference in the mortality rate between the stent group and the emergency surgery group; the postoperative complication rate (37.84% versus 54.87%, P = 0.02), the stoma rate (28.8% versus 46.02%, P < 0.0001), and the incidence of wound infection (8.11% versus 15.49%, P = 0.01) were reduced after stent as a bridge to surgery. Conclusion Colonic stenting as a bridge to surgery appears to be a safe approach to malignant large bowel obstruction. Possible advantages of this treatment can be identified in a reduced incidence of postoperative complications and a lower stoma rate. Further RCTs considering long-term outcomes and cost-effectiveness analysis are needed. PMID:28761765
Triadic awareness predicts partner choice in male-infant-male interactions in Barbary macaques.
Kubenova, Barbora; Konecna, Martina; Majolo, Bonaventura; Smilauer, Petr; Ostner, Julia; Schülke, Oliver
2017-03-01
Social knowledge beyond one's direct relationships is a key in successfully manoeuvring the social world. Individuals gather information on the quality of social relationships between their group companions, which has been termed triadic awareness. Evidence of the use of triadic awareness in natural contexts is limited mainly to conflict management. Here we investigated triadic awareness in wild Barbary macaques (Macaca sylvanus) in the context of bridging interactions defined as male-infant-male interactions whereby a male (initiator, holder) presents an infant to another male (receiver, non-holder) in order to initiate an affiliative interaction with that male. Analyses based on 1263 h of focal observations on ten infants of one wild social group in Morocco supported the hypothesis that males use their knowledge of the relationship between infants and other adult males when choosing a male as a partner for bridging interactions. Specifically, (i) the number of bridging interactions among holder-infant-receiver triads was positively affected by the strength of the infant-receiver relationship and (ii) when two males were available as bridging partners, a male was more likely to be chosen as the receiver the stronger his social relationship with the infant relative to the other available male. This demonstrates that non-human primates establish triadic awareness of temporary infant-male relationships and use it in a naturally occurring affiliative context. Our results contribute to the discussion about the mechanism underlying the acquisition of triadic awareness and the benefits of its usage, and lend support to hypotheses linking social complexity to the evolution of complex cognition.
Nucleoplasmic bridges as a biomarker of DNA damage exposed to radon.
Meenakshi, C; Sivasubramanian, K; Venkatraman, B
2017-02-01
Radon is a naturally occurring radionuclide in the environment, during decay it emits high linear energy transfer (LET) alpha particles. When radon exposure is accompanied by smoking it has been reported that lung cancer risk is higher. Blood samples were collected after prior consent, 25 smokers and 25 non smokers (only males) exposed in vitro to radon gas with doses ranging between 0.3-12.6mGy Ionizing radiation is a strong clastogenic agent and a potent inducer of MN. Cytokinesis-Blocked Micro Nucleus (CBMN) assay has proven to be a reliable, thoroughly validated and standardised technique in the field of radiation biology. In view of this, an invitro study has been undertaken using CBMN assay to suggest Nucleoplasmic bridges (NPBs) as a potential bio-dosimeter and to investigate the existence of a possible influence of smoking on genetic damage induced by ionizing radiation. The mean percentages frequencies of micronuclei, nucleoplasmic bridges and nuclear buds among the exposed smoker group were 4.82±0.271, 0.6±0.04 and 0.12±0.02 respectively and these values for exposed non-smoker group were 2.78±0.285, 0.4±0.04 and 0.06±0.01 respectively. Spearman rank correlation for the frequency of nucleoplasmic bridge with respect to dose was considered to be significant (P<0.05) in non-smokers. This study is first of its kind to investigate NPB as a biomarker of early DNA damage induced by radon. Copyright © 2017 Elsevier B.V. All rights reserved.
NASA Astrophysics Data System (ADS)
Yamanaka, Shoji; Yasuda, Akira; Miyata, Hajime
2010-01-01
Titanium trifluoride TiF 3 has the distorted ReO 3 structure composed of corner sharing TiF 6 octahedra linked with Ti-F-Ti bridges. Potassium fluoride KF was inserted into the bridges using high-pressure and high-temperature conditions (5 GPa, 1000-1200 °C). When the molar ratio KF/TiF 3≥1, a few low dimensional compounds were obtained forming non-bridged F ions. At the composition KF/TiF 3=1/2, a new compound KTi 2F 7 was formed, which crystallizes with the space group Cmmm and the lattice parameters of a=6.371(3), b=10.448(6), c=3.958(2) Å, consisting of edge-sharing pentagonal bipyramids [TiF 7] forming ribbons running along the a axis. The ribbons are linked by corners to construct a three-dimensional framework without forming non-bridged F ions. The compound is antiferromagnetic with the Néel temperature T N=75 K, and the optical band gap was 6.4 eV. A new fluoride K 2TiF 5 (KF/TiF 3=2) with the space group Pbcn and the lattice parameters of a=7.4626(2), b=12.9544(4) and c=20.6906(7) Å was also obtained by the high pressure and high temperature treatment (5 GPa at 1000 °C) of a molar mixture of 2 KF+TiF 3. The compound contains one-dimensional chains of corner-sharing TiF 6 octahedra.
A SOLAR FLARE DISTURBING A LIGHT WALL ABOVE A SUNSPOT LIGHT BRIDGE
DOE Office of Scientific and Technical Information (OSTI.GOV)
Hou, Yijun; Zhang, Jun; Li, Ting
With the high-resolution data from the Interface Region Imaging Spectrograph , we detect a light wall above a sunspot light bridge in the NOAA active region (AR) 12403. In the 1330 Å slit-jaw images, the light wall is brighter than the ambient areas while the wall top and base are much brighter than the wall body, and it keeps oscillating above the light bridge. A C8.0 flare caused by a filament activation occurred in this AR with the peak at 02:52 UT on 2015 August 28, and the flare’s one ribbon overlapped the light bridge, which was the observational basemore » of the light wall. Consequently, the oscillation of the light wall was evidently disturbed. The mean projective oscillation amplitude of the light wall increased from 0.5 to 1.6 Mm before the flare and decreased to 0.6 Mm after the flare. We suggest that the light wall shares a group of magnetic field lines with the flare loops, which undergo a magnetic reconnection process, and they constitute a coupled system. When the magnetic field lines are pushed upward at the pre-flare stage, the light wall turns to the vertical direction, resulting in the increase of the light wall’s projective oscillation amplitude. After the magnetic reconnection takes place, a group of new field lines with smaller scales are formed underneath the reconnection site, and the light wall inclines. Thus, the projective amplitude notably decrease at the post-flare stage.« less
Technology Transfer: A Contact Sport
NASA Technical Reports Server (NTRS)
Paynter, Nina P.
1995-01-01
Technology transfer is a dynamic process, involving dynamic people as the bridge between NASA Langley Research Center and the outside world. This bridge, for nonaerospace applications, is known as the Technology Applications Group. The introduction of new innovations and expertise where they are needed occurs through a 'push' and 'pull' process. A 'push' occurs when a new technology is first developed with high commercial potential and then a company is found to licence or further develop the technology. The 'pull' process occurs through problem statements. A company or group will submit a written statement of what they need and the shortcomings of commercially available technology. The Technology Transfer Team (T3) reviews these problem statements and decides where NASA LaRC can offer assistance. A researcher or group of researchers are then identified who can help solve the problem and they are put in contact with the company. Depending upon the situation in either method, a Space Act Agreement (SAA), or outline of the responsibilities for each party, is developed.
Roche, Abigail; Goto, Keiko; Zhao, Yanling; Wolff, Cindy
2015-01-01
To examine perceived social and cultural capitals associated with family eating practices among Hmong, Latino, and white mothers and fathers. Six focus groups composed of 52 Hmong, Latino, and white mothers and fathers of young children were conducted to examine parental perceptions of social and cultural capitals associated with eating practices. Whereas Hmong participants unanimously emphasized the healthfulness of their traditional food, Latino groups had divergent views on their traditional foods' healthfulness. Hmong parents highly valued their traditional foods whereas white and Latino mothers were more accepting of new foods from other cultures. Participants noted divergent views on gender roles in family eating practices and food culture preservation efforts. Identifying and promoting bonding and bridging of cultural assets for healthy dietary practices among different cultural groups may be important for developing successful nutrition education programs across ethnicities in the community. Copyright © 2015 Society for Nutrition Education and Behavior. Published by Elsevier Inc. All rights reserved.
Savelkoul, Michael; Hewstone, Miles; Scheepers, Peer; Stolle, Dietlind
2015-07-01
We test whether a larger percentage of non-Whites in neighborhoods decreases associational involvement and build on earlier research in three ways. First, we explicitly consider the ethnic composition of organizations, distinguishing involvement in bridging (with out-group members) and bonding (only in-group members) organizations. Second, we start from constrict theory and test competing sets of predictions derived from conflict and contact theories to explain these relationships. Third, we examine whether relative out-group size affects involvement in different types of voluntary organizations equally. Using data from the 2005 U.S. 'Citizenship, Involvement, Democracy' survey, the percentage of non-Whites in neighborhoods is largely unrelated with associational involvement or perceived ethnic threat. However, perceiving ethnic threat is consistently negatively related with involvement in bridging organizations. Simultaneously, a larger percentage of non-Whites fosters intergroup contact, which is negatively related with perceptions of ethnic threat and involvement in bonding leisure organizations. Our results shed more light on the relationship between the relative out-group size in neighborhoods and associational involvement as well as underlying explanations for this link. Copyright © 2015 Elsevier Inc. All rights reserved.
The Abundances of the Fe Group Elements in Early B Stars in the Magellanic Clouds and Bridge
NASA Astrophysics Data System (ADS)
Peters, Geraldine J.; Adelman, Saul J.
2016-01-01
The abundances of three Fe Group elements (V, Cr, and Fe) in 9 early main-sequence band B stars in the LMC, 7 in the SMC , and two in the Magellanic Bridge have been determined from archival FUSE observations and the Hubeny/Lanz NLTE programs TLUSTY/SYNSPEC. Lines from the Fe group elements, except for a few weak multiplets of Fe III, are not observable in the optical spectral region. The best set of lines in the FUSE spectral region are Fe III (UV1), V III 1150 Å, and Cr III 1137 Å. The abundances of these elements in early B stars are a marker for recent SNe Ia activity, as a single exploding white dwarf can deliver 0.5 solar masses of Ni-56 that decays into Fe to the ISM. The Fe group abundances in an older population of stars primarily reflect SNe II activity, in which a single explosion delivers only 0.07 solar masses of Ni-56 to the ISM (the rest remains trapped in the neutron star). The abundances of the Fe group elements in early B stars not only track SNe Ia activity but are also important for computing evolutionary tracks for massive stars. In general, the Fe abundance relative to the sun's value is comparable to the mean abundances for the lighter elements in the Clouds/Bridge but the values of [V,Cr/Fe]sun are smaller. This presentation will discuss the spatial distribution of the Fe Group elements in the Magellanic Clouds, and compare it with our galaxy in which the abundance of Fe declines with radial distance from the center. Support from NASA grants NAG5-13212, NNX10AD66G, STScI HST-GO-13346.22, and USC's Women in Science and Engineering (WiSE) program is greatly appreciated.
Army ants dynamically adjust living bridges in response to a cost–benefit trade-off
Reid, Chris R.; Lutz, Matthew J.; Powell, Scott; Kao, Albert B.; Couzin, Iain D.; Garnier, Simon
2015-01-01
The ability of individual animals to create functional structures by joining together is rare and confined to the social insects. Army ants (Eciton) form collective assemblages out of their own bodies to perform a variety of functions that benefit the entire colony. Here we examine ‟bridges” of linked individuals that are constructed to span gaps in the colony’s foraging trail. How these living structures adjust themselves to varied and changing conditions remains poorly understood. Our field experiments show that the ants continuously modify their bridges, such that these structures lengthen, widen, and change position in response to traffic levels and environmental geometry. Ants initiate bridges where their path deviates from their incoming direction and move the bridges over time to create shortcuts over large gaps. The final position of the structure depended on the intensity of the traffic and the extent of path deviation and was influenced by a cost–benefit trade-off at the colony level, where the benefit of increased foraging trail efficiency was balanced by the cost of removing workers from the foraging pool to form the structure. To examine this trade-off, we quantified the geometric relationship between costs and benefits revealed by our experiments. We then constructed a model to determine the bridge location that maximized foraging rate, which qualitatively matched the observed movement of bridges. Our results highlight how animal self-assemblages can be dynamically modified in response to a group-level cost–benefit trade-off, without any individual unit’s having information on global benefits or costs. PMID:26598673
Synthesis and spectral and redox properties of three triply bridged complexes of ruthenium
Llobet, A.; Curry, M.E.; Evans, H.T.; Meyer, T.J.
1989-01-01
Syntheses are described for the ligand-bridged complexes [(tpm)RuIII(??-O)(??-L)2RuIII(tpm) n+ (L = O2P(O)(OH), n = 0 (1); L = O2CO, n = 0 (2); L = O2CCH3, n = 2 (3); tpm is the tridentate, facial ligand tris(1-pyrazolyl)methane. The X-ray crystal structure of [(tpm)Ru(??-O)(??-O2P(O)(OH))2Ru(tpm)]??8H 2O was determined from three-dimensional X-ray counter data. The complex crystallizes in the trigonal space group P3221 with three molecules in a cell of dimensions a = 18.759 (4) A?? and c = 9.970 (6) A??. The structure was refined to a weighted R factor of 0.042 based on 1480 independent reflections with I ??? 3??(I). The structure reveals that the complex consists of two six-coordinate ruthenium atoms that are joined by a ??-oxo bridge (rRU-O = 1.87 A??; ???RuORu = 124.6??) and two ??-hydrogen phosphato bridges (average rRu-O = 2.07 A??) which are capped by two tpm ligands. The results of cyclic voltammetric and coulometric experiments show that the complexes undergo both oxidative and reductive processes in solution. Upon reduction, the ligand-bridged structure is lost and the monomer [(tpm)Ru(H2O)3]2+ appears quantitatively. All three complexes are diamagnetic in solution. The diamagnetism is a consequence of strong electronic coupling between the low-spin d5 Ru(III) metal ions through the oxo bridge and the relatively small Ru-O-Ru angle. ?? 1989 American Chemical Society.
Voltage gradient mapping and electrophysiologically guided cryoablation in children with AVNRT.
Drago, Fabrizio; Battipaglia, Irma; Russo, Mario Salvatore; Remoli, Romolo; Pazzano, Vincenzo; Grifoni, Gino; Allegretti, Greta; Silvetti, Massimo Stefano
2018-04-01
Recently, voltage gradient mapping of Koch's triangle to find low-voltage connections, or 'voltage bridges', corresponding to the anatomic position of the slow pathway, has been introduced as a method to ablate atrioventricular nodal reentry tachycardia (AVNRT) in children. Thus, we aimed to assess the effectiveness of voltage mapping of Koch's triangle, combined with the search for the slow potential signal in 'low-voltage bridges', to guide cryoablation of AVNRT in children. From June 2015 to May 2016, 35 consecutive paediatric patients (mean age 12.1 ± 4.5 years) underwent 3D-guided cryoablation of AVNRT at our Institution. Fifteen children were enrolled as control group (mean age 14 ± 4 years). A voltage gradient mapping of Koch's triangle was obtained in all patients, showing low-voltage connections in all children with AVNRT but not in controls. Prior to performing cryoablation, we looked for the typical 'hump and spike' electrogram, generally considered to be representative of slow pathway potential within a low-voltage bridge. In all patients the 'hump and spike' electrogram was found inside bridges of low voltage. Focal or high-density linear lesions, extended or not, were delivered guided by low-voltage bridge visualization. Acute success rate was 100%, and no recurrence was reported at a mean follow-up of 8 ± 3 months. Voltage gradient mapping of Koch's triangle, combined with the search for the slow potential signal in low-voltage bridges, is effective in guiding cryoablation of AVNRT in paediatric patients, with a complete acute success rate and no AVNRT recurrences at mid-term follow-up.
Pasán, Jorge; Sanchiz, Joaquín; Ruiz-Pérez, Catalina; Lloret, Francesc; Julve, Miguel
2005-10-31
Two new phenylmalonate-bridged copper(II) complexes with the formulas [Cu(4,4'-bpy)(Phmal)](n).2nH(2)O (1) and [Cu(2,4'-bpy)(Phmal)(H(2)O)](n)() (2) (Phmal = phenylmalonate dianion, 4,4'-bpy = 4,4'-bipyridine, 2,4'-bpy = 2,4'-bipyridine) have been synthesized and characterized by X-ray diffraction. Complex 1 crystallizes in monoclinic space group P2(1), Z = 4, with unit cell parameters of a = 9.0837(6) Angstroms, b = 9.3514(4) Angstroms, c = 11.0831(8) Angstroms, and beta = 107.807(6) degrees , whereas complex 2 crystallizes in orthorhombic space group C2cb, Z = 8, with unit cell parameters of a = 10.1579(7) Angstroms, b = 10.3640(8) Angstroms, and c = 33.313(4) Angstroms. The structures of 1 and 2 consist of layers of copper(II) ions with bridging bis-monodentate phenylmalonate (1 and 2) and 4,4'-bpy (1) ligands and terminal monodentate 2,4'-bpy (2) groups. Each layer in 1 contains rectangles with dimensions of 11.08 x 4.99 Angstroms(2), the edges being defined by the Phmal and 4,4'-bpy ligands. The intralayer copper-copper separations in 1 through the anti-syn equatorial-apical carboxylate-bridge and the 4,4'-bpy molecule are 4.9922(4) and 11.083(1) Angstroms, respectively. The anti-syn equatorial-equatorial carboxylate bridge links the copper(II) atoms in complex 2 within each layer with a mean copper-copper separation of 5.3709(8) Angstroms. The presence of 2,4'-bpy as a terminal ligand accounts for the large interlayer separation of 15.22 Angstroms. The copper(II) environment presents a static pseudo-Jahn-Teller disorder which has been studied by EPR and low-temperature X-ray diffraction. Magnetic susceptibility measurements of both compounds in the temperature range 2-290 K show the occurrence of weak antiferromagnetic [J = -0.59(1) cm(-1) (1)] and ferromagnetic [J = +0.77(1) cm(-1) (2)] interactions between the copper(II) ions. The conformation of the phenylmalonate-carboxylate bridge and other structural factors, such as the planarity of the exchange pathway in 1, account for the different nature of the magnetic interaction.
Cultural psychology as a bridge between anthropology and cognitive science.
Fryberg, Stephanie A
2012-07-01
The theory and methods of cultural psychology begin with the assumption that psychological processes are socioculturally and historically grounded. As such, they offer a new approach for understanding the diversity of human functioning because they (a) question the presumed neutrality of the majority group perspective; (b) take the target's point-of-view (i.e., what it means to be a person in a particular context); (c) assume that there is more than one viable way of being a competent or effective person; and (d) provide a road map for understanding and reducing social inequities. As illustrated in this essay, a cultural psychological approach provides a bridge between anthropology and the cognitive sciences, and in so doing it offers an alternative set of explanations and interventions for group differences. Copyright © 2012 Cognitive Science Society, Inc.
A Bridge to Coordination Isomer Selection in Lanthanide(III) DOTA-tetraamide Complexes
Vipond, Jeff; Woods, Mark; Zhao, Piyu; Tircso, Gyula; Ren, Jimin; Bott, Simon G.; Ogrin, Doug; Kiefer, Garry E.; Kovacs, Zoltan; Sherry, A.Dean
2008-01-01
Interest in macrocyclic lanthanide complexes such as DOTA is driven largely through interest in their use as contrast agents for MRI. The lanthanide tetraamide derivatives of DOTA have shown considerable promise as PARACEST agents, taking advantage of the slow water exchange kinetics of this class of complex. We postulated that water exchange in these tetraamide complexes could be slowed even further by introducing a group to sterically encumber the space above the water coordination site, thereby hindering the departure and approach of water molecules to the complex. The ligand 8O2-bridged-DOTAM was synthesized in a 34% yield from cyclen. It was found that the lanthanide complexes of this ligand did not possess a water molecule in the inner coordination sphere of the bound lanthanide. The crystal structure of the ytterbium complex revealed that distortions to the coordination sphere were induced by the steric constraints imposed on the complex by the bridging unit. The extent of the distortion was found to increase with increasing ionic radius of the lanthanide ion, eventually resulting in a complete loss of symmetry in the complex. Because this ligand system is bicyclic, the conformation of each ring in the system is constrained by that of the other, in consequence inclusion of the bridging unit in the complexes means only a twisted square antiprismatic coordination geometry is observed for complexes of 8O2-bridged-DOTAM. PMID:17295475
Yang, Yan; Liu, Yuxiu; Song, Hongjian; Li, Yongqiang; Wang, Qingmin
2016-11-01
Numerous compounds containing urea bridge and biurea moieties are used in a variety of fields, especially as drugs and pesticides. To search for novel, environmentally benign and ecologically safe pesticides with unique modes of action, four series of novel triazone analogues containing urea, thiourea, biurea, and thiobiurea bridge, respectively, were designed and synthesized, according to various calcium ion channel inhibitors which act on transient receptor potential protein. Their structures were characterized by [Formula: see text] NMR, [Formula: see text] NMR, and HRMS. The insecticidal activities of the new compounds were obtained. The bioassay results indicated that compounds containing a thiourea bridge and a thiobiurea bridge exhibited excellent insecticidal activities against bean aphid. Specifically, compounds [Formula: see text], [Formula: see text], and [Formula: see text] exhibited 85, 90, and 95 % activities, respectively, at 10 mg/kg. Compounds [Formula: see text] (30 %), [Formula: see text] (35 %), [Formula: see text] (30 %), and [Formula: see text] (40 %) exhibited the approximate aphicidal activity of pymetrozine (30 %) at 5 mg/kg. In addition, some target compounds exhibited insecticidal activities against lepidopteran pests. From a molecular design standpoint, the information obtained in this study could help in the further design of new derivatives with improved insecticidal activities.
Scorpion venom peptides with no disulfide bridges: a review.
Almaaytah, Ammar; Albalas, Qosay
2014-01-01
Scorpion venoms are rich sources of biologically active peptides that are classified into disulfide-bridged peptides (DBPs) and non-disulfide-bridged peptides (NDBPs). DBPs are the main scorpion venom components responsible for the neurotoxic effects observed during scorpion envenomation as they usually target membrane bound ion channels of excitable and non-excitable cells. Several hundred DBPs have been identified and functionally characterized in the past two decades. The NDBPs represent a novel group of molecules that have gained great interest only recently due to their high diversity both in their primary structures and bioactivities. This review provides an overview of scorpion NDBPs focusing on their therapeutic applications, modes of discovery, mechanisms of NDBPs genetic diversity and structural properties. It also provides a simple classification for NDBPs that could be adopted and applied to other NDBPs identified in future studies. Copyright © 2013 Elsevier Inc. All rights reserved.
Langmuir-Blodgett deposition selects carboxylate headgroup coordination
NASA Astrophysics Data System (ADS)
Mukherjee, Smita; Datta, Alokmay
2011-10-01
Infrared reflection-absorption spectroscopy results on stearic acid Langmuir monolayers containing Mn, Co, and Cd ions show that on the water surface, the ions induce unidentate and bidentate (both chelate and bridged) coordination in the carboxylate headgroup with some trace of undissociated acid. Moreover, with Cd and Mn ions in subphase, the preferred coordination is found to be unidentate, whereas for Co, bidentate chelate is most preferred. After transfer onto amorphous substrate, not all coordinations are found to exist in the same ratio for the deposited metal stearate monolayers. More specifically, after transfer, Mn is found to coordinate with the carboxylate group as bidentate chelate, Cd as unidentate and bidentate bridged (with unidentate as the preferred coordination), and Co as preferably bidentate bridged (although all coordinations are present). Results suggest a specific interaction in each case, as the metal-carboxylate pair at the water surface is transferred to the substrate surface during Langmuir-Blodgett deposition.
Gerhardt, Christian; Hug, Konstantin; Pauly, Stephan; Marnitz, Tim; Scheibel, Markus
2012-12-01
Arthroscopic double-row fixation of supraspinatus tendon tears compared with single-row techniques is still a matter of debate. Arthroscopic double-row rotator cuff repair using the suture bridge technique provides better clinical results and lower retear rates than does single-row repair using a modified Mason-Allen stitch technique. Cohort study; Level of evidence 3. Forty patients underwent either an arthroscopic single-row modified Mason-Allen stitch (SR) (n = 20; mean age ± SD, 61.5 ± 7.4 y) or a modified suture bridge double-row repair (DR) (n = 20; age, 61.2 ± 7.5 y). The anteroposterior extension was classified as Bateman I in 10% and Bateman II in 90% of patients in the SR group and as Bateman II in 80% and Bateman III in 20% of patients in the DR group. Patients were matched for sex and age. The subjective shoulder value (SSV), Constant-Murley score (CS), and Western Ontario Rotator Cuff Index (WORC) were used for clinical follow-up. Furthermore, MRI scans were conducted for analysis of tendon integrity, muscle atrophy, and fatty infiltration via semiquantitative signal intensity analysis. In addition, re-defect patterns were evaluated. The mean follow-up time in the SR group was 16.8 ± 4.6 months. The mean SSV was 91.0% ± 8.8%, mean CS was 82.2 ± 8.1 (contralateral side, 88.8 ± 5.3), and mean WORC score was 96.5% ± 3.2%. The mean follow-up time in the DR group was 23.4 ± 2.9 months, with patients achieving scores of 92.9% ± 9.6% for the SSV, 77.0 ± 8.6 for the CS (contralateral side, 76.7 ± 17.1), and 90.7% ± 12.6% for the WORC (P > .05). No significant differences were detected in the clinical outcome between groups. Tendon integrity was as follows. Type 1, none in either group; type 2, 4 SR and 5 DR; type 3, 9 SR and 10 DR; type 4, 3 SR and 3 DR; and type 5, 3 SR and 2 DR. The failure rate was 31.6% (n = 6) in the SR group and 25% (n = 5) in the DR group (P > .05). No significant differences were obtained for muscular atrophy or fatty degeneration (SR group, 0.94 ± 0.16; DR group, 1.15 ± 0.5) (P > .05). Re-defects revealed lateral cuff failure in 83.3% of SR patients in contrast to patients treated with DR techniques. The re-defect pattern was medial cuff failure in 80% of the patients. The clinical results after modified Mason-Allen single-row versus double-mattress suture bridge technique did not demonstrate significant differences in a matched patient cohort. Concerning the failure mode, single- and double-row techniques seem to demonstrate different re-defect patterns.
Banded electromagnetic stator core
Fanning, A.W.; Gonzales, A.A.; Patel, M.R.; Olich, E.E.
1996-06-11
A stator core for an electromagnetic pump includes a plurality of circumferentially adjoining groups of flat laminations disposed about a common centerline axis and collectively defining a central bore and a discontinuous outer perimeter, with adjacent groups diverging radially outwardly to form V-shaped gaps. An annular band surrounds the groups and is predeterminedly tensioned to clamp together the laminations, and has a predetermined flexibility in a radial direction to form substantially straight bridge sections between the adjacent groups. 5 figs.
Banded electromagnetic stator core
Fanning, A.W.; Gonzales, A.A.; Patel, M.R.; Olich, E.E.
1994-04-05
A stator core for an electromagnetic pump includes a plurality of circumferentially adjoining groups of flat laminations disposed about a common centerline axis and collectively defining a central bore and a discontinuous outer perimeter, with adjacent groups diverging radially outwardly to form V-shaped gaps. An annular band surrounds the groups and is predeterminedly tensioned to clamp together the laminations, and has a predetermined flexibility in a radial direction to form substantially straight bridge sections between the adjacent groups. 5 figures.
Polyimides containing amide and perfluoroisopropylidene connecting groups
NASA Technical Reports Server (NTRS)
Dezern, James F. (Inventor)
1993-01-01
New, thermooxidatively stable polyimides were prepared from the reaction of aromatic dianhydrides containing isopropylidene bridging groups with aromatic diamines containing amide connecting groups between the rings. Several of these polyimides were shown to be semi-crystalline as evidenced by wide angle x ray scattering and differential scanning calorimetry. Most of the polyimides form tough, flexible films with high tensile properties. These polyimide films exhibit enhanced solubility in organic solvents.
Characterization of dental pulp defect and repair in a canine model.
Yildirim, Sibel; Can, Alp; Arican, Mustafa; Embree, Mildred C; Mao, Jeremy J
2011-12-01
To explore a relationship between the size of pulp chamber perforation and reparative dentin formation in a canine model. Pulp defects were created in the pulp chambers of maxillary and mandibular premolars (N = 64) in 17 healthy mongrel dogs in three different sizes (diameter/depth: 1/1, 2/1, and 2/2 mm3) with sterile round burs under general anesthesia. The perforations were immediately capped with hard-setting calcium hydroxide (CH) in the control group or sealed with Teflon membrane (TM) in the experimental group, followed by restoration with reinforced zinc oxide eugenol cement in vivo. Seven and 30 days after pulp chamber perforation and restoration all treated and control premolars were extracted and prepared for histomorphometric and statistical analyses. Reparative dentin formation was more pronounced for defect sizes up to 2/1 mm3 when treated with CH, and completely bridged the surgically created dentin defects only after 30 days. However, reparative dentin upon CH treatment failed to completely bridge pulp chamber exposure for 2/2 defects. By contrast, TM treatment only yielded mild reparative dentin bridging for defects up to 1/1, but not for either 2/1 or 2/2 defects at 30 days. Inflammatory responses of the exposed dental pulp tissue were more robust with the TM group than with the CH group. Thus, dental pulp tissue possesses a capacity for spontaneous repair by the formation of reparative dentin in this preclinical model, but only up to a defect size of -2 mm in diameter and 1 mm in depth. All observations are based on 30 days post-treatment in the canine model. These findings may serve as baseline for regenerative endodontic studies.
Center Director Bridges opens Super Safety and Health Day at KSC.
NASA Technical Reports Server (NTRS)
1999-01-01
Center Director Roy Bridges opens the second Super Safety and Health Day at Kennedy Space Center, an entire day when most normal work activities are suspended to allow personnel to attend safety- and health-related activities. The theme, 'Safety and Health Go Hand in Hand,' emphasized KSC's commitment to place the safety and health of the public, astronauts, employees and space- related resources first and foremost. Events included a keynote address, a panel session about related issues, vendor exhibits, and safety training in work groups. The keynote address and panel session were also broadcast internally over NASA television.
Organizing urban ecosystem services through environmental stewardship governance in New York City
James J. Connolly; Erika S. Svendsen; Dana R. Fisher; Lindsay K. Campbell
2013-01-01
How do stewardship groups contribute to the management of urban ecosystem services? In this paper, we integrate the research on environmental stewardship with the social-ecological systems literature to explain how stewardship groups serve as bridge organizations between public agencies and civic organizations, working across scales and sectors to build the flexible...
ERIC Educational Resources Information Center
Hamm, Jill V.
2001-01-01
Using interviews and focus groups, lower and middle socioeconomic status (SES) African American parents and middle SES white parents discussed their objectives regarding cross-ethnic relations and how they helped their children forge positive cross-ethnic relations. The groups relied on different methods to promote socialization. Parents' efforts…
Managing IceBridge Airborne Mission Data at the National Snow and Ice Data Center
NASA Astrophysics Data System (ADS)
Brodzik, M.; Kaminski, M. L.; Deems, J. S.; Scambos, T. A.
2010-12-01
Operation IceBridge (OIB) is a NASA airborne geophysical survey mission conducting laser altimetry, ice-penetrating radar profiling, gravimetry and other geophysical measurements to monitor and characterize the Earth's cryosphere. The IceBridge mission will operate from 2009 until after the launch of ICESat-II (currently planned for 2015), and provides continuity of measurements between that mission and its predecessor. Data collection sites include the Greenland and Antarctic Ice Sheets and the sea ice pack regions of both poles. These regions include some of the most rapidly changing areas of the cryosphere. IceBridge is also collecting data in East Antarctica via the University of Texas ICECAP program and in Alaska via the University of Alaska, Fairbanks glacier mapping program. The NSIDC Distributed Active Archive Center at the University of Colorado at Boulder provides data archive and distribution support for the IceBridge mission. Our IceBridge work is based on two guiding principles: ensuring preservation of the data, and maximizing usage of the data. This broadens our work beyond the typical scope of a data archive. In addition to the necessary data management, discovery, distribution, and outreach functions, we are also developing tools that will enable broader use of the data, and integrating diverse data types to enable new science research. Researchers require expeditious access to data collected from the IceBridge missions; our archive approach balances that need with our long-term preservation goal. We have adopted a "fast-track" approach to publish data quickly after collection and make it available via FTP download. Subsequently, data sets are archived in the NASA EOSDIS ECS system, which enables data discovery and distribution with the appropriate backup, documentation, and metadata to assure its availability for future research purposes. NSIDC is designing an IceBridge data portal to allow interactive data search, exploration, and subsetting via a map-based interface. This portal will provide flight line rendering and multi-instrument data previewing capabilities to facilitate use of the wide array of data types, resolutions, and configurations in this dynamic airborne mission. Together with the IceBridge Science Team and Ice Bridge Science Working Groups, NSIDC is generating value-added products from the Ice Bridge data streams and other ancillary data. These products will provide simple, useful combinations of Ice Bridge products and regional maps of important geophysical parameters from other sources. Planned value-added products include: (1) gridded products in which new profiles from Ice Bridge (e.g. elevation or ice thickness) are combined with existing DEMs or bed maps to produce revised grids and (2) flight-profile multi-instrument products in which data from several instruments are combined into ice sheet profiles (surface elevation, ice thickness, internal reflection data, bed reflection intensity, and gravimetry), sea ice profiles (freeboard, snow cover, and thickness), and surface data profiles (elevation, slope, roughness, near-surface layering, and imagery).
Li, Yuanzuo; Sun, Chaofan; Song, Peng; Ma, Fengcai; Yang, Yanhui
2017-02-17
A series of dyes, containing thiophene and thieno[3,2-b]thiophene as π-conjugated bridging units and six kinds of groups as electron acceptors, were designed for dye-sensitized solar cells (DSSCs). The ground- and excited-state properties of the designed dyes were investigated by using density functional theory (DFT) and time-dependent DFT, respectively. Moreover, the parameters affecting the short-circuit current density and open-circuit voltage were calculated to predict the photoelectrical performance of each dye. In addition, the charge difference density was presented through a three-dimensional (3D) real-space analysis method to investigate the electron-injection mechanism in the complexes. Our results show that the longer conjugated bridge would inhibit the intramolecular charge transfer, thereby affecting the photoelectrical properties of DSSCs. Similarly, owing to the lowest chemical hardness, largest electron-accepting ability, dipole moment (μnormal ) and the change in the energy of the TiO 2 conduction band (ΔECB ), the dye with a (E)-3-(4-(benzo[c][1,2,5]thiadiazol-4-yl)phenyl)-2-cyanoacrylic acid (TCA) acceptor group would exhibit the most significant photoelectrical properties among the designed dyes. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
Molecular diodes and ultra-thin organic rectifying junctions: Au-S-CnH2n-Q3CNQ and TCNQ derivatives.
Ashwell, Geoffrey J; Moczko, Katarzyna; Sujka, Marta; Chwialkowska, Anna; Hermann High, L R; Sandman, Daniel J
2007-02-28
Attempts to obtain derivatives of the molecular diode, 2-{4-[1-cyano-2-(1-(omega-acetylsulfanylalkyl)-1H-quinolin-4-ylidene)-ethylidene]-cyclohexa-2,5-dienylidene}-malonitrile [1, CH(3)CO-S-C(n)H(2n)-Q3CNQ], from either 2,3,5,6-tetrafluoro-7,7,8,8-tetracyano-p-quinodimethane (TCNQF(4)) or 2,3,5,6-tetramethyl-7,7,8,8-tetracyano-p-quinodimethane (TMTCNQ) result in ring closure via the cyano group of the pi-bridge and yield di-substituted analogues: 2-{2,3,5,6-tetrafluoro-4-[6-(10-acetylsulfanyldecyl)-3-(1-(10-acetylsulfanyldecyl)-1H-quinolin-4-ylidenemethyl)-6H-benzo[f][1,7]naphthyridin-2-ylidene]-cyclohexa-2,5-dienylidene}-malonitrile (2a) and the 2,3,5,6-tetramethyl derivative (2b). Self-assembled monolayers (SAMs) of these donor-(pi-bridge)-acceptor molecular diodes exhibit asymmetric current-voltage characteristics with electron flow at forward bias from the top contact to surface C(CN)(2) groups. Comparison is made with I-V curves from ultra-thin films of an organic rectifying junction in which TCNQ(-) is electron-donating and a donor-(sigma-bridge)-acceptor diode in which TCNQ degrees is electron-accepting.
Identification of nucleotides in E. coli 16S rRNA essential for ribosome subunit association.
Pulk, Arto; Maiväli, Ulo; Remme, Jaanus
2006-05-01
The ribosome consists of two unequal subunits, which associate via numerous intersubunit contacts. Medium-resolution structural studies have led to grouping of the intersubunit contacts into 12 directly visualizable intersubunit bridges. Most of the intersubunit interactions involve RNA. We have used an RNA modification interference approach to determine Escherichia coli 16S rRNA positions that are essential for the association of functionally active 70S ribosomes. Modification of the N1 position of A702, A1418, and A1483 with DMS, and of the N3 position of U793, U1414, and U1495 with CMCT in 30S subunits strongly interferes with 70S ribosome formation. Five of these positions localize into previously recognized intersubunit bridges, namely, B2a (U1495), B2b (U793), B3 (A1483), B5 (A1418), and B7a (A702). The remaining position displaying interference, U1414, forms a base pair with G1486, which is a part of bridge B3. We contend that these five intersubunit bridges are essential for reassociation of the 70S ribosome, thus forming the functional core of the intersubunit contacts.
Identification of nucleotides in E. coli 16S rRNA essential for ribosome subunit association
Pulk, Arto; Maiväli, Ülo; Remme, Jaanus
2006-01-01
The ribosome consists of two unequal subunits, which associate via numerous intersubunit contacts. Medium-resolution structural studies have led to grouping of the intersubunit contacts into 12 directly visualizable intersubunit bridges. Most of the intersubunit interactions involve RNA. We have used an RNA modification interference approach to determine Escherichia coli 16S rRNA positions that are essential for the association of functionally active 70S ribosomes. Modification of the N1 position of A702, A1418, and A1483 with DMS, and of the N3 position of U793, U1414, and U1495 with CMCT in 30S subunits strongly interferes with 70S ribosome formation. Five of these positions localize into previously recognized intersubunit bridges, namely, B2a (U1495), B2b (U793), B3 (A1483), B5 (A1418), and B7a (A702). The remaining position displaying interference, U1414, forms a base pair with G1486, which is a part of bridge B3. We contend that these five intersubunit bridges are essential for reassociation of the 70S ribosome, thus forming the functional core of the intersubunit contacts. PMID:16556933
Gandolla, Marta; Costa, Andrea; Aquilante, Lorenzo; Gfoehler, Margit; Puchinger, Markus; Braghin, Francesco; Pedrocchi, Alessandra
2017-07-01
People with neuromuscular diseases such as muscular dystrophy experience a distributed and evolutive weakness in the whole body. Recent technological developments have changed the daily life of disabled people strongly improving the perceived quality of life, mostly concentrating on powered wheelchairs, so to assure autonomous mobility and respiratory assistance, essential for survival. The key concept of the BRIDGE project is to contrast the everyday experience of losing functions by providing them of a system able to exploit the best their own residual capabilities in arm movements so to keep them functional and autonomous as much as possible. BRIDGE is composed by a light, wearable and powered five degrees of freedom upper limb exoskeleton under the direct control of the user through a joystick or gaze control. An inverse kinematic model allows to determine joints position so to track patient desired hand position. BRIDGE prototype has been successfully tested in simulation environment, and by a small group of healthy volunteers. Preliminary results show a good tracking performance of the implemented control scheme. The interaction procedure was easy to understand, and the interaction with the system was successful.
Escuer, Albert; Vicente, Ramon; Kumar, Sujit B.; Solans, Xavier; Font-Bardía, Mercé; Caneschi, Andrea
1996-05-22
The trinuclear complex (&mgr;(3)-CO(3))[Ni(3)(Medpt)(3)(NCS)(4)] was obtained by reaction of basic solutions of nickel(II), Medpt (bis(3aminopropyl)methylamine) and thiocyanate ligand with atmospheric CO(2) or by simple reaction with carbonate anion. (&mgr;(3)-CO(3))[Ni(3)(Medpt)(3)(NCS)(4)] crystallizes in the triclinic system, space group P&onemacr;, with a = 12.107(5) Å, b = 12.535(7) Å, c = 16.169(9) Å, alpha = 102.69(5) degrees, beta = 92.91(5) degrees, gamma = 118.01(4) degrees, Z = 2, and R = 0.043. The three nickel atoms are asymmetrically bridged by one pentadentate carbonato ligand, which shows a novel coordination mode. The (&mgr;(3)-CO(3))[Ni(3)(Medpt)(3)(NCS)(4)] compound shows a very strong antiferromagnetic coupling. Fit as irregular triangular arrangement gave J(1) = -88.4, J(2) = -57.7, and J(3) = -9.6 cm(-)(1), which is the strongest AF coupling observed to date for Ni(3) compounds. The magnetic behavior of the carbonato bridge is discussed.
A novel bridge scour monitoring and prediction system
NASA Astrophysics Data System (ADS)
Valyrakis, Manousos; Michalis, Panagiotis; Zhang, Hanqing
2015-04-01
Earth's surface is continuously shaped due to the action of geophysical flows. Erosion due to the flow of water in river systems has been identified as a key problem in preserving ecological health but also a threat to our built environment and critical infrastructure, worldwide. As an example, it has been estimated that a major reason for bridge failure is due to scour. Even though the flow past bridge piers has been investigated both experimentally and numerically, and the mechanisms of scouring are relatively understood, there still lacks a tool that can offer fast and reliable predictions. Most of the existing formulas for prediction of bridge pier scour depth are empirical in nature, based on a limited range of data or for piers of specific shape. In this work, the use of a novel methodology is proposed for the prediction of bridge scour. Specifically, the use of an Adaptive Neuro-Fuzzy Inference System (ANFIS) is proposed to estimate the scour depth around bridge piers. In particular, various complexity architectures are sequentially built, in order to identify the optimal for scour depth predictions, using appropriate training and validation subsets obtained from the USGS database (and pre-processed to remove incomplete records). The model has five variables, namely the effective pier width (b), the approach velocity (v), the approach depth (y), the mean grain diameter (D50) and the skew to flow. Simulations are conducted with data groups (bed material type, pier type and shape) and different number of input variables, to produce reduced complexity and easily interpretable models. Analysis and comparison of the results indicate that the developed ANFIS model has high accuracy and outstanding generalization ability for prediction of scour parameters. The effective pier width (as opposed to skew to flow) is amongst the most relevant input parameters for the estimation. Training of the system to new bridge geometries and flow conditions can be achieved by obtaining real time data, via novel electromagnetic sensors monitoring scour depth. Once the model is trained with data representative of the new system, bridge scour prediction can be performed for high/design flows or floods.
Najar, Adel M; Tidmarsh, Ian S; Adams, Harry; Ward, Michael D
2009-12-21
Reaction of two structurally related bridging ligands L(26Py) and L(13Ph), in which two bidentate chelating pyrazolyl-pyridine units are connected to either a 2,6-pyridine-diyl or 1,3-benzene-diyl central group via methylene spacers, with first-row transition metal dications, results in a surprising variety of structures. The commonest is that of an octanuclear coordination cage [M(8)L(12)]X(16) [M = Co(II) or Zn(II); X = perchlorate or tetrafluoroborate] in which a metal ion is located at each of the eight vertices of an approximate cube, and one bis-bidentate bridging ligand spans each edge. The arrangement of fac and mer tris-chelate metal centers around the inversion center results in approximate (non-crystallographic) S(6) symmetry. Another structural type observed in the solid state is a hexanuclear complex [Co(6)(L(13Ph))(9)](ClO(4))(12) in which the six metal ions are in a rectangular array (two rows of three), folded about the central Co-Co vector like a partially open book, with each metal-metal edge containing one bridging ligand apart from the two outermost metal-metal edges which are spanned by a pair of bridging ligands in a double helical array. The final structural type we observed is a tetranuclear square [Ni(4)(L(26Py))(6)](BF(4))(8), with the four Ni-Ni edges spanned alternately by one and two bridging ligand such that it effectively consists of two dinuclear double helicates cross-linked by additional bridging ligands. A balance between the "cube" and "book" forms, which varied from compound to compound, was observed in solution in many cases by (1)H NMR and ES mass spectrometry studies.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Yang, Dong; Momeni, Mohammad R.; Demir, Hakan
The metal–organic framework NU-1000, with Zr 6-oxo, hydroxo, and aqua nodes, was modified by incorporation of hydroxylated Al(iii) ions by ALD-like chemistry with [Al(CH 3) 2(iso-propoxide)] 2followed by steam (ALD = atomic layer deposition). Al ions were installed to the extent of approximately 7 per node. Single-site iridium diethylene complexes were anchored to the nodes of the modified and unmodified MOFs by reaction with Ir(C 2H 4) 2(acac) (acac = acetylacetonate) and converted to Ir(CO) 2complexes by treatment with CO. Infrared spectra of these supported complexes show that incorporation of Al weakened the electron donor tendency of the MOF. Correspondingly,more » the catalytic activity of the initial supported iridium complexes for ethylene hydrogenation increased, as did the selectivity for ethylene dimerization. The results of density functional theory calculations with a simplified model of the nodes incorporating Al(iii) ions are in qualitative agreement with some catalyst performance data.« less
NASA Astrophysics Data System (ADS)
Karabıyık, Hasan; Kırılmış, Cumhur; Karabıyık, Hande
2017-08-01
The molecular and crystal structure of the title compound in which two thiazole-2-amine rings are linked to each other by disulfide bridge (sbnd Csbnd Ssbnd Ssbnd Csbnd) were studied by single-crystal X-ray diffraction, FT-IR, NMR spectroscopy, quantum chemical calculations and topological analyses on the electron density. A novel synthesis route for the compounds having symmetrical disulfide bridge is reported. The most important result regarding the compound is about electron donating or accepting properties of the terminal amine groups. Planar amine group acts as an electron-donating group, while pyramidal amine behaves as electron-accepting group. This inference was confirmed by scrutiny of crystallographic geometry and quantum chemical studies. To ascertain underlying reasons for this fact, intermolecular interactions (Nsbnd H⋯N type H-bonds and Csbnd H···π interactions) were studied. These interactions involving aromatic thiazole rings are verified by topological electron density and Hirshfeld surface analyses. Intermolecular interactions do not have an effect on the differentiation in electron donating or accepting ability of amine groups, because both amine groups are involved in Nsbnd H⋯N type H-bonds. In methodological sense, it has been understood that Ehrenfest forces acting on electron density are useful theoretical probe to analyze intra-molecular charge transfer processes.
Bridge Busters: The 397th Bombardment Group (Medium) and the B-26 Marauder in World War II
2015-06-01
up largely of new pilots from the training pipeline, these established groups transitioned from flying other aircraft. Unfortunately, four fatal...The 322 BG became the first of four initial B-26 groups to join the Eighth AF’s Third Bombardment Wing. With its first aircraft arriving in England...AF refused the suggestion. Marauders continued in the medium bombing role.101 In October 1943, the AAF transferred all four B-26 groups in
Dry paths effectively reduce road mortality of small and medium-sized terrestrial vertebrates.
Niemi, Milla; Jääskeläinen, Niina C; Nummi, Petri; Mäkelä, Tiina; Norrdahl, Kai
2014-11-01
Wildlife passages are widely used mitigation measures designed to reduce the adverse impacts of roads on animals. We investigated whether road kills of small and medium-sized terrestrial vertebrates can be reduced by constructing dry paths adjacent to streams that pass under road bridges. The study was carried out in southern Finland during the summer of 2008. We selected ten road bridges with dry paths and ten bridges without them, and an individual dry land reference site for each study bridge on the basis of landscape and traffic features. A total of 307 dead terrestrial vertebrates were identified during the ten-week study period. The presence of dry paths decreased the amount of road-killed terrestrial vertebrates (Poisson GLMM; p < 0.001). That was true also when considering amphibians alone (p < 0.001). The evidence on road-kills on mammals was not such clear. In the mammal model, a lack of dry paths increased the amount of carcasses (p = 0.001) whereas the number of casualties at dry path bridges was comparable with dry land reference sites. A direct comparison of the dead ratios suggests an average efficiency of 79% for the dry paths. When considering amphibians and mammals alone, the computed effectiveness was 88 and 70%, respectively. Our results demonstrate that dry paths under road bridges can effectively reduce road-kills of small and medium-sized terrestrial vertebrates, even without guiding fences. Dry paths seemed to especially benefit amphibians which are a threatened species group worldwide and known to suffer high traffic mortality. Copyright © 2014 Elsevier Ltd. All rights reserved.
Mechanical circulatory support as a bridge to cardiac retransplantation: a single center experience.
Clerkin, Kevin J; Thomas, Sunu S; Haythe, Jennifer; Schulze, P Christian; Farr, Maryjane; Takayama, Hiroo; Jorde, Ulrich P; Restaino, Susan W; Naka, Yoshifumi; Mancini, Donna M
2015-02-01
Cardiac retransplantation is increasing in frequency. Recent data have shown that retransplantation outcomes are now comparable with primary transplantation. The use of mechanical circulatory support (MCS) as a bridge to retransplantation has similar post-retransplant outcomes to those without MCS, but the success of bridging patients to retransplant with MCS has not been well studied. From January 2000 to February 2014 at Columbia University Medical Center, 84 patients were listed for retransplantation. Of this cohort, 48 patients underwent retransplantation, 15 were bridged with MCS, 24 died, and 6 clinically improved. A retrospective analysis was performed examining waiting list time, survival to retransplantation, and survival after retransplant. The effect of the United Network of Organ Sharing (UNOS) allocation policy change in 2006 on waiting list time and MCS use was also investigated. Of 48 patients who underwent retransplantation, 11 were bridged with MCS. Overall 1-year survival to retransplantation was 81.3%. There was no significant difference in waiting list survival (p = 0.71) in those with and without MCS. Death from cardiac arrest or multiorgan failure with infection was more frequent in the medically managed group (p = 0.002). After the UNOS 2006 allocation policy change, waiting list time (599 ± 936 days in Era 1 vs 526 ± 498 days in Era 2, p = 0.65) and waiting list survival (p = 0.22) between eras were comparable, but there was a trend toward greater use of MCS (p = 0.13). Survival after retransplant was acceptable. The use of MCS as a bridge to cardiac retransplantation is a reasonable strategy. Copyright © 2015 International Society for Heart and Lung Transplantation. Published by Elsevier Inc. All rights reserved.
Consensus on Bridges for Barriers to Insulin Therapy.
Kalra, Sanjay; Ghosal, Samit; Shah, Parag
2017-03-01
Insulin is an effective, safe and well-tolerated drug for glycaemic control. However, there are significant barriers to its use. This consensus statement aims to define these barriers and suggest bridges to overcome them. The consensus statements are based upon deliberations of a meeting held at New Delhi, India on 20 August 2016. The expert group committee reviewed various barriers to insulin use and categorized them into various categories: patient/community-related, physician-related and drug-related. The committee further proposed recommendations, based on published literature and their clinical experience, to address each of these barriers. Barriers (and bridges) can be classified as patient/community, physician/provider, and drug/device. Patient and physician barriers can further be categorized as those related to perceived inadequacy, perceived high cost, and perceived lack of benefit. Drug and device barriers can similarly be classified as those linked with perceived inadequacy, perceived high cost, and perceived lack of tolerability. Such a classification allows diabetes care providers to build appropriate bridges, which in turn facilitate timely insulin usage. Patient related barriers can be bridged by education, support and counselling. Use of modern insulin regimes and social marketing can address barriers related to perceived cost and lack of benefit. Physician related barriers can be resolved by training on various aspects of diabetes care. This will also help to break drug and device barriers, by ensuring appropriate choice of regimes, preparations and delivery devices. The consensus statements provide an easily understandable taxonomic structure of barriers to insulin use. By using a reader-friendly rubric, and by focusing on bridges (rather than barriers alone), it promotes a proactive and positive approach to diabetes management. The consensus statement should serve as a useful pedagogic and clinical tool for diabetes care professionals, and facilitate good diabetes care across the world.
Gartsman, Gary M; Drake, Gregory; Edwards, T Bradley; Elkousy, Hussein A; Hammerman, Steven M; O'Connor, Daniel P; Press, Cyrus M
2013-11-01
The purpose of this study was to compare the structural outcomes of a single-row rotator cuff repair and double-row suture bridge fixation after arthroscopic repair of a full-thickness supraspinatus rotator cuff tear. We evaluated with diagnostic ultrasound a consecutive series of ninety shoulders in ninety patients with full-thickness supraspinatus tears at an average of 10 months (range, 6-12) after operation. A single surgeon at a single hospital performed the repairs. Inclusion criteria were full-thickness supraspinatus tears less than 25 mm in their anterior to posterior dimension. Exclusion criteria were prior operations on the shoulder, partial thickness tears, subscapularis tears, infraspinatus tears, combined supraspinatus and infraspinatus repairs and irreparable supraspinatus tears. Forty-three shoulders were repaired with single-row technique and 47 shoulders with double-row suture bridge technique. Postoperative rehabilitation was identical for both groups. Ultrasound criteria for healed repair included visualization of a tendon with normal thickness and length, and a negative compression test. Eighty-three patients were available for ultrasound examination (40 single-row and 43 suture-bridge). Thirty of 40 patients (75%) with single-row repair demonstrated a healed rotator cuff repair compared to 40/43 (93%) patients with suture-bridge repair (P = .024). Arthroscopic double-row suture bridge repair (transosseous equivalent) of an isolated supraspinatus rotator cuff tear resulted in a significantly higher tendon healing rate (as determined by ultrasound examination) when compared to arthroscopic single-row repair. Copyright © 2013 Journal of Shoulder and Elbow Surgery Board of Trustees. Published by Mosby, Inc. All rights reserved.
Lam, Sonia Y.; Yeung, Rachel C. Y.; Yu, Tsz-Ha; Sze, Kong-Hung; Wong, Kam-Bo
2011-01-01
Background Thermophilic enzymes are often less active than their mesophilic homologues at low temperatures. One hypothesis to explain this observation is that the extra stabilizing interactions increase the rigidity of thermophilic enzymes and hence reduce their activity. Here we employed a thermophilic acylphosphatase from Pyrococcus horikoshii and its homologous mesophilic acylphosphatase from human as a model to study how local rigidity of an active-site residue affects the enzymatic activity. Methods and Findings Acylphosphatases have a unique structural feature that its conserved active-site arginine residue forms a salt-bridge with the C-terminal carboxyl group only in thermophilic acylphosphatases, but not in mesophilic acylphosphatases. We perturbed the local rigidity of this active-site residue by removing the salt-bridge in the thermophilic acylphosphatase and by introducing the salt-bridge in the mesophilic homologue. The mutagenesis design was confirmed by x-ray crystallography. Removing the salt-bridge in the thermophilic enzyme lowered the activation energy that decreased the activation enthalpy and entropy. Conversely, the introduction of the salt-bridge to the mesophilic homologue increased the activation energy and resulted in increases in both activation enthalpy and entropy. Revealed by molecular dynamics simulations, the unrestrained arginine residue can populate more rotamer conformations, and the loss of this conformational freedom upon the formation of transition state justified the observed reduction in activation entropy. Conclusions Our results support the conclusion that restricting the active-site flexibility entropically favors the enzymatic activity at high temperatures. However, the accompanying enthalpy-entropy compensation leads to a stronger temperature-dependency of the enzymatic activity, which explains the less active nature of the thermophilic enzymes at low temperatures. PMID:21423654
Lam, Sonia Y; Yeung, Rachel C Y; Yu, Tsz-Ha; Sze, Kong-Hung; Wong, Kam-Bo
2011-03-01
Thermophilic enzymes are often less active than their mesophilic homologues at low temperatures. One hypothesis to explain this observation is that the extra stabilizing interactions increase the rigidity of thermophilic enzymes and hence reduce their activity. Here we employed a thermophilic acylphosphatase from Pyrococcus horikoshii and its homologous mesophilic acylphosphatase from human as a model to study how local rigidity of an active-site residue affects the enzymatic activity. Acylphosphatases have a unique structural feature that its conserved active-site arginine residue forms a salt-bridge with the C-terminal carboxyl group only in thermophilic acylphosphatases, but not in mesophilic acylphosphatases. We perturbed the local rigidity of this active-site residue by removing the salt-bridge in the thermophilic acylphosphatase and by introducing the salt-bridge in the mesophilic homologue. The mutagenesis design was confirmed by x-ray crystallography. Removing the salt-bridge in the thermophilic enzyme lowered the activation energy that decreased the activation enthalpy and entropy. Conversely, the introduction of the salt-bridge to the mesophilic homologue increased the activation energy and resulted in increases in both activation enthalpy and entropy. Revealed by molecular dynamics simulations, the unrestrained arginine residue can populate more rotamer conformations, and the loss of this conformational freedom upon the formation of transition state justified the observed reduction in activation entropy. Our results support the conclusion that restricting the active-site flexibility entropically favors the enzymatic activity at high temperatures. However, the accompanying enthalpy-entropy compensation leads to a stronger temperature-dependency of the enzymatic activity, which explains the less active nature of the thermophilic enzymes at low temperatures.
2013-01-01
The global healthcare industry is undergoing substantial changes and adaptations to the constant decline of approved new medical entities. This decrease in internal research productivity is resulting in a major decline of patent-protected sales (patent cliff) of most of the pharmaceutical companies. Three major global adaptive trends as driving forces to cope with these challenges are evident: cut backs of internal research and development jobs in the western hemisphere (Europe and USA), following the market growth potential of Asia by building up internal or external research and development capabilities there and finally, ‘early innovation hunting’ with an increased focus on identifying and investing in very early innovation sources within academia and small start-up companies. Early innovation hunting can be done by different approaches: increased corporate funding, establishment of translational institutions to bridge innovation, increasing sponsored collaborations and formation of technology hunting groups for capturing very early scientific ideas and concepts. This emerging trend towards early innovation hunting demands special adaptations from both the pharmaceutical industry and basic researchers in academia to bridge the translation into new medicines which deliver innovative medicines that matters to the patient. This opinion article describes the different modalities of cross-fertilisation between basic university or publicly funded institutional research and the applied research and development activities within the pharmaceutical industry. Two key factors in this important translational bridge can be identified: preparation of both partnering organisations to open up for new and sometime disruptive ideas and creation of truly trust-based relationships between the different groups allowing long-term scientific collaborations while acknowledging that value-creating differences are an essential factor for successful collaboration building. PMID:23496921
Germann, Paul G; Schuhmacher, Alexander; Harrison, Juan; Law, Ronald; Haug, Kevin; Wong, Gordon
2013-03-05
The global healthcare industry is undergoing substantial changes and adaptations to the constant decline of approved new medical entities. This decrease in internal research productivity is resulting in a major decline of patent-protected sales (patent cliff) of most of the pharmaceutical companies. Three major global adaptive trends as driving forces to cope with these challenges are evident: cut backs of internal research and development jobs in the western hemisphere (Europe and USA), following the market growth potential of Asia by building up internal or external research and development capabilities there and finally, 'early innovation hunting' with an increased focus on identifying and investing in very early innovation sources within academia and small start-up companies. Early innovation hunting can be done by different approaches: increased corporate funding, establishment of translational institutions to bridge innovation, increasing sponsored collaborations and formation of technology hunting groups for capturing very early scientific ideas and concepts. This emerging trend towards early innovation hunting demands special adaptations from both the pharmaceutical industry and basic researchers in academia to bridge the translation into new medicines which deliver innovative medicines that matters to the patient. This opinion article describes the different modalities of cross-fertilisation between basic university or publicly funded institutional research and the applied research and development activities within the pharmaceutical industry. Two key factors in this important translational bridge can be identified: preparation of both partnering organisations to open up for new and sometime disruptive ideas and creation of truly trust-based relationships between the different groups allowing long-term scientific collaborations while acknowledging that value-creating differences are an essential factor for successful collaboration building.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Lemus-Santana, A.A.; Rodriguez-Hernandez, J.; Institute of Materials Science and Technology, University of Havana
2011-08-15
The formation of T-pyz-Ni bridges (pyz=pyrazine) in the T[Ni(CN){sub 4}].2pyz series is known for T=Mn, Zn, Cd and Co but not with T=Fe, Ni. In this contribution the existence of such bridges also for T=Fe, Ni is discussed. The obtained pillared solids, T[Ni(CN){sub 4}].2pyz, were characterized from XRD, TG, UV-Vis, IR, Raman, Moessbauer and magnetic data. Their crystal structures were refined in the orthorhombic Pmna space group from XRD powder patterns. The structural behavior of these solids on cooling down to 77 K was also studied. In the 180-200 K temperature range the occurrence of a structural transition to amore » monoclinic structure (P2{sub 1}/c space group) was observed. No temperature induced spin transition was observed for Fe[Ni(CN){sub 4}].2pyz. The iron (II) was found to be in high spin electronic state and this configuration is preserved on cooling down to 2 K. The magnetic data indicate the occurrence of a low temperature weak anti-ferromagnetic interaction between T metal centers within the T[Ni(CN){sub 4}] layer. In the paramagnetic region for Ni[Ni(CN){sub 4}].2pyz, a reversible temperature induced spin transition for the inner Ni atom was detected. - Graphical abstract: Rippled sheets structure for the pillared solids T[Ni(CN){sub 4}].2pyz. The pyrazine molecule is found forming T-pyz-Ni bridges between neighboring layers. Highlights: > Pillared 2D solids. > Inorganic-organic solids. > Assembling of molecular blocks. > From 1D and 2D building blocks to 3D solids.« less
Fabelo, Oscar; Pasán, Jorge; Cañadillas-Delgado, Laura; Delgado, Fernando S; Lloret, Francesc; Julve, Miguel; Ruiz-Pérez, Catalina
2008-09-15
The hydrothermal preparation, crystal structure determination, and magnetic study of two isomers made up of 1,2,4,5-benzenetetracarboxylate and high-spin Co(II) ions of formula [Co2(bta)(H2O)4]n x 2n H2O (1 and 2; H4bta = 1,2,4,5-benzenetetracarboxylic acid) are reported. 1 and 2 are three-dimensional compounds whose structures can be described as (4,4) rectangular layers of trans-diaquacobalt(II) units with the bta(4-) anion acting as tetrakis-monodentate ligand through the four carboxylate groups, which are further connected through other trans-[Co(H2O)2](2+) (1) and planar [Co(H2O)4](2+) (2) entities, with the bridging units being a carboxylate group in either the anti-syn (1) or syn-syn (2) conformations and a water molecule (2). The study of the magnetic properties of 1 and 2 in the temperature range 1.9-300 K shows the occurrence of weak antiferromagnetic interactions between the high-spin Co(II) ions, with the strong decrease of chi(M)T upon cooling being mainly due to the depopulation of the higher energy Kramers doublets of the six-coordinated Co(II) ions. The computed values of the exchange coupling between the Co(II) ions across anti-syn carboxylate (1) and syn-syn carboxylate/water (2) bridges are J = -0.060 (1) and -1.90 (2) cm(-1) (with the Hamiltonian being defined as H = -Jsigma(i,j)S(i) x S(j)). These values follow the different conformations of the carboxylate bridge in 1 (anti-syn) and 2 (syn-syn) with the occurrence of a double bridge in 2 (water/carboxylate).
Fukazawa, Aiko; Ichihashi, Yasunori; Kosaka, Youhei; Yamaguchi, Shigehiro
2009-11-02
The intramolecular trans-halophosphanylation of 2-(aminophosphanyl)phenylacetylenes mediated by PBr3 followed by the oxidation with H2O2, produces 3-bromobenzo[b]phosphole oxide derivatives. This cyclization is also used for the synthesis of a 3-iodo derivative by conducting the reaction in the presence of LiI. Based on this synthetic method, various benzophosphole-containing pi-conjugated compounds, including a phosphoryl and methylene-bridged stilbene 10, 2,3,6,7-tetraphenylbenzo[1,2-b:4,5-b']diphosphole-P,P'-dioxides 11, and their phosphine sulfide derivatives 12, are synthesized. The study of the structure-property relationships in a series of the bridged stilbenes, including a bis(methylene)-bridged stilbene 10, and a bis(phosphoryl)-bridged stilbene, reveals that as the contribution of the phosphoryl groups increased, the absorption and emission maxima substantially shift to longer wavelengths. The intrinsic substituent effects of the phosphoryl group in this skeleton are to decrease the oscillator strength of the electronic transition and thus decrease the radiative decay rate constants from the singlet excited state. Nevertheless, these compounds maintain high fluorescence quantum yields (Phi(F)>0.8) owing to the significantly retarded nonradiative decay process. In the study of the benzodiphosphole derivatives 11 and 12, their cyclic voltammetry revealed that both of the phosphoryl and phosphine sulfide derivatives have low reduction potentials (-1.7 to -1.8 V vs ferrocene/ferrocenium couple) with the high reversibility of the redox waves. These compounds also showed high thermal stabilities with the high glass transition temperatures of 147-159 degrees C, indicative of their potential utilities as amorphous materials.
eHealth and IMIA's Strategic Planning Process - IMIA conference introductory address.
Murray, Peter; Haux, Reinhold; Lorenzi, Nancy
2008-01-01
The International Medical Informatics Association (IMIA) is the only organization in health and biomedical informatics which is fully international in scope, bridging the academic, health practice, education, and health industry worlds through conferences, working groups, special interest groups and publications. Authored by the IMIA Interim Vice President for Strategic Planning Implementation and co-authored by the current IMIA President and the IMIA Past-President, the intention of this paper is to introduce IMIA's current strategic planning process and to set this process in relation to 'eHealth: Combining Health Telematics, Telemedicine, Biomedical Engineering and Bioinformatics to the Edge', the theme of this conference. From the viewpoint of an international organization such as IMIA, an eHealth strategy needs to be considered in a comprehensive way, including broadly stimulating high-quality health and biomedical informatics research and education, as well as providing support to bridging outcomes towards a new practice of health care in a changing world.
The oldest Mahonia (Berberidaceae) fossil from East Asia and its biogeographic implications.
Huang, Jian; Su, Tao; Lebereton-Anberrée, Julie; Zhang, Shi-Tao; Zhou, Zhe-Kun
2016-03-01
Interpretation of the biogeography of the genus Mahonia (Berberidaceae) is limited by the lack of fossil records in East Asia. Compressed fossil foliage, described here as Mahonia mioasiatica sp. nov., were collected from the Upper Miocene Xiaolongtan Formation in Wenshan, Yunnan, southwest China. These specimens represent the oldest reliable fossil record of Mahonia in East Asia. This new fossil species shows a general similarity to Group Orientales and is most similar to the extant eastern Asian Mahonia conferta. Considering other fossil evidence of Mahonia, we propose a migration route of this genus to Asia over the North Atlantic Land Bridge rather than the Bering Land Bridge. Our results also suggest that North America, Europe and East Asia have been successive centers of diversity for the genus, as a consequence of diversification in Group Orientales potentially related to historical climate change.
Brosnan, Caragh; Cribb, Alan
2014-12-01
This paper presents findings from an empirical study that explored the meaning of ethics in the everyday work of neuroscientists. Observation and interviews were carried out in one neuroscience research group that was involved in bench-to-bedside translational research. We focus here specifically on the scientists' perceptions of bioethics. Interviewees were often unfamiliar with bioethics as a discipline, particularly the more junior members of the group. Those who were aware of its existence largely viewed it as something distant from them, and as either too abstract, not relevant or an alien imposition on their work. Some interviewees themselves pointed to the need for better 'bridge building' between ethical principles and real-world examples drawn from scientific practice, and we argue that this space is where a more empirically grounded ethics may be useful in terms of actually engaging scientists at both the bench and the bedside.
Strategies for Developing Family Nursing Communities of Practice Through Social Media.
Isaacson, Kris; Looman, Wendy S
2017-02-01
This discussion article presents communities of practice (CoPs) and bridging social capital as conceptual frameworks to demonstrate how social media can be leveraged for family nursing knowledge, scholarship, and practice. CoPs require a shared domain of interest, exchange of resources, and dedication to expanding group knowledge. Used strategically and with a professional presence, mainstream social media channels such as Twitter, Facebook, and YouTube can support the family nurse in developing and contributing to CoPs related to family nursing. This article presents four strategies-curate, connect, collaborate, and contribute-for establishing and growing a social media presence that fits one's professional goals and time availability. Family nurses who leverage social media using these strategies can strengthen existing CoPs and at the same time bridge networks to reach new audiences, such as family advocacy groups, policy makers, educators, practitioners, and a wide array of other extended networks.
Key participants in codeveloped technology pose for group picture
NASA Technical Reports Server (NTRS)
1997-01-01
Following the presentation of the Universal Signal Conditioning Amplifier (USCA), a new piece of technology developed through a National Aeronautics and Space Administration (NASA) partnership with industry, to Kennedy Space Center (KSC) Director Roy Bridges, Jr., key participants in the partnership pose for a group portrait. They are (from left) Bill Larson, NASA; Dr. Pedro Medelius, INET; Roy Bridges, Jr., KSC Director; Ed Gladney and William Saputo, L-3 Communications; Pam Gillespi, representing Congressman Dave Weldon; and Frank Kinney, Technological Research and Development Authority. The USCA is a key component of the codeveloped Automated Data Acquisition System (ADAS) that measures temperature, pressure and vibration at KSC's launch pads. The breakthrough technology is expected to reduce sensor setup and configuration times from hours to seconds. KSC teamed up with Florida's Technological Research and Development Authority and manufacturer L-3 Communications to produce a system that would benefit the aerospace industry and other commercial markets.
NASA Astrophysics Data System (ADS)
Bian, He-Dong; Yang, Xiao-E.; Yu, Qing; Chen, Zi-Lu; Liang, Hong; Yan, Shi-Ping; Liao, Dai-Zheng
2008-01-01
Two helical coordination polymeric copper(II) complexes bearing amino acid Schiff bases HL or HL', which are condensed from 2-hydroxy-1-naphthaldehyde with 2-aminobenzoic acid or L-valine, respectively, have been prepared and characterised by X-ray crystallography. In [CuL] n ( 1) the copper(II) atoms are bridged by syn- anti carboxylate groups giving infinite 1-D right-handed helical chains which are further connected by weak C-H⋯Cu interactions to build a 2-D network. While in [CuL'] n ( 2) the carboxylate group acts as a rare monatomic bridge to connect the adjacent copper(II) atoms leading to the formation of a left-handed helical chain. Magnetic susceptibility measurements indicate that 1 exhibits weak ferromagnetic interactions whereas an antiferromagnetic coupling is established for 2. The magnetic behavior can be satisfactorily explained on the basis of the structural data.
Kawahara, Yohei; Terada, Itsuro; Terai, Shiro; Watanabe, Toshifumi; Amaya, Koji; Yamamoto, Seiichi; Kaji, Masahide; Maeda, Kiichi; Shimizu, Koichi
2015-11-01
In our institution, placement of a self-expanding metallic stent (SEMS) for obstructive colorectal cancer to avoid emergency operations, namely as a bridge to surgery (BTS), was introduced in April 2012. Here, we assess the efficacy and safety of pre-operative SEMS placement for treatment of Stage Ⅳ obstructive colorectal cancer. We analyzed a total of 44 cases of Stage Ⅳ colorectal cancer, which consisted of 13 obstructive cases that were surgically resected following SEMS placement as BTS (BTS group), and 31 cases that were resected in elective operations without pre-operative SEMS placement (Ope group), from April 2012 to August 2014. None of the patients had any adverse events during the SEMS procedure or after SEMS placement, and all patients of BTS group could undergo the planned operations after sufficient decompression. In the postoperative period, 1 patient of BTS group (7.7%) had anastomosis bleeding, but no other complications, including anastomosis leakage, were observed in BTS group. However more progressive primary tumors were resected in BTS group (p=0.0115), there were no significant differences for post-operative course between the 2 groups; this indicated avoiding high-risk emergency operations contributed to adequate short-term outcomes in BTS group comparable to those in Ope group. SEMS placement as BTS could be performed safely for Stage Ⅳ obstructive colorectal cancer cases, and was 1 of the effective strategies for local treatment.
NASA Astrophysics Data System (ADS)
Bilinski, Halka; Horvath, Laszlo; Ingri, Nils; Sjöberg, Staffan
1986-09-01
The conditions necessary for initial clay formation have been studied in different model systems comprising different organic acids besides Si and Al. In the present paper the solid phases and the precipitation boundary characterizing the subsystem H +-Al 3+-oxalic acid (H 2L) are discussed. pH and tyndallometric measurements were performed in an ionic medium of 0.6 M Na(Cl) at 25 °C. The two phases Al 3(OH) 7(C 2O 4) · 3H 2O (phase I) and NaAl(OH) 2(C 2O 4) · 3H 2O (phase II) determine the precipitation boundary. The following formation constants for the two phases were deduced: lgβ1 = lg([ Al3+] -3[ H2C2O4] -1[ H+] 9 = -21.87 ± 0.08 and lgβ11 = lg([ Al3+] -1[ H2C2O4] -1[ H+] 4 = -5.61 ± 0.06. Phase I exists in the range [ Al] tot≥ 10 -4.4moldm-3,[ H2C2O4] tot ≥ 10 -4.9moldm-3 and at pH < 6.8, thus being a possible precipitate in oxalic-rich natural waters. The more soluble sodium phase is unlikely to exist in natural waters. The two phases are metastable relative to crystalline gibbsite and may be considered as the first precipitation step in the transition from aqueous Al oxalates down to stable Al hydroxide. Model calculations illustrating these competing hydrolysis-complexation reactions are discussed in terms of predominance and speciation diagrams. The solid phases have been characterized by X-ray analysis of powders, TGA and IR spectra, and tentative structures are proposed. Phase I seems to be an octahedral layer structure, in which 3/5 of the octahedral sites between two close packed oxygen sheets are occupied by Al 3+ and the oxalate ion acts as a bridge ligand between two aluminium atoms. Phase II forms a more open sheet structure and has ion exchange properties. Powder data for a phase crystallized from the studied solution after a year are also presented. This phase, Na 4Al 2(OH) 2(C 2O 4) 4 · 10H 2O, supports the results from the equilibrium analysis of recent solution data by SJöBERG and ÖHMAN (1985), who have found the dinuclear complex Al 2(OH) 2(C 2O 4) 44- to exist in a solution in which the ligand is in excess.
Crystal structures of two mixed-valence copper cyanide complexes with N-methylethylenediamine
Sabatino, Alexander
2017-01-01
The crystal structures of two mixed-valence copper cyanide compounds involving N-methylethylenediamine (meen), are described. In compound (I), poly[bis(μ3-cyanido-κ3 C:C:N)tris(μ2-cyanido-κ2 C:N)bis(N-methylethane-1,2-diamine-κ2 N,N′)tricopper(I)copper(II)], [Cu4(CN)5(C3H10N2)2] or Cu4(CN)5meen2, cyanide groups link CuI atoms into a three-dimensional network containing open channels parallel to the b axis. In the network, two tetrahedrally bound CuI atoms are bonded by the C atoms of two end-on bridging CN groups to form Cu2(CN)6 moieties with the Cu atoms in close contact at 2.560 (1) Å. Other trigonally bound CuI atoms link these units together to form the network. The CuII atoms, coordinated by two meen units, are covalently linked to the network via a cyanide bridge, and project into the open network channels. In the molecular compound (II), [(N-methylethylenediamine-κ2 N,N′)copper(II)]-μ2-cyanido-κ2 C:N-[bis(cyanido-κC)copper(I)] monohydrate, [Cu2(CN)3(C3H10N2)2]·H2O or Cu2(CN)3meen2·H2O, a CN group connects a CuII atom coordinated by two meen groups with a trigonal–planar CuI atom coordinated by CN groups. The molecules are linked into centrosymmetric dimers via hydrogen bonds to two water molecules. In both compounds, the bridging cyanide between the CuII and CuI atoms has the N atom bonded to CuII and the C atom bonded to CuI, and the CuII atoms are in a square-pyramidal coordination. PMID:28217329
Healing disturbance with suture bridge configuration repair in rabbit rotator cuff tear.
Kim, Sae Hoon; Kim, Jangwoo; Choi, Young Eun; Lee, Hwa-Ryeong
2016-03-01
Medial row failure has been reported in the suture bridge technique of rotator cuff repair. This study compared the healing response of suture bridge configuration repair (SBCR) and parallel type transosseous repair (PTR). Acute rotator cuff repair was performed in 32 rabbits. Both shoulders were repaired using PTR or SBCR. In PTR, simple PTR was performed through 2 parallel transosseous tunnels created using a microdrill. In SBCR, 2 additional crisscross transosseous tunnels were added to mimic arthroscopic SBCR. At 1, 2, and 5 weeks postoperatively, comparative biomechanical testing was performed in 8 rabbits, and histologic analysis, including immunohistochemical staining for CD31, was performed in 4 rabbits. Failure loads at 1 week (38.12 ± 20.43 N vs 52.00 ± 27.23 N; P = .284) and 5 weeks (97.93 ± 48.35 N vs 119.60 ± 60.81 N; P = .218) were not statistically different between the SBCR and PTR groups, respectively, but were significantly lower in the SBCR group than in the PTR group (23.56 ± 13.56 N vs. 44.25 ± 12.53 N; P = .009), respectively, at 2 weeks. Markedly greater fibrinoid deposition was observed in the SBCR group than in the PTR group at 2 weeks. For vascularization, there was a tendency that more vessels could be observed in PTR than in SBCR at 2 weeks (15.9 vs 5.6, P = .068). In a rabbit acute rotator cuff repair model, SBCR exhibited inferior mechanical strength, and fewer blood vessels were observed at the healing site at 2 weeks postoperatively. Medial row tendon failure was more common in SBCR. Surgeons should consider the clinical effect of SBCR when performing rotator cuff repair. Copyright © 2016 Journal of Shoulder and Elbow Surgery Board of Trustees. Published by Elsevier Inc. All rights reserved.
ERIC Educational Resources Information Center
Weston, Mark E.; Bain, Alan
2015-01-01
This study reports findings from a matched-comparison, repeated-measure for intact groups design of the mediating effect of a suite of software on the quality of classroom instruction provided to students by teachers. The quality of instruction provided by teachers in the treatment and control groups was documented via observations that were…
ERIC Educational Resources Information Center
Hamm, Jill V.; Bradford Brown, B.; Heck, Daniel J.
2005-01-01
Based on the revised social contact theory, correlates of cross-ethnic friend nomination among 580 African American, 948 Asian-descent, 860 Latino, and 3986 White adolescents were examined. Socioeconomic and academic disparities between ethnic groups differentiated cross-ethnic friend nomination between schools for all groups but African…
ERIC Educational Resources Information Center
Johnston, Keith; Conneely, Claire; Murchan, Damian; Tangney, Brendan
2015-01-01
Bridge21 is an innovative approach to learning for secondary education that was originally conceptualised as part of a social outreach intervention in the authors' third-level institution whereby participants attended workshops at a dedicated learning space on campus focusing on a particular model of technology-mediated group-based learning. This…
Gonzalez Rodriguez, Pablo; Dral, A Petra; van den Nieuwenhuijzen, Karin J H; Lette, Walter; Schipper, Dik J; Ten Elshof, Johan E
2018-01-24
In view of their possible application as high temperature solid lubricants, the tribological and thermochemical properties of several organosilica networks were investigated over a range of temperatures between 25 and 580 °C. Organosilica networks, obtained from monomers with terminal and bridging organic groups, were synthesized by a sol-gel process. The influence of carbon content, crosslink density, rotational freedom of incorporated hydrocarbon groups, and network connectivity on the high temperature friction properties of the polymer was studied for condensed materials from silicon alkoxide precursors with terminating organic groups, i.e., methyltrimethoxysilane, propyltrimethoxysilane, diisopropyldimethoxysilane, cyclohexyltrimethoxysilane, phenyltrimethoxysilane and 4-biphenylyltriethoxysilane networks, as well as precursors with organic bridging groups between Si centers, i.e., 1,4-bis(triethoxysilyl)benzene and 4,4'-bis(triethoxysilyl)-1,1'-biphenyl. Pin-on-disc measurements were performed using all selected solid lubricants. It was found that materials obtained from phenyltrimethoxysilane and cyclohexyltrimethoxysilane precursors showed softening above 120 °C and performed best in terms of friction reduction, reaching friction coefficients as low as 0.01. This value is lower than that of graphite films (0.050 ± 0.005), a common bench mark for solid lubricants.
Thermochemical Stability and Friction Properties of Soft Organosilica Networks for Solid Lubrication
Gonzalez Rodriguez, Pablo; van den Nieuwenhuijzen, Karin J. H.; Lette, Walter; Schipper, Dik J.
2018-01-01
In view of their possible application as high temperature solid lubricants, the tribological and thermochemical properties of several organosilica networks were investigated over a range of temperatures between 25 and 580 °C. Organosilica networks, obtained from monomers with terminal and bridging organic groups, were synthesized by a sol-gel process. The influence of carbon content, crosslink density, rotational freedom of incorporated hydrocarbon groups, and network connectivity on the high temperature friction properties of the polymer was studied for condensed materials from silicon alkoxide precursors with terminating organic groups, i.e., methyltrimethoxysilane, propyltrimethoxysilane, diisopropyldimethoxysilane, cyclohexyltrimethoxysilane, phenyltrimethoxysilane and 4-biphenylyltriethoxysilane networks, as well as precursors with organic bridging groups between Si centers, i.e., 1,4-bis(triethoxysilyl)benzene and 4,4′-bis(triethoxysilyl)-1,1′-biphenyl. Pin-on-disc measurements were performed using all selected solid lubricants. It was found that materials obtained from phenyltrimethoxysilane and cyclohexyltrimethoxysilane precursors showed softening above 120 °C and performed best in terms of friction reduction, reaching friction coefficients as low as 0.01. This value is lower than that of graphite films (0.050 ± 0.005), a common bench mark for solid lubricants. PMID:29364164
Olechnowicz, Frank; Hillhouse, Gregory L; Jordan, Richard F
2015-03-16
The (IPr)Ni scaffold stabilizes low-coordinate, mononuclear and dinuclear complexes with a diverse range of sulfur ligands, including μ(2)-η(2),η(2)-S2, η(2)-S2, μ-S, and μ-SH motifs. The reaction of {(IPr)Ni}2(μ-Cl)2 (1, IPr = 1,3-bis(2,6-diisopropylphenyl)imidazolin-2-ylidene) with S8 yields the bridging disulfide species {(IPr)ClNi}2(μ(2)-η(2),η(2)-S2) (2). Complex 2 reacts with 2 equiv of AdNC (Ad = adamantyl) to yield a 1:1 mixture of the terminal disulfide compound (IPr)(AdNC)Ni(η(2)-S2) (3a) and trans-(IPr)(AdNC)NiCl2 (4a). 2 also reacts with KC8 to produce the Ni-Ni-bonded bridging sulfide complex {(IPr)Ni}2(μ-S)2 (6). Complex 6 reacts with H2 to yield the bridging hydrosulfide compound {(IPr)Ni}2(μ-SH)2 (7), which retains a Ni-Ni bond. 7 is converted back to 6 by hydrogen atom abstraction by 2,4,6-(t)Bu3-phenoxy radical. The 2,6-diisopropylphenyl groups of the IPr ligand provide lateral steric protection of the (IPr)Ni unit but allow for the formation of Ni-Ni-bonded dinuclear species and electronically preferred rather than sterically preferred structures.
Determination of the Bridging Ligand in the Active Site of Tyrosinase.
Zou, Congming; Huang, Wei; Zhao, Gaokun; Wan, Xiao; Hu, Xiaodong; Jin, Yan; Li, Junying; Liu, Junjun
2017-10-28
Tyrosinase is a type-3 copper enzyme that is widely distributed in plants, fungi, insects, and mammals. Developing high potent inhibitors against tyrosinase is of great interest in diverse fields including tobacco curing, food processing, bio-insecticides development, cosmetic development, and human healthcare-related research. In the crystal structure of Agaricus bisporus mushroom tyrosinase, there is an oxygen atom bridging the two copper ions in the active site. It is unclear whether the identity of this bridging oxygen is a water molecule or a hydroxide anion. In the present study, we theoretically determine the identity of this critical bridging oxygen by performing first-principles hybrid quantum mechanics/molecular mechanics/Poisson-Boltzmann-surface area (QM/MM-PBSA) calculations along with a thermodynamic cycle that aim to improve the accuracy. Our results show that the binding with water molecule is energy favored and the QM/MM-optimized structure is very close to the crystal structure, whereas the binding with hydroxide anions causes the increase of energy and significant structural changes of the active site, indicating that the identity of the bridging oxygen must be a water molecule rather than a hydroxide anion. The different binding behavior between water and hydroxide anions may explain why molecules with a carboxyl group or too many negative charges have lower inhibitory activity. In light of this, the design of high potent active inhibitors against tyrosinase should satisfy both the affinity to the copper ions and the charge neutrality of the entire molecule.
Nwaejike, Nnamdi; Son, Andre Y; Milano, Carmelo A; Daneshmand, Mani A
2017-10-01
A best evidence topic in cardiac surgery was written according to a structured protocol. The question addressed was: Is there a role for upper-extremity intra-aortic balloon pump counterpulsation (UE-IABP) in the treatment of end-stage heart failure? Altogether 230 papers were found using the reported search, of which 6 papers represented the best evidence to answer the clinical question. The authors, journal, date and country of publication, patient group studied, study type, relevant outcomes and results of these papers are tabulated. Of the 163 bridge-to-transplantation (BTT) patients, 141 (86.5%) were successfully transplanted and of the 9 bridge-to-recovery (BTR) patients, 6 (66.7%) were successfully weaned from the device. Length of support ranged from 3 to 152 days, and the most frequent complications were device malfunction or migration necessitating exchange or repositioning, occurring at a collective rate of 37.3%. UE-IABP is a minimally invasive and cost-effective strategy that provides haemodynamic support while preserving both the mediastinum and the functional status in BTR and BTT patients who may not tolerate more invasive modes of mechanical circulatory support. We conclude that UE-IABP can be used as a bridge-to-recovery (BTR) or transplant (BTT) in patients with end-stage heart failure. © The Author 2017. Published by Oxford University Press on behalf of the European Association for Cardio-Thoracic Surgery. All rights reserved.
Chu, Tien-Min G.; Warden, Stuart J.; Turner, Charles H.; Stewart, Rena L.
2006-01-01
Segmental defect regeneration has been a clinical challenge. Current tissue engineering approach using porous biodegradable scaffolds to delivery osteogenic cells and growth factors demonstrated success in facilitating bone regeneration in these cases. However, due to the lack of mechanical property, the porous scaffolds were evaluated in non-load bearing area or were stabilized with stress-shielding devices (bone plate or external fixation). In this paper, we tested a scaffold that does not require a bone plate because it has sufficient biomechanical strength. The tube-shaped scaffolds were manufactured from poly(propylene) fumarate/tricalcium phosphate (PPF/TCP) composites. Dicalcium phosphate dehydrate (DCPD) were used as bone morphogenetic protein -2 (BMP-2) carrier. Twenty two scaffolds were implanted in 5 mm segmental defects in rat femurs stabilized with k-wire for 6 and 15 weeks with and without 10 μg of rhBMP-2. Bridging of the segmental defect was evaluated first radiographically and was confirmed by histology and micro- computer tomography (μ-CT) imaging. The scaffolds in the BMP group maintained the bone length throughout the duration of the study and allow for bridging. The scaffolds in the control group failed to induce bridging and collapsed at 15 weeks. Peripheral computed tomography (pQCT) showed that BMP-2 does not increase the bone mineral density in the callus. Finally, the scaffold in BMP group was found to restore the mechanical property of the rat femur after 15 weeks. Our results demonstrated that the load-bearing BMP-2 scaffold can maintain bone length and allow successfully regeneration in segmental defects. PMID:16996588
NASA Astrophysics Data System (ADS)
Kang, Jeung Ku; Musgrave, Charles B.
2002-03-01
We use density functional theory to investigate atomic layer deposition (ALD) mechanism of silicon dioxide on the Si(100)-2×1 surface from the precursors SiCl4 and H2O. First, we explore the reaction mechanism of water with the bare Si(100)-2×1 surface to produce surface hydroxyl groups. We find that this reaction proceeds through a two-step pathway with an overall barrier of 33.3 kcal/mol. Next, we investigate the ALD mechanism for the binary reaction sequence: the SiCl4 half reaction and the H2O half reaction. For the SiCl4 half reaction, SiCl4 first forms a σ-bond with the oxygen of the surface OH group and then releases an HCl molecule. The predicted barrier for this process is 15.8 kcal/mol. Next, adsorbed SiCl3 reacts with a neighboring OH group to form bridged SiCl2 with a barrier of 22.6 kcal/mol. The H2O half reaction also proceeds through two sequential steps with an overall barrier of 19.1 kcal/mol for the reaction of H2O with bridged SiCl2 to form bridged Si(OH)2. The predicted barrier of 22.6 kcal/mol for the rate-limiting step of the ALD binary reaction mechanism is consistent with the experimental value of 22.0 kcal/mol. In addition, we find that the calculated frequencies are in good agreement with the experimentally measured IR spectra.
Cohn Yakubovich, Doron; Sheyn, Dmitriy; Bez, Maxim; Schary, Yeshai; Yalon, Eran; Sirhan, Afeef; Amira, May; Yaya, Alin; De Mel, Sandra; Da, Xiaoyu; Ben-David, Shiran; Tawackoli, Wafa; Ley, Eric J; Gazit, Dan; Gazit, Zulma; Pelled, Gadi
2017-03-09
A devastating condition that leads to trauma-related morbidity, multiple rib fractures, remain a serious unmet clinical need. Systemic administration of mesenchymal stem cells (MSCs) has been shown to regenerate various tissues. We hypothesized that parathyroid hormone (PTH) therapy would enhance MSC homing and differentiation, ultimately leading to bone formation that would bridge rib fractures. The combination of human MSCs (hMSCs) and a clinically relevant PTH dose was studied using immunosuppressed rats. Segmental defects were created in animals' fifth and sixth ribs. The rats were divided into four groups: a negative control group, in which animals received vehicle alone; the PTH-only group, in which animals received daily subcutaneous injections of 4 μg/kg teriparatide, a pharmaceutical derivative of PTH; the hMSC-only group, in which each animal received five injections of 2 × 10 6 hMSCs; and the hMSC + PTH group, in which animals received both treatments. Longitudinal in vivo monitoring of bone formation was performed biweekly using micro-computed tomography (μCT), followed by histological analysis. Fluorescently-dyed hMSCs were counted using confocal microscopy imaging of histological samples harvested 8 weeks after surgery. PTH significantly augmented the number of hMSCs that homed to the fracture site. Immunofluorescence of osteogenic markers, osteocalcin and bone sialoprotein, showed that PTH induced cell differentiation in both exogenously administered cells and resident cells. μCT scans revealed a significant increase in bone volume only in the hMSC + PTH group, beginning by the 4 th week after surgery. Eight weeks after surgery, 35% of ribs in the hMSC + PTH group had complete bone bridging, whereas there was complete bridging in only 6.25% of ribs (one rib) in the PTH-only group and in none of the ribs in the other groups. Based on the μCT scans, biomechanical analysis using the micro-finite element method demonstrated that the healed ribs were stiffer than intact ribs in torsion, compression, and bending simulations, as expected when examining bone callus composed of woven bone. Administration of both hMSCs and PTH worked synergistically in rib fracture healing, suggesting this approach may pave the way to treat multiple rib fractures as well as additional fractures in various anatomical sites.
Yoshizawa, K; Kamachi, T; Shiota, Y
2001-10-10
Dynamic aspects of alkane hydroxylation mediated by Compound I of cytochrome P450 are discussed from classical trajectory calculations at the B3LYP level of density functional theory. The nuclei of the reacting system are propagated from a transition state to a reactant or product direction according to classical dynamics on a Born-Oppenheimer potential energy surface. Geometric and energetic changes in both low-spin doublet and high-spin quartet states are followed along the ethane to ethanol reaction pathway, which is partitioned into two chemical steps: the first is the H-atom abstraction from ethane by the iron-oxo species of Compound I and the second is the rebound step in which the resultant iron-hydroxo complex and the ethyl radical intermediate react to form the ethanol complex. Molecular vibrations of the C-H bond being dissociated and the O-H bond being formed are significantly activated before and after the transition state, respectively, in the H-atom abstraction. The principal reaction coordinate that can represent the first chemical step is the C-H distance or the O-H distance while other geometric parameters remain almost unchanged. The rebound process begins with the iron-hydroxo complex and the ethyl radical intermediate and ends with the formation of the ethanol complex, the essential process in this reaction being the formation of the C-O bond. The H-O-Fe-C dihedral angle corresponds to the principal reaction coordinate for the rebound step. When sufficient kinetic energy is supplied to this rotational mode, the rebound process should efficiently take place. Trajectory calculations suggest that about 200 fs is required for the rebound process under specific initial conditions, in which a small amount of kinetic energy (0.1 kcal/mol) is supplied to the transition state exactly along the reaction coordinate. An important issue about which normal mode of vibration is activated during the hydroxylation reaction is investigated in detail from trajectory calculations. A large part of the kinetic energy is distributed to the C-H and O-H stretching modes before and after the transition state for the H-atom abstraction, respectively, and a small part of the kinetic energy is distributed to the Fe-O and Fe-S stretching modes and some characteristic modes of the porphyrin ring. The porphyrin marker modes of nu(3) and nu(4) that explicitly involve Fe-N stretching motion are effectively enhanced in the hydroxylation reaction. These vibrational modes of the porphyrin ring can play an important role in the energy transfer during the enzymatic process.
Coordination chemistry with phosphine and phosphine oxide-substituted hydroxyferrocenes.
Atkinson, Robert C J; Gibson, Vernon C; Long, Nicholas J; White, Andrew J P
2010-08-28
New unsymmetrical hydroxyferrocenes were synthesised from dibromoferrocene. The oxygen heteroatom was introduced via lithiation and quenching with bis-trimethylsilylperoxide followed by hydrolysis to unmask the hydroxyl functionality. The coordination chemistry of 1'-(diphenylphosphino)-1-hydroxyferrocene 2 was explored with palladium and rhodium precursors. A dinuclear palladium methyl complex with bridging ferrocenyloxo groups was obtained from the reaction between 2 and (cyclooctadiene)methylchloropalladium(II). With tetracarbonyldichlorodirhodium(I), two complexes were isolated. The major product was a bis ligand cis phosphine ligated complex with one ligand bound in a chelating mode and one with a pendant hydroxyl group. A minor product was crystallographically characterised as a dinuclear ferrocenyloxo-bridged rhodium carbonyl complex. The coordination chemistry of 2 and the corresponding phosphine oxide 3 was examined with group 4 metals and the resulting complexes examined as ethylene polymerisation catalysts. The ligands were found to bind in either a chelating fashion or with pendant phosphine donors. In all cases, low to moderately active ethylene polymerisation catalysts were found. The catalysts were very unstable and catalyst residues were observed in the isolated polymer indicating a short catalyst lifetime.
Three Bridge Fryer's Ford Bridge, Nimrod Bridge, and Ward's ...
Three Bridge - Fryer's Ford Bridge, Nimrod Bridge, and Ward's Crossing Bridge - Fryer's Ford Bridge, Spanning East Fork of Point Remove Creek at Fryer Bridge Road (CR 67), Solgohachia, Conway County, AR
Diethyl 4,4′-(3,6-dioxaoctane-1,8-diyldioxy)dibenzoate
Ma, Zhen; Qin, Haisha; Lai, Gang; Fan, Jingjie
2012-01-01
The title compound, C24H30O8, was obtained by reaction of ethyl 4-hydroxybenzoate with 1,2-dichloroethane. The molecule occupies a crystallographic inversion center, with its central ethylene bridge in an anti conformation. The other ethylene bridge has a gauche conformation, with the corresponding O—C—C—O torsion angle being 74.2 (1)°. The benzene rings are almost coplanar with the adjacent ethoxycarbonyl groups, with an r.m.s. deviation of 0.078 Å. PMID:22412598
47 CFR 80.1007 - Bridge-to-bridge radiotelephone installation.
Code of Federal Regulations, 2011 CFR
2011-10-01
... 47 Telecommunication 5 2011-10-01 2011-10-01 false Bridge-to-bridge radiotelephone installation. 80.1007 Section 80.1007 Telecommunication FEDERAL COMMUNICATIONS COMMISSION (CONTINUED) SAFETY AND... Bridge-to-Bridge Act § 80.1007 Bridge-to-bridge radiotelephone installation. Use of the bridge-to-bridge...
47 CFR 80.1007 - Bridge-to-bridge radiotelephone installation.
Code of Federal Regulations, 2010 CFR
2010-10-01
... 47 Telecommunication 5 2010-10-01 2010-10-01 false Bridge-to-bridge radiotelephone installation. 80.1007 Section 80.1007 Telecommunication FEDERAL COMMUNICATIONS COMMISSION (CONTINUED) SAFETY AND... Bridge-to-Bridge Act § 80.1007 Bridge-to-bridge radiotelephone installation. Use of the bridge-to-bridge...
In vitro validation of a shape-optimized fiber-reinforced dental bridge.
Chen, YungChung; Li, Haiyan; Fok, Alex
2011-12-01
To improve its mechanical performance, structural optimization had been used in a previous study to obtain an alternative design for a 3-unit inlay-retained fiber-reinforced composite (FRC) dental bridge. In that study, an optimized layout of the FRC substructure had been proposed to minimize stresses in the veneering composite and interfacial stresses between the composite and substructure. The current work aimed to validate in vitro the improved fracture resistance of the optimized design. All samples for the 3-unit inlay-retained FRC dental bridge were made with glass-fibers (FibreKor) as the substructure, surrounded by a veneering composite (GC Gradia). Two different FRC substructure designs were prepared: a conventional (n=20) and an optimized design (n=21). The conventional design was a straight beam linking one proximal box to the other, while the optimized design was a curved beam following the lower outline of the pontic. All samples were loaded to 400N on a universal test machine (MTS 810) with a loading speed of 0.2mm/min. During loading, the force and displacement were recorded. Meanwhile, a two-channel acoustic emission (AE) system was used to monitor the development of cracks during loading. The load-displacement curves of the two groups displayed significant differences. For the conventional design, there were numerous drops in load corresponding to local damage of the sample. For the optimized design, the load curves were much smoother. Cracks were clearly visible on the surface of the conventional group only, and the directions of those cracks were perpendicular to those of the most tensile stresses. Results from the more sensitive AE measurement also showed that the optimized design had, on average, fewer cracking events: 38 versus 2969 in the conventional design. The much lower number of AE events and smoother load-displacement curves indicated that the optimized FRC bridge design had a higher fracture resistance. It is expected that the optimized design will significantly improve the clinical performance of FRC bridges. Copyright © 2011 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.
Synthesis of 5- and 6-Carboxy-X-rhodamines
2008-01-01
An efficient route is reported to 5- and 6-carboxy-X-rhodamines (compounds 1 and 2) that contain multiple n-propylene or γ,γ-dimethylpropylene groups bridging terminal nitrogen atoms and the central xanthene core. Gram quantities of these dyes are synthesized from inexpensive starting materials. The isolated products are activated by selective transformation of the carboxylic acid group into N-hydroxysuccinimidyl esters in situ and then conjugated with an amino group of a molecule of interest. PMID:18837556
Two-photon or higher-order absorbing optical materials and methods of use
NASA Technical Reports Server (NTRS)
Perry, Joseph (Inventor); Marder, Seth (Inventor)
2001-01-01
Compositions capable of simultaneous two-photon absorption and higher order absorptivities are disclosed. Many of these compositions are compounds satisfying the formulae D-.PI.-D, A-.PI.-A, D-A-D and A-D-A, wherein D is an electron donor group, A is an electron acceptor group and .PI. comprises a bridge of .pi.-conjugated bonds connecting the electron donor groups and electron acceptor groups. In A-D-A and D-A-D compounds, the .pi. bridge is substituted with electron donor groups and electron acceptor groups, respectively. Also disclosed are methods that generate an electronically excited state of a compound, including those satisfying one of these formulae. The electronically excited state is achieved in a method that includes irradiating the compound with light. Then, the compound is converted to a multi-photon electronically excited state upon simultaneous absorption of at least two photons of light. The sum of the energies of all of the absorbed photons is greater than or equal to the transition energy from a ground state of the compound to the multi-photon excited state. The energy of each absorbed photon is less than the transition energy between the ground state and the lowest single-photon excited state of the compound is less than the transition energy between the multi-photon excited state and the ground state.
Effects of Weaning and Spatial Enrichment on Behavior of Turkish Saanen Goat Kids.
Tölü, Cemil; Göktürk, Semra; Sava, Türker
2016-06-01
As is in all economic activities, the highest yield per unit area is the main goal in animal production, while addressing the temperamental needs of animals often is ignored. Animal welfare is not only an ethical fact; it also has an economic value. Spatial environmental enrichment contributes positively to animal welfare by addressing their behavioral and mental requirements. The present study was conducted to determine the effects of weaning and spatial environmental arrangements on behaviors of goat-kids. Experimental groups were arranged in structured and unstructured spatial environments. Roughage feeder, semi-automatic concentrate feeder, bunk, bridge, and wood block were placed in the structured environment. No equipment was placed in the unstructured environment and paddock sides were enclosed with an iron sheet to prevent bipedal stance and to provide environmental isolation. In the study 10 male and 10 female Turkish Saanen goat kids were used in each group. Spatial environmental arrangements did not have significant impacts on the growth performance of kids (p>0.05). All objects in the structured group were accepted by the kids. Average use ratios of roughage feeder, semi-automatic concentrate feeder, bunk, bridge and wood block were observed as 19.3%, 14.0%, 12.6%, 3.8%, and 0.7%, respectively. There were significant differences between before- and after-weaning in use of all objects except for underneath bridge (p≤0.05). Concentrate feed consumption, locomotion, and resting behaviors in kids showed significant differences by structural group and growth period. Roughage consumption was similar between groups, while it differed by growth period (p≤0.05). Interaction frequency was significantly higher in structured group (p = 0.0023). Playing behavior significantly differentiated based on the growth period rather than on groups (p≤0.05). Playing behavior significantly decreased after weaning. Abnormal oral activity was significantly higher in the structured group before weaning (p≤0.05). Despite there being no installations facilitating climbing and bipedal stance, the kids of the unstructured group were able to exhibit 1/3 as much bipedal stance behavior as the kids of the structured group through leaning over slippery paddock wall or over their groupmates. Bipedal stance behavior of unstructured group was similar before and after weaning, while bipedal stance behavior before weaning was about 2 times that of after weaning in structured group. It was concluded that unstructured environmental arrangement limited the behavior repertoire of the goat kids.
Effects of Weaning and Spatial Enrichment on Behavior of Turkish Saanen Goat Kids
Tölü, Cemil; Göktürk, Semra; Sava, Türker
2016-01-01
As is in all economic activities, the highest yield per unit area is the main goal in animal production, while addressing the temperamental needs of animals often is ignored. Animal welfare is not only an ethical fact; it also has an economic value. Spatial environmental enrichment contributes positively to animal welfare by addressing their behavioral and mental requirements. The present study was conducted to determine the effects of weaning and spatial environmental arrangements on behaviors of goat-kids. Experimental groups were arranged in structured and unstructured spatial environments. Roughage feeder, semi-automatic concentrate feeder, bunk, bridge, and wood block were placed in the structured environment. No equipment was placed in the unstructured environment and paddock sides were enclosed with an iron sheet to prevent bipedal stance and to provide environmental isolation. In the study 10 male and 10 female Turkish Saanen goat kids were used in each group. Spatial environmental arrangements did not have significant impacts on the growth performance of kids (p>0.05). All objects in the structured group were accepted by the kids. Average use ratios of roughage feeder, semi-automatic concentrate feeder, bunk, bridge and wood block were observed as 19.3%, 14.0%, 12.6%, 3.8%, and 0.7%, respectively. There were significant differences between before- and after-weaning in use of all objects except for underneath bridge (p≤0.05). Concentrate feed consumption, locomotion, and resting behaviors in kids showed significant differences by structural group and growth period. Roughage consumption was similar between groups, while it differed by growth period (p≤0.05). Interaction frequency was significantly higher in structured group (p = 0.0023). Playing behavior significantly differentiated based on the growth period rather than on groups (p≤0.05). Playing behavior significantly decreased after weaning. Abnormal oral activity was significantly higher in the structured group before weaning (p≤0.05). Despite there being no installations facilitating climbing and bipedal stance, the kids of the unstructured group were able to exhibit 1/3 as much bipedal stance behavior as the kids of the structured group through leaning over slippery paddock wall or over their groupmates. Bipedal stance behavior of unstructured group was similar before and after weaning, while bipedal stance behavior before weaning was about 2 times that of after weaning in structured group. It was concluded that unstructured environmental arrangement limited the behavior repertoire of the goat kids. PMID:26954169
Yang, Ming; Zhang, Chunye; Zhang, Michael Z; Zhang, Shuping
2017-02-23
Avian β-defensins (AvBD) possess broad-spectrum antimicrobial, LPS neutralizing and chemotactic properties. AvBD-12 is a chemoattractant for avian immune cells and mammalian dendritic cells (JAWSII) - a unique feature that is relevant to the applications of AvBDs as chemotherapeutic agents in mammalian hosts. To identify the structural components essential to various biological functions, we have designed and evaluated seven AvBD analogues. In the first group of analogues, the three conserved disulfide bridges were eliminated by replacing cysteines with alanine and serine residues, peptide hydrophobicity and charge were increased by changing negatively charged amino acid residues to hydrophobic (AvBD-12A1) or positively charged residues (AvBD-12A2 and AvBD-12A3). All three analogues in this group showed improved antimicrobial activity, though AvBD-12A3, with a net positive charge of +9, hydrophobicity of 40% and a predicted CCR2 binding domain, was the most potent antimicrobial peptide. AvBD-12A3 also retained more than 50% of wild type chemotactic activity. In the second group of analogues (AvBD-12A4 to AvBD-12A6), one to three disulfide bridges were removed via substitution of cysteines with isosteric amino acids. Their antimicrobial activity was compromised and chemotactic activity abolished. The third type of analogue was a hybrid that had the backbone of AvBD-12 and positively charged amino acid residues AvBD-6. The antimicrobial and chemotactic activities of the hybrid resembled that of AvBD-6 and AvBD-12, respectively. While the net positive charge and charge distribution have a dominating effect on the antimicrobial potency of AvBDs, the three conserved disulfide bridges are essential to the chemotactic property and the maximum antimicrobial activity. Analogue AvBD-12A3 with a high net positive charge, a moderate degree of hydrophobicity and a CCR2-binding domain can serve as a template for the design of novel antimicrobial peptides with chemotactic property and salt resistance.
Cardiac transplantation after bridged therapy with continuous flow left ventricular assist devices.
Deo, Salil V; Sung, Kiick; Daly, Richard C; Shah, Ishan K; Altarabsheh, Salah E; Stulak, John M; Joyce, Lyle D; Boilson, Barry A; Kushwaha, Sudhir S; Park, Soon J
2014-03-01
Cardiac transplantation is an effective surgical therapy for end-stage heart failure. Patients (pts) may need to be bridged with a continuous flow left ventricular assist device (CF-LVAD) while on the transplant list as logistic factors like organ availability are unknown. Cardiac transplantation post-LVAD can be a surgically challenging procedure and outcome in these pts is perceived to be poorer based on experience with earlier generation pulsatile flow pumps. Data from a single institution comparing these pts with those undergoing direct transplantation in the present era of continuous flow device therapy are limited. Evaluate results of cardiac transplantation in pts bridged with a CF-LVAD (BTx) and compare outcomes with pts undergoing direct transplantation (Tx) in a single institution. From June 2007 till January 2012, 106 pts underwent cardiac transplantation. Among these, 37 (35%) pts (51±11 years; 85% male) were bridged with a CF-LVAD (BTx), while 70 (65%) comprised the Tx group (53±12 years; 72% males). The median duration of LVAD support was 227 (153,327) days. During the period of LVAD support, 10/37 (27%) pts were upgraded to status 1A and all were successfully transplanted. Median hospital stay in the BTx (14 days) was slightly longer than the Tx group (12 days) but not statistically significant (p=0.21). In-hospital mortality in the BTx (5%) and Tx (1%) were comparable (p=0.25). Estimated late survival in the BTx cohort was 94±7, 90±10 and 83±16% at the end of one, two and three years, respectively which was comparable to 97±4%, 93±6% and 89±9% for the Tx group (p=0.50). Cardiac transplantation after LVAD implant can be performed with excellent results. Patients can be supported on the left ventricular assist device even for periods close to a year with good outcome after cardiac transplantation. Copyright © 2013 Australian and New Zealand Society of Cardiac and Thoracic Surgeons (ANZSCTS) and the Cardiac Society of Australia and New Zealand (CSANZ). Published by Elsevier B.V. All rights reserved.
Characterization of the NTPR and BD1 interacting domains of the human PICH-BEND3 complex.
Pitchai, Ganesha P; Hickson, Ian D; Streicher, Werner; Montoya, Guillermo; Mesa, Pablo
2016-08-01
Chromosome integrity depends on DNA structure-specific processing complexes that resolve DNA entanglement between sister chromatids. If left unresolved, these entanglements can generate either chromatin bridging or ultrafine DNA bridging in the anaphase of mitosis. These bridge structures are defined by the presence of the PICH protein, which interacts with the BEND3 protein in mitosis. To obtain structural insights into PICH-BEND3 complex formation at the atomic level, their respective NTPR and BD1 domains were cloned, overexpressed and crystallized using 1.56 M ammonium sulfate as a precipitant at pH 7.0. The protein complex readily formed large hexagonal crystals belonging to space group P6122, with unit-cell parameters a = b = 47.28, c = 431.58 Å and with one heterodimer in the asymmetric unit. A complete multiwavelength anomalous dispersion (MAD) data set extending to 2.2 Å resolution was collected from a selenomethionine-labelled crystal at the Swiss Light Source.
Sexual risk and bridging behaviors among young people in Hai Phong, Vietnam.
Duong, Cong Thanh; Nguyen, Tran Hien; Hoang, Thi Thanh Ha; Nguyen, Van Vi; Do, Thi Minh Nguyet; Pham, Van Han; Detels, Roger
2008-07-01
The risk of the HIV epidemic spreading from high-risk groups to the general population in Vietnam depends on sexual risk and bridging behaviors between high- and low-risk individuals. A cross-sectional study was used to describe sexual activities of youth aged 18-29 years. Nearly half (41.4%) were sexually active. Premarital sex was reported by 43.3% of them; 78.3% of sexually active males and 13.5% of sexually active females. Multiple sex partners were reported by 31.0%; 56.7% of males and 9.2% of females. Almost 27% of males and 5% of females engaged in sexual bridging behaviors. Being unmarried was significantly associated with having sex with non-regular partners. Being unmarried and early age at first intercourse were associated with having sex with a sex worker. Consistent condom use was high with commercial sex workers but low with regular partners. Education to delay early sexual debut, increased employment, and strategies to inform young sexually active people to adopt safer behaviors are urgently needed.
Wasserman, Michael R.; Pulk, Arto; Zhou, Zhou; Altman, Roger B.; Zinder, John C.; Green, Keith D.; Garneau-Tsodikova, Sylvie; Doudna Cate, Jamie H.; Blanchard, Scott C.
2015-01-01
Dynamic remodelling of intersubunit bridge B2, a conserved RNA domain of the bacterial ribosome connecting helices 44 (h44) and 69 (H69) of the small and large subunit, respectively, impacts translation by controlling intersubunit rotation. Here we show that aminoglycosides chemically related to neomycin—paromomycin, ribostamycin and neamine—each bind to sites within h44 and H69 to perturb bridge B2 and affect subunit rotation. Neomycin and paromomycin, which only differ by their ring-I 6′-polar group, drive subunit rotation in opposite directions. This suggests that their distinct actions hinge on the 6′-substituent and the drug's net positive charge. By solving the crystal structure of the paromomycin–ribosome complex, we observe specific contacts between the apical tip of H69 and the 6′-hydroxyl on paromomycin from within the drug's canonical h44-binding site. These results indicate that aminoglycoside actions must be framed in the context of bridge B2 and their regulation of subunit rotation. PMID:26224058
Crossing the Bridge from GCSE To A-Level Chemistry: What Do the Students Think?
ERIC Educational Resources Information Center
Winn, Pauline
1998-01-01
Reports on a study that explores student perspectives on the transfer to A-level chemistry from GCSE chemistry. Explores the attitudes of groups of new A-level chemistry students at a sixth-form college. (DDR)
ERIC Educational Resources Information Center
Reynolds, Ruth; Lane, Sue
2009-01-01
In an attempt to develop tolerance and acceptance of other cultural groups, teacher educators from the University of Newcastle worked with members of the local African community and teachers from a local school to develop a Creative Arts and Geography program for young school children (aged 7-9 years). The program developed put together the…
ERIC Educational Resources Information Center
Association for Quality and Participation, Cincinnati, OH.
Among the 96 papers presented at this conference are the following: "Team Building Techniques that Get Results" (Berg); "The Subtleties of Communication in Small Group Meetings" (Henry); "Feedback--Its Role in Team Building" (Lucas); "Group Dynamics--Success through Interaction" (Manning, Johnson); "The Able-Bodied Handicapped: Bridging the Gap"…
Kruse, A; Jung, R E; Nicholls, F; Zwahlen, R A; Hämmerle, C H F; Weber, F E
2011-05-01
A comparison of synthetic hydroxyapatite/silica oxide, xenogenic hydroxyapatite-based bone substitute materials with empty control sites in terms of bone regeneration enhancement in a rabbit calvarial four non-critical-sized defect model. In each of six rabbits, four bicortical calvarial bone defects were generated. The following four treatment modalities were randomly allocated: (1) empty control site, (2) synthetic hydroxyapatite/silica oxide-based (HA/SiO) test granules, (3) xenogenic hydroxyapatite -based granules, (4) synthetic hydroxyapatite/silica oxide -based (HA/SiO) test two granules. The results of the latter granules have not been reported due to their size being three times bigger than the other two granule types. After 4 weeks, the animals were sacrificed and un-decalcified sections were obtained for histological analyses. For statistical analysis, the Kruskal-Wallis test was applied (P<0.05). Histomorphometric analysis showed an average area fraction of newly formed bone of 12.32±10.36% for the empty control, 17.47±6.42% for the xenogenic hydroxyapatite -based granules group, and 21.2±5.32% for the group treated with synthetic hydroxyapatite/silica oxide -based granules. Based on the middle section, newly formed bone bridged the defect to 38.33±37.55% in the empty control group, 54.33±22.12% in the xenogenic hydroxyapatite -based granules group, and to 79±13.31% in the synthetic hydroxyapatite/silica oxide -based granules group. The bone-to-bone substitute contact was 46.38±18.98% for the xenogenic and 59.86±14.92% for the synthetic hydroxyapatite/silica oxide-based granules group. No significant difference in terms of bone formation and defect bridging could be detected between the two bone substitute materials or the empty defect. There is evidence that the synthetic hydroxyapatite/silica oxide granules provide comparable results with a standard xenogenic bovine mineral in terms of bone formation and defect bridging in non-critical size defects. © 2010 John Wiley & Sons A/S.
Vinci, John C; Ferrer, Ivonne M; Guterry, Nathan W; Colón, Verónica M; Destino, Joel F; Bright, Frank V; Colón, Luis A
2015-09-01
We synthesized sub-10 nm carbon nanoparticles (CNPs) consistent with photoluminescent carbon dots (C-dots) from carbon fiber starting material. The production of different C-dots fractions was monitored over seven days. During the course of the reaction, one fraction of C-dots species with relatively high photoluminescence was short-lived, emerging during the first hour of reaction but disappearing after one day of reaction. Isolation of this species during the first hour of the reaction was crucial to obtaining higher-luminescent C-dots species. When the reaction proceeded for one week, the appearance of larger nanostructures was observed over time, with lateral dimensions approaching 200 nm. The experimental evidence suggests that these larger species are formed from small C-dot nanoparticles bridged together by sulfur-based moieties between the C-dot edge groups, as if the C-dots polymerized by cross-linking the edge groups through sulfur bridges. Their size can be tailored by controlling the reaction time. Our results highlight the variety of CNP products, from sub-10 nm C-dots to ~200 nm sulfur-containing carbon nanostructures, that can be produced over time during the oxidation reaction of the graphenic starting material. Our work provides a clear understanding of when to stop the oxidation reaction during the top-down production of C-dots to obtain highly photoluminescent species or a target average particle size.
Crystal structures of two cross-bridged chromium(III) tetraazamacrocycles
Prior, Timothy J.; Maples, Danny L.; Maples, Randall D.; Hoffert, Wesley A.; Parsell, Trenton H.; Silversides, Jon D.; Archibald, Stephen J.; Hubin, Timothy J.
2014-01-01
The crystal structure of dichlorido(4,10-dimethyl-1,4,7,10-tetraazabicyclo[5.5.2]tetradecane)chromium(III) hexafluoridophosphate, [CrCl2(C12H26N4)]PF6, (I), has monoclinic symmetry (space group P21/n) at 150 K. The structure of the related dichlorido(4,11-dimethyl-1,4,8,11-tetraazabicyclo[6.6.2]hexadecane)chromium(III) hexafluoridophosphate, [CrCl2(C14H30N4)]PF6, (II), also displays monoclinic symmetry (space group P21/c) at 150 K. In each case, the CrIII ion is hexacoordinate with two cis chloride ions and two non-adjacent N atoms bound cis equatorially and the other two non-adjacent N atoms bound trans axially in a cis-V conformation of the macrocycle. The extent of the distortion from the preferred octahedral coordination geometry of the CrIII ion is determined by the parent macrocycle ring size, with the larger cross-bridged cyclam ring in (II) better able to accommodate this preference and the smaller cross-bridged cyclen ring in (I) requiring more distortion away from octahedral geometry. PMID:25309165
Developing Engineering and Science Process Skills Using Design Software in an Elementary Education
NASA Astrophysics Data System (ADS)
Fusco, Christopher
This paper examines the development of process skills through an engineering design approach to instruction in an elementary lesson that combines Science, Technology, Engineering, and Math (STEM). The study took place with 25 fifth graders in a public, suburban school district. Students worked in groups of five to design and construct model bridges based on research involving bridge building design software. The assessment was framed around individual student success as well as overall group processing skills. These skills were assessed through an engineering design packet rubric (student work), student surveys of learning gains, observation field notes, and pre- and post-assessment data. The results indicate that students can successfully utilize design software to inform constructions of model bridges, develop science process skills through problem based learning, and understand academic concepts through a design project. The final result of this study shows that design engineering is effective for developing cooperative learning skills. The study suggests that an engineering program offered as an elective or as part of the mandatory curriculum could be beneficial for developing students' critical thinking, inter- and intra-personal skills, along with an increased their understanding and awareness for scientific phenomena. In conclusion, combining a design approach to instruction with STEM can increase efficiency in these areas, generate meaningful learning, and influence student attitudes throughout their education.
Bock, Lars V.; Blau, Christian; Vaiana, Andrea C.; Grubmüller, Helmut
2015-01-01
During ribosomal translation, the two ribosomal subunits remain associated through intersubunit bridges, despite rapid large-scale intersubunit rotation. The absence of large barriers hindering rotation is a prerequisite for rapid rotation. Here, we investigate how such a flat free-energy landscape is achieved, in particular considering the large shifts the bridges undergo at the periphery. The dynamics and energetics of the intersubunit contact network are studied using molecular dynamics simulations of the prokaryotic ribosome in intermediate states of spontaneous translocation. Based on observed occupancies of intersubunit contacts, residues were grouped into clusters. In addition to the central contact clusters, peripheral clusters were found to maintain strong steady interactions by changing contacts in the course of rotation. The peripheral B1 bridges are stabilized by a changing contact pattern of charged residues that adapts to the rotational state. In contrast, steady strong interactions of the B4 bridge are ensured by the flexible helix H34 following the movement of protein S15. The tRNAs which span the subunits contribute to the intersubunit binding enthalpy to an almost constant degree, despite their different positions in the ribosome. These mechanisms keep the intersubunit interaction strong and steady during rotation, thereby preventing dissociation and enabling rapid rotation. PMID:26109353
NASA Astrophysics Data System (ADS)
Godinez-Azcuaga, Valery F.; Inman, Daniel J.; Ziehl, Paul H.; Giurgiutiu, Victor; Nanni, Antonio
2011-04-01
This paper presents the most recent advances in the development of a self powered wireless sensor network for steel and concrete bridges monitoring and prognosis. This five-year cross-disciplinary project includes development and deployment of a 4-channel acoustic emission wireless node powered by structural vibration and wind energy harvesting modules. In order to accomplish this ambitious goal, the project includes a series of tasks that encompassed a variety of developments such as ultra low power AE systems, energy harvester hardware and especial sensors for passive and active acoustic wave detection. Key studies on acoustic emission produced by corrosion on reinforced concrete and by crack propagation on steel components to develop diagnosis tools and models for bridge prognosis are also a part of the project activities. It is important to mention that the impact of this project extends beyond the area of bridge health monitoring. Several wireless prototype nodes have been already requested for applications on offshore oil platforms, composite ships, combat deployable bridges and wind turbines. This project was awarded to a joint venture formed by Mistras Group Inc, Virginia Tech, University of South Carolina and University of Miami and is sponsored through the NIST-TIP Grant #70NANB9H007.
Zhang, Li-Hong; Jiang, Tao; Wu, Lian-Bin; Wan, Jun-Hua; Chen, Chih-Hsien; Pei, Yong-Bing; Lu, Hua; Deng, Yuan; Bian, Gao-Feng; Qiu, Hua-Yu; Lai, Guo-Qiao
2012-06-01
A series of linear 2,5-tetraphenylsilole-vinylene-type polymers were successfully synthesized for the first time. The tetraphenylsilole moieties were linked at their 2,5-positions through a vinylene bridge with p-dialkoxybenzenes to obtain polymer PSVB and with 3,6-carbazole to obtain polymer PSVC. For comparison, 2,5-tetraphenylsilole-ethyne-type polymer PSEB was also synthesized, in which the vinylene bridge of PSVB was replaced with an ethyne bridge. Very interestingly, the bridging group (vinylene or ethyne) had a significant effect on the photophysical properties of the corresponding polymers. The fluorescence peak of PSEB at 504 nm in solution originated from the emission of its silole moieties, whereas PSVB and PSVC emitted yellow light and no blueish-green emission from the silole moieties was observed, thus demonstrating that the emissions of PSVB and PSVC were due to their polymer backbones. More importantly, the 2,5-tetraphenylsilole-ethyne polymer exhibited a pronounced aggregation-enhanced emission (AEE) effect but the 2,5-tetraphenylsilole-vinylene polymer was AEE-inactive. Moreover, both AEE-active 2,5-tetraphenylsilole-ethyne polymer and AEE-inactive 2,5-tetraphenylsilole-vinylene polymers were successfully applied as fluorescent chemosensors for the detection of explosive compounds. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Keilhoff, Gerburg; Prätsch, Florian; Wolf, Gerald; Fansa, Hisham
2005-01-01
Defects of peripheral nerves are bridged with autologous nerve grafts. Tissue-engineered nerve grafts offer a laboratory-based alternative to overcome limited donor nerve availability. Our objective was to evaluate whether a graft made from acellular muscle enriched with cultivated Schwann cells can bridge extra large gaps where conventional conduits usually fail. Our well-established rat sciatic nerve model was used with an increased gap length of 50 mm. The conduits consisted of freeze-thawed or chemically extracted homologous acellular rat rectus muscles and implanted Schwann cells. Autologous nerve grafts were used for control purposes. Biocompatibility of the grafts was demonstrated by Schwann cell settlement, revascularization, and macrophage recruitment. After 12 weeks regeneration was assessed clinically, histologically, and morphometrically. The control group showed superior results regarding axon counts, histologic appearance, and functional recovery compared with the muscle grafts. The chemically extracted conduits completely failed to support nerve regeneration. They were not stable enough to bridge longer nerve gaps with an expanded regeneration time. On the basis of morphological parameters freeze-thawed muscle grafts were, however, able to support peripheral nerve regeneration even over the extralong distance of 50 mm, and therefore are of potential benefit for new therapeutic strategies.
Neves-Petersen, Maria Teresa; Snabe, Torben; Klitgaard, Søren; Duroux, Meg; Petersen, Steffen B
2006-02-01
Photonic induced immobilization is a novel technology that results in spatially oriented and spatially localized covalent coupling of biomolecules onto thiol-reactive surfaces. Immobilization using this technology has been achieved for a wide selection of proteins, such as hydrolytic enzymes (lipases/esterases, lysozyme), proteases (human plasminogen), alkaline phosphatase, immunoglobulins' Fab fragment (e.g., antibody against PSA [prostate specific antigen]), Major Histocompability Complex class I protein, pepsin, and trypsin. The reaction mechanism behind the reported new technology involves "photonic activation of disulfide bridges," i.e., light-induced breakage of disulfide bridges in proteins upon UV illumination of nearby aromatic amino acids, resulting in the formation of free, reactive thiol groups that will form covalent bonds with thiol-reactive surfaces (see Fig. 1). Interestingly, the spatial proximity of aromatic residues and disulfide bridges in proteins has been preserved throughout molecular evolution. The new photonic-induced method for immobilization of proteins preserves the native structural and functional properties of the immobilized protein, avoiding the use of one or more chemical/thermal steps. This technology allows for the creation of spatially oriented as well as spatially defined multiprotein/DNA high-density sensor arrays with spot size of 1 microm or less, and has clear potential for biomedical, bioelectronic, nanotechnology, and therapeutic applications.
Hernández-Molina, María; Ruiz-Pérez, Catalina; López, Trinidad; Lloret, Francesc; Julve, Miguel
2003-09-08
The novel gadolinium(III) complex of formula [Gd(2)(mal)(3)(H(2)O)(6)] (1) (H(2)mal = 1,3-propanedioic acid) has been prepared and characterized by X-ray diffraction analysis. Crystal data for 1: monoclinic, space group I2/a, a = 11.1064(10) A, b = 12.2524(10) A, c =13.6098(2) A, beta = 92.925(10) degrees, U = 1849.5(3) A(3), Z = 4. Compound 1 is a three-dimensional network made up of malonate-bridged gadolinium(III) ions where the malonate exhibits two bridging modes, eta(5)-bidentate + unidentate and eta(3):eta(3) + bis(unidentate). The gadolinium atom is nine-coordinate with three water molecules and six malonate oxygen atoms from three malonate ligands forming a distorted monocapped square antiprism. The shortest metal-metal separations are 4.2763(3) A [through the oxo-carboxylate bridge] and 6.541(3) A [through the carboxylate in the anti-syn coordination mode]. The value of the angle at the oxo-carboxylate atom is 116.8(2) degrees. Variable-temperature magnetic susceptibility measurements reveal the occurrence of a significant ferromagnetic interaction through the oxo-carboxylate pathway (J = +0.048(1) cm(-1), H = -JS(Gd(1)) x S(Gd(1a))).
Zhang, Yan; Ma, Defu; Cui, Renzhe; Haregot Hilawe, Esayas; Chiang, Chifa; Hirakawa, Yoshihisa; Hu, Yonghua; Wang, Peiyu; Iso, Hiroyasu; Aoyama, Atsuko
2016-05-01
Non-communicable diseases (NCDs) are the major public health concerns in China. However, little has been known yet about the background social factors that influence lifestyles as possible NCD risk factors. This qualitative study aimed to explore facilitators and barriers of adopting healthy lifestyles among residents in a rural community of China. Three age-stratified focus group discussions (FGDs) were conducted in Fangshan district of Beijing in 2013. A FGD guide was designed to elicit the participants' perception and experience regarding their lifestyles. The audio-records were transcribed, and data were qualitatively analyzed through thematic approach. Through social capital framework with bonding, bridging, and linking classifications, we identified the following facilitators and barriers to adopt healthy lifestyles. (1) Facilitators: mutual support from family/friends and motivation to participate in regular exercises (bonding); cooperative relationships with community health workers (bridging); and nationwide high level of healthy lifestyle awareness (linking). (2) Barriers: negative influence from family/friends, insufficient support from family/friends, peer pressure and tolerance towards unhealthy lifestyles (bonding); insufficient support from health professionals (bridging); and inequity in allocation of public resources (linking). This study revealed that bonding, bridging and linking social capital would work as facilitators and barriers to adopt healthy lifestyles among rural residents in China.
An organizational typology for self-help groups.
Schubert, M A; Borkman, T J
1991-10-01
Those investigating the nature and functioning of self-help groups have been handicapped by the lack of a conceptual framework to bridge the diversity among such groups as well as to clarify the boundaries between consumer-owned and professionally owned groups. This paper describes a typology that classifies local units of these groups in terms of differences and similarities in their organizational structures. Rooted in organizational theory, it has two dimensions: external dependence upon resources and internal extent of experiential authority. Using it, the authors identified five types of groups, referred to as Unaffiliated, Federated, Affiliated, Hybrid, and Managed. The typology was validated with actual groups.
Enhancing the safety of visually impaired travelers in and around transit stations.
DOT National Transportation Integrated Search
2016-01-01
The TechBridge World research group at Carnegie Mellon University has been exploring specific needs and constraints encountered by blind or visually impaired (B/VI) adults when using transit stations. Through this work, the findings indicated a stron...
Code of Federal Regulations, 2012 CFR
2012-07-01
... beneath the surface of the earth or within a cliff or ledge and which is large enough to permit a person... and communication bridges between various socioeconomic groups; and further the administration... General Prohibitions § 261.2 Definitions. The following definitions apply to this part: Administrative...
Code of Federal Regulations, 2014 CFR
2014-07-01
... beneath the surface of the earth or within a cliff or ledge and which is large enough to permit a person... and communication bridges between various socioeconomic groups; and further the administration... General Prohibitions § 261.2 Definitions. The following definitions apply to this part: Administrative...
Code of Federal Regulations, 2010 CFR
2010-10-01
... located on a ship's navigational bridge or main control station operating on a specified frequency which... Union Radiocommunication (ITU-R) Sector, used to establish contact with a station or group of stations... (ITU), Place des Nations, CH-1211 Geneva 20, Switzerland. Direction finder (radio compass). Apparatus...
Code of Federal Regulations, 2011 CFR
2011-10-01
... located on a ship's navigational bridge or main control station operating on a specified frequency which... Union Radiocommunication (ITU-R) Sector, used to establish contact with a station or group of stations... (ITU), Place des Nations, CH-1211 Geneva 20, Switzerland. Direction finder (radio compass). Apparatus...
Remote sensing research activities related to academic institutions
NASA Technical Reports Server (NTRS)
Myers, V. I.
1980-01-01
The role of research in the educational setting is discussed. Curriculum developments for integrating teaching and research are described. Remote sensing technology is used as an example of bridging the gap between research and application. Recommendations are presented for strengthing research groups.
Optimizing pKa computation in proteins with pH adapted conformations.
Kieseritzky, Gernot; Knapp, Ernst-Walter
2008-05-15
pK(A) in proteins are determined by electrostatic energy computations using a small number of optimized protein conformations derived from crystal structures. In these protein conformations hydrogen positions and geometries of salt bridges on the protein surface were determined self-consistently with the protonation pattern at three pHs (low, ambient, and high). Considering salt bridges at protein surfaces is most relevant, since they open at low and high pH. In the absence of these conformational changes, computed pK(A)(comp) of acidic (basic) groups in salt bridges underestimate (overestimate) experimental pK(A)(exp), dramatically. The pK(A)(comp) for 15 different proteins with 185 known pK(A)(exp) yield an RMSD of 1.12, comparable with two other methods. One of these methods is fully empirical with many adjustable parameters. The other is also based on electrostatic energy computations using many non-optimized side chain conformers but employs larger dielectric constants at short distances of charge pairs that diminish their electrostatic interactions. These empirical corrections that account implicitly for additional conformational flexibility were needed to describe the energetics of salt bridges appropriately. This is not needed in the present approach. The RMSD of the present approach improves if one considers only strongly shifted pK(A)(exp) in contrast to the other methods under these conditions. Our method allows interpreting pK(A)(comp) in terms of pH dependent hydrogen bonding pattern and salt bridge geometries. A web service is provided to perform pK(A) computations. 2007 Wiley-Liss, Inc.
NASA Astrophysics Data System (ADS)
Gildenhuys, Johandie; Müller, Ronel; le Roex, Tanya; de Villiers, Katherine A.
2017-03-01
The crystal structures of the μ-propionato dimer and π-π dimer of ferriprotoporphyrin IX (Fe(III)PPIX) have been determined by single crystal X-ray diffraction (SCD). Both species were obtained in the presence of the synthetic 4-aminoquinoline antimalarial drug, amodiaquine (AQ). The solution that afforded the μ-propionato dimer contained AQ as a free base (i.e. with both quinoline and terminal amine nitrogen atoms neutral). On the other hand, when the diprotic salt of AQ was included in the crystallization medium, the Fe(III)PPIX π-π dimer was obtained. The structure of the μ-propionato dimer, which is the discrete structural unit that constitutes haemozoin (malaria pigment), is identical to that obtained previously in presence of chloroquine free base. We suspect that the drug, via its two available basic sites, facilitates dissociation of one of the two Fe(III)PPIX propionic acid groups to yield a propionate group that is required for reciprocal coordination of the metal centre to form the centrosymmetric dimer. On the other hand, this proton transfer is not possible when the drug is present as a diprotic salt. In this case, the π-π dimer of Fe(III)PPIX is obtained. In the current study, the π-π dimer of haemin (chloro-Fe(III)PPIX) was obtained as a DMF solvate from non-aqueous aprotic solution (dimethyl formamide and chloroform), however the π-π dimer is also known to exist in aqueous solution (as aqua- or hydroxo-Fe(III)PPIX), where it is purportedly involved in the nucleation of haemozoin. We have been able to unambiguously determine the positions of all non-hydrogen atoms, as well as locate or assign all hydrogen atoms in the structure of the π-π dimer, which was not possible in the SCD structure of haemin reported by Koenig in 1965 owing to disorder in the vinyl and methyl substituents. Interestingly, no disorder in the methyl and vinyl groups is observed in the current structure. Both the π-π and μ-propionato dimers of Fe(III)PPIX are important species in the haem detoxification pathway in the malaria parasite and other blood-feeding organisms, and the structural insight gained in this study may assist target-driven design of new chemotherapeutic agents.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Vener, M. V., E-mail: mikhail.vener@gmail.com; Odinokov, A. V.; Wehmeyer, C.
Salt bridges and ionic interactions play an important role in protein stability, protein-protein interactions, and protein folding. Here, we provide the classical MD simulations of the structure and IR signatures of the arginine (Arg)–glutamate (Glu) salt bridge. The Arg-Glu model is based on the infinite polyalanine antiparallel two-stranded β-sheet structure. The 1 μs NPT simulations show that it preferably exists as a salt bridge (a contact ion pair). Bidentate (the end-on and side-on structures) and monodentate (the backside structure) configurations are localized [Donald et al., Proteins 79, 898–915 (2011)]. These structures are stabilized by the short {sup +}N–H⋯O{sup −} bonds.more » Their relative stability depends on a force field used in the MD simulations. The side-on structure is the most stable in terms of the OPLS-AA force field. If AMBER ff99SB-ILDN is used, the backside structure is the most stable. Compared with experimental data, simulations using the OPLS all-atom (OPLS-AA) force field describe the stability of the salt bridge structures quite realistically. It decreases in the following order: side-on > end-on > backside. The most stable side-on structure lives several nanoseconds. The less stable backside structure exists a few tenth of a nanosecond. Several short-living species (solvent shared, completely separately solvated ionic groups ion pairs, etc.) are also localized. Their lifetime is a few tens of picoseconds or less. Conformational flexibility of amino acids forming the salt bridge is investigated. The spectral signature of the Arg-Glu salt bridge is the IR-intensive band around 2200 cm{sup −1}. It is caused by the asymmetric stretching vibrations of the {sup +}N–H⋯O{sup −} fragment. Result of the present paper suggests that infrared spectroscopy in the 2000–2800 frequency region may be a rapid and quantitative method for the study of salt bridges in peptides and ionic interactions between proteins. This region is usually not considered in spectroscopic studies of peptides and proteins.« less
Clerkin, Kevin J.; Naka, Yoshifumi; Mancini, Donna M.; Colombo, Paolo C.; Topkara, Veli K.
2017-01-01
Objectives This study sought to determine if obese patients had worse post-LVAD implantation outcomes and if the implantation of an LVAD allowed for weight loss. Background Obesity is a risk factor for cardiovascular disease including heart failure. Obese heart failure patients have better outcomes than those with normal weight; however obese patients have worse outcomes following heart transplantation. Methods Patients were identified in the UNOS database that underwent LVAD implantation as bridge to transplantation from May 2004 and April 2014, with follow-up through June 2014. Patients were grouped according to BMI based on the WHO classification Results Among 3,856 patients the risk of death or delisting was not significantly different between BMI groups (p=0.347). There was no increased risk of death (p=0.234) or delisting (p=0.918). The risk of complication requiring UNOS status upgrade was increased for those with Class II obesity or greater (HR 1.48, 95% CI 1.14–1.93, p=0.004), driven by increased infection and thromboembolism. Obese patients had worse post-transplant outcomes. Weight loss substantial enough to decrease BMI group was achieved by a small proportion of patients listed with Class I obesity or greater (9.6–15.5%). Conclusions Patients with obesity had similar freedom from death or delisting while on LVAD support. However, Class II obese or greater patients had an increased risk of complications requiring UNOS status upgrade compared with those with normal BMI during LVAD support and decreased post-transplant survival. Weight loss on device therapy was possible, but uncommon. Careful consideration is needed when a bridge to weight loss strategy is proposed. PMID:27614942
DOE Office of Scientific and Technical Information (OSTI.GOV)
Pan, Guirong; Schaefer, Dale W.; van Ooij, Wim J.
2010-12-03
Functional organosilanes are powerful interface-active agents that find applications as adhesion promoters as well as optical, dielectric and protective coatings. Bis-silanes are of particular interest because they are highly crosslinked leading to very robust films. In almost all applications, the water resistance of the films is a critical performance measure. Here we use neutron reflectivity to address the effect of bridging group on the hydrothermal response of bis-silane films prepared using bis[3-(triethoxysilyl) propyl]tetrasulfide and bis-[trimethoxysilylpropyl]amine. Neat and mixed films are examined as-prepared, after exposure to water vapor and then in the re-dried state. The bridging group is the key factormore » that controls the morphology and water resistance of silane films. Although bis-sulfur silane is not as condensed as bis-amino silane, bis-sulfur swells less in water because of the hydrophobic nature of bridging group. The reflectivity of bis-sulfur silane film is reversible after room-temperature water conditioning but not at 80 C, indicating chemical alternation of the film at 80 C. The water resistance of mixed silane is roughly that of both components weighted by their volume fraction. But based on the enhanced shrinkage that occurs following water-vapor conditioning of the mixed film, condensation is accelerated in the mixed silane. Regarding the precursor solution, bis-amino silane may act as a catalyst in the hydrolysis of bis-sulfur silane leading to more silanols in the solution and further condensation in the film. Variation in the structure normal to the substrate is also examined by swelling the film with d-nitrobenzene, a non-reacting swelling agent.« less
Abuhamdah, R M; Hussain, M D; Chazot, P L; Ennaceur, A
2016-10-01
Familiarity can imply a reduction of fear and anxiety, which may render learning and memory performance insensitive to NMDA receptor antagonism. Our previous study indicates that MK-801 (dizocilpine), NMDA antagonist, increased anxiety and prevented the acquisition of a spatial memory task. Here, we examined whether MK-801 will produce anxiety in mice that were familiar with the test environment. Male C57BL/6J mice were exposed, one session a day for 7days, to a 3D maze, which consisted of nine arms attached to upward inclined bridges radiating from a nonagonal platform. In this maze, high anxiety mice avoid the arms in the first sessions. One group of mice received saline (SAL) while a second group received MK-801 (MKD1), both on day one. A third group received saline in the first 3 sessions, and MK 801 in subsequent sessions (MKD4). Saline and MK-801 (0.1mg/kg) were administered intraperitoneally 30min before the test. MKD4 mice demonstrated an increase in bridge and arm visits, and reached arm/bridge entries ratio close to 1 in session 5. SAL mice also crossed frequently onto the arms, and reached a comparable ratio, but this was achieved with a lower number of arm visits. MKD1 mice demonstrated a reduced number of arm visits in each session compared to SAL and MKD4 mice. Dizocilpine produced anxiety in mice treated from day 1 of the test, but not in those treated from day 4. It also impaired habituation in animals familiar with the test environment; it produced sustained non-habituating hyperactivity. Copyright © 2016 Elsevier Inc. All rights reserved.
47 CFR 80.331 - Bridge-to-bridge communication procedure.
Code of Federal Regulations, 2011 CFR
2011-10-01
... 47 Telecommunication 5 2011-10-01 2011-10-01 false Bridge-to-bridge communication procedure. 80..., Alarm, Urgency and Safety Procedures § 80.331 Bridge-to-bridge communication procedure. (a) Vessels subject to the Bridge-to-Bridge Act transmitting on the designated navigational frequency must conduct...
47 CFR 80.331 - Bridge-to-bridge communication procedure.
Code of Federal Regulations, 2010 CFR
2010-10-01
... 47 Telecommunication 5 2010-10-01 2010-10-01 false Bridge-to-bridge communication procedure. 80..., Alarm, Urgency and Safety Procedures § 80.331 Bridge-to-bridge communication procedure. (a) Vessels subject to the Bridge-to-Bridge Act transmitting on the designated navigational frequency must conduct...
Czakler, Matthias; Puchberger, Michael; Artner, Christine; Schubert, Ulrich
The coordination polymer [Ti(O i Pr) 3 (OOCCH 2 CH 2 CH 2 C 3 N 2 H 3 )] n was prepared from 4-(imidazol-1-yl)butyric acid and titanium isopropoxide. The structure of the compound is remarkable, as the carboxylate group is coordinated in a chelating manner and no dimerization of the Ti(O i Pr) 3 groups through OR bridges was observed.
NASA Astrophysics Data System (ADS)
Wherton, Joseph; Prendergast, David
There are a variety of factors that can lead to social isolation and loneliness in old age, including decline in physical and mental health, as well as change to social environment. The Building Bridges project explores how communication technology can help older adults remain socially connected. This paper will first provide an overview of a prototype communication system designed to support peer-to-peer group interaction. A description of the user-centered design process will be provided to demonstrate the importance of involving older adults at the earliest stages. The implications for designing new technology for older adults are discussed.
Neumann, Verena
2016-01-01
A biophysical model of the excitation-contraction pathway, which has previously been validated for slow-twitch and fast-twitch skeletal muscles, is employed to investigate key biophysical processes leading to peripheral muscle fatigue. Special emphasis hereby is on investigating how the model's original parameter sets can be interpolated such that realistic behaviour with respect to contraction time and fatigue progression can be obtained for a continuous distribution of the model's parameters across the muscle units, as found for the functional properties of muscles. The parameters are divided into 5 groups describing (i) the sarcoplasmatic reticulum calcium pump rate, (ii) the cross-bridge dynamics rates, (iii) the ryanodine receptor calcium current, (iv) the rates of binding of magnesium and calcium ions to parvalbumin and corresponding dissociations, and (v) the remaining processes. The simulations reveal that the first two parameter groups are sensitive to contraction time but not fatigue, the third parameter group affects both considered properties, and the fourth parameter group is only sensitive to fatigue progression. Hence, within the scope of the underlying model, further experimental studies should investigate parvalbumin dynamics and the ryanodine receptor calcium current to enhance the understanding of peripheral muscle fatigue. PMID:27980606
Choi, Soohwan; Park, Hyung Joo
2017-10-01
To compare the complications associated with age and technique groups in patients undergoing pectus excavatum (PE) repair. The data of 994 patients who underwent PE repair from March 2011 to December 2015 were retrospectively reviewed. Mean age was 9.59 years (range 31 months-55 years), and 756 patients were men (76.1%). The age groups were defined as follows: Group 1, <5 years; Group 2, 5-9 years; Group 3, 10-14 years; Group 4, 15-17 years; Group 5, 18-19 years; Group 6, 20-24 years; and Group 7, >24 years. The technique groups were defined as follows: Group 1, patients who underwent repair with claw fixators and hinge plates; Group 2, patients who underwent repair with our 'bridge' technique. Complications were compared between age groups and technique groups. No cases of mortality occurred. Complication rates in the age groups 1-7 were 5.4%, 3.6%, 12.1%, 18.2%, 17.3%, 13.9% and 16.7%, respectively. The complication rate tripled after the age of 10. In multivariable analysis, odds ratio of Groups 4, 5 and 7 and asymmetric types were 3.04, 2.81, 2.97 and 1.70 (P < 0.01, P = 0.02, 0.03 and 0.03, respectively). The bar dislocation rate in technique Group 1 was 0.8% (6 of 780). No bar dislocations occurred in technique Group 2. Older patients have more asymmetric pectus deformity and they are also risk factors for complications following PE repair. The bridge technique provides a bar dislocation rate of 0%, even in adult patients. This procedure seems to reduce or prevent major complications following PE repair. © The Author 2017. Published by Oxford University Press on behalf of the European Association for Cardio-Thoracic Surgery. All rights reserved.
A Metaphorical Insight into Educational Planning.
ERIC Educational Resources Information Center
Inbar, Dan E.
1991-01-01
Considers educational planning as a communication of shared symbols creating intent geared toward change. Elaborates 11 groups of metaphorical images of planning (as circle, recipe, compass, map, puzzle, tree, maze, Ariadne's thread, prediction, art, and spider's web) bridging impression and expression. Relates this metaphorical analysis to…
Toward Community-Wide Interest in Other Peoples.
ERIC Educational Resources Information Center
Nostrand, Howard Lee
1981-01-01
Describes experiment called Bonjour Seattle designed to build interest in a foreign people through a citywide program of cultural and commercial events. Program built bridges between education, business and government, between an ethnic group and a community, and between the Pacific Northwest and France. (Author/BK)
To bridge the gaps between traditional mesoscale modelling and microscale modelling, the National Center for Atmospheric Research, in collaboration with other agencies and research groups, has developed an integrated urban modelling system coupled to the weather research and fore...
DOE Office of Scientific and Technical Information (OSTI.GOV)
None
Articles include: Arizona Apache tribe set to break ground on new solar project; Native leaders give tribes a voice on White House Climate Task Force; Chaninik Wind Group Pursues Innovative Solutions to native Alaska energy challenges; and sections, Message from the Director, Tracey Lebeau; On the Horizon, Sharing Knowledge, and Building Bridges.
ERIC Educational Resources Information Center
Stewart, Pearl
2011-01-01
Within the last year, two Minnesota school districts have reached agreements with the U.S. departments of Education and Justice to settle complaints of harassment brought by Somali-American parents and a civil rights group. The complaints alleged that district officials failed to take action when students made "inflammatory and…
The free energy of locking a ring: Changing a deoxyribonucleoside to a locked nucleic acid.
Xu, You; Villa, Alessandra; Nilsson, Lennart
2017-06-05
Locked nucleic acid (LNA), a modified nucleoside which contains a bridging group across the ribose ring, improves the stability of DNA/RNA duplexes significantly, and therefore is of interest in biotechnology and gene therapy applications. In this study, we investigate the free energy change between LNA and DNA nucleosides. The transformation requires the breaking of the bridging group across the ribose ring, a problematic transformation in free energy calculations. To address this, we have developed a 3-step (easy to implement) and a 1-step protocol (more efficient, but more complicated to setup), for single and dual topologies in classical molecular dynamics simulations, using the Bennett Acceptance Ratio method to calculate the free energy. We validate the approach on the solvation free energy difference for the nucleosides thymidine, cytosine, and 5-methyl-cytosine. © 2017 The Authors. Journal of Computational Chemistry Published by Wiley Periodicals, Inc. © 2017 The Authors. Journal of Computational Chemistry Published by Wiley Periodicals, Inc.
Angelstam, Per; Elbakidze, Marine; Axelsson, Robert; Dixelius, Malcolm; Törnblom, Johan
2013-03-01
There are multiple challenges regarding use and governance of landscapes' goods, functions and intangible values for ecosystem health and human well-being. One group of challenges is to measure and assess principal sustainability dimensions through performance targets, so stakeholders have transparent information about states and trends. Another group is to develop adaptive governance at multiple levels, and management of larger geographical areas across scales. Addressing these challenges, we present a framework for transdisciplinary research using multiple landscapes as place-based case studies that integrates multiple research disciplines and non-academic actors: (1) identify a suite of landscapes, and for each (2) review landscape history, (3) map stakeholders, use and non-use values, products and land use, (4) analyze institutions, policies and the system of governance, (5) measure ecological, economic, social and cultural sustainability, (6) assess sustainability dimensions and governance, and finally (7) make comparisons and synthesize. Collaboration, communication and dissemination are additional core features. We discuss barriers bridges and bridges for applying this approach.
Time-Varying, Multi-Scale Adaptive System Reliability Analysis of Lifeline Infrastructure Networks
DOE Office of Scientific and Technical Information (OSTI.GOV)
Gearhart, Jared Lee; Kurtz, Nolan Scot
2014-09-01
The majority of current societal and economic needs world-wide are met by the existing networked, civil infrastructure. Because the cost of managing such infrastructure is high and increases with time, risk-informed decision making is essential for those with management responsibilities for these systems. To address such concerns, a methodology that accounts for new information, deterioration, component models, component importance, group importance, network reliability, hierarchical structure organization, and efficiency concerns has been developed. This methodology analyzes the use of new information through the lens of adaptive Importance Sampling for structural reliability problems. Deterioration, multi-scale bridge models, and time-variant component importance aremore » investigated for a specific network. Furthermore, both bridge and pipeline networks are studied for group and component importance, as well as for hierarchical structures in the context of specific networks. Efficiency is the primary driver throughout this study. With this risk-informed approach, those responsible for management can address deteriorating infrastructure networks in an organized manner.« less
NASA Astrophysics Data System (ADS)
Liu, Chong-Bo; Wen, Hui-Liang; Tan, Sheng-Shui; Yi, Xiu-Guang
2008-05-01
Two new lanthanide coordination polymers with mixed-carboxylates, [Ln(OX)(HAPA)(H 2O)] n[Ln = Eu ( 1), Ho ( 2); H 2APA = 5-aminoisophthalic acid; OX = oxalate] were obtained by hydrothermal reactions, and characterized by single crystal X-ray diffraction, elemental analysis and IR spectra. Complexes 1 and 2 are both 3-D supramolecular structure, in which lanthanide ions are bridged by oxalate and 5-aminoisophthalate ligands forming 2-D metal-organic framework, and 2-D networks are further architectured to form 3-D supramolecular structures by hydrogen bonds. The two carboxylate groups of H 2APA ligand are all deprotonated and exhibit chelating and bridging bidentate coordination modes, respectively, and the amino group in HAPA presents - NH3+ in the titled complexes. The thermogravimetric analysis was carried out to examine the thermal stability of the titled complexes. And the photoluminescence property of 1 was investigated.
Center Director Bridges visits Disability Awareness and Action working Group Technology Fair
NASA Technical Reports Server (NTRS)
1999-01-01
Center Director Roy Bridges stops to talk to one of the vendors at the Disability Awareness and Action Working Group (DAAWG) Technology Fair being held Oct. 20-21 at Kennedy Space Center. With him at the far left is Sterling Walker, director of Engineering Development at KSC and chairman of DAAWG, and Nancie Strott, a multi-media specialist with Dynacs and chairperson of the Fair; at the right is Carol Cavanaugh, with KSC Public Services. The Fair is highlighting vendors demonstrating mobility, hearing, vision and silent disability assistive technology. The purpose is to create an awareness of the types of technology currently available to assist people with various disabilities in the workplace. The theme is that of this year's National Disability Employment Awareness Month, 'Opening Doors to Ability.' Some of the vendors participating are Canine Companions for Independence, Goodwill Industries, Accessible Structures, Division of Blind Services, Space Coast Center for Independent Living, KSC Fitness Center and Delaware North Parks Services.
Min, Chung Ki; Lee, Donghyoun; Jung, Kyung Uk; Lee, Sung Ryol; Kim, Hungdai; Chun, Ho-Kyung
2016-01-01
Purpose This study compared a subtotal colectomy to self-expandable metallic stent (SEMS) insertion as a bridge to surgery for patients with left colon-cancer obstruction. Methods Ninety-four consecutive patients with left colon-cancer obstruction underwent an emergency subtotal colectomy or elective SEMS insertion between January 2007 and August 2014. Using prospectively collected data, we performed a retrospective comparative analysis on an intention-to-treat basis. Results A subtotal colectomy and SEMS insertion were attempted in 24 and 70 patients, respectively. SEMS insertion technically failed in 5 patients (7.1%). The mean age and rate of obstruction in the descending colon were higher in the subtotal colectomy group than the SEMS group. Sex, underlying disease, American Society of Anesthesiologists physical status, and pathological stage showed no statistical difference. Laparoscopic surgery was performed more frequently in patients in the SEMS group (62 of 70, 88.6%) than in patients in the subtotal colectomy group (4 of 24, 16.7%). The overall rate of postoperative morbidity was higher in the SEMS group. No Clavien-Dindo grade III or IV complications occurred in the subtotal colectomy group, but 2 patients (2.9%) died from septic complications in the SEMS group. One patient (4.2%) in the subtotal colectomy group had synchronous cancer. The total hospital stay was shorter in the subtotal colectomy group. The median number of bowel movements in the subtotal colectomy group was twice per day at postoperative 3–6 months. Conclusion A subtotal colectomy for patients with obstructive left-colon cancer is a clinically and oncologically safer, 1-stage, surgical strategy compared to SEMS insertion as a bridge to surgery. PMID:28119864
Gonzalo, Esther; Suárez, Maria J; Serrano, Benjamin; Lozano, Jose F L
2009-12-01
Marginal discrepancies of zirconia posterior fixed dental prostheses (FDPs) fabricated using various systems have been assessed to determine the quality of the restorations and facilitate clinical use; however, studies are limited and results are ambiguous because of the sample sizes and measurement methods. The purpose of this in vitro study was to compare changes in marginal fit of posterior fixed dental prostheses of 3 zirconia systems manufactured using CAD/CAM technology and metal ceramic posterior fixed dental protheses fabricated with the conventional lost-wax technique, before and after cementation. Forty standardized master steel dies with 2 abutments simulating first mandibular premolars were fabricated to receive a posterior 3-unit FDP (from first molar to first premolar) and divided into 4 groups (n=10): Lava All-Ceramic System, Procera Bridge Zirconia, VITA In-Ceram 2000 YZ, and metal ceramic (control group). All FDPs were prepared for an internal space of 50 microm. The external marginal gap of the restorations was investigated by measuring 30 points in the middle of the buccal and lingual surfaces; therefore, 60 measurements per abutment were recorded. Measurements were made with an image analysis program on the master steel model before and after conventional cementation with a glass ionomer agent (Ketac Cem Easymix). The data obtained were statistically analyzed using 1-way ANOVA, Duncan's multiple range post hoc test, and Student's paired t test (alpha=.05). No significant differences in the vertical marginal fit before and after cementation were recorded for the analyzed groups. The marginal discrepancy of Procera abutments before and after cementation (9 +/-10 microm and 12 +/-9 microm, respectively) was less than that of the other groups. Significant differences (P=.001) were observed in marginal adaptation between Procera Bridge Zirconia and the other groups. The results of this study showed that cementation did not cause a significant increase in the vertical marginal discrepancies of the FDPs and that an internal space of 50 mum provided a high precision of fit of the restorations. The accuracy of fit achieved for the 3 zirconium oxide groups analyzed was within the range of clinical acceptance, and the discrepancies were lower than in the metal ceramic group. Procera Bridge Zirconia showed the lowest vertical discrepancies.
Guardrails for use on historic bridges: volume 2--bridge deck overhang design.
DOT National Transportation Integrated Search
2016-11-01
Bridges that are designated historic present a special challenge to bridge engineers whenever rehabilitation work or improvements are : made to the bridges. Federal and state laws protect historically significant bridges, and railings on these bridge...
Basel, Halil; Ekim, Hasan; Odabasi, Dolunay; Kiymaz, Adem; Aydin, Cemalettin; Dostbil, Aysenur
2011-07-01
Basilic vein transposition fistulas (BVTFs) and prosthetic bridge grafts (PBGs) provide good vascular access for hemodialysis. To evaluate the patency and complication rates after arteriovenous fistula formation, a concurrent series of patients was reviewed. Between September 2003 and September 2009, 147 hemodialysis access procedures were performed in 147 consecutive patients at Van Research and Training Hospital and Yuzuncu Yil University Hospital, Van, Turkey. All access procedures were planned on the basis of preoperative duplex scans of arm and forearm veins. Functional patency was defined as the ability to cannulate hemodialysis patients successfully. Primary and secondary cumulative functional patency rates of BVTFs and PBGs were determined with life-table analysis and differences were analyzed with retrospective study. Differences in revision rates, including thrombolysis thrombectomies and operative revisions, were analyzed with the Fisher exact t-test. Mean follow-up was 15 months (range, 3-24 months). Risk factors were similar between the two groups. BVTFs had better patency at 15 months. The dialysis access complications were higher in the PBG group versus BVTF group, and the PBG group had a higher infection rate than the BVTF group. The primary and secondary patency rates were superior in the BVTF group. Our data strongly support the contention that as long as the patient is a candidate for an upper arm BVTF based on anatomical criteria, BVTF always be considered before a PBG. Copyright © 2011. Published by Elsevier Inc.
47 CFR 80.163 - Operator requirements of the Bridge-to-Bridge Act.
Code of Federal Regulations, 2011 CFR
2011-10-01
... 47 Telecommunication 5 2011-10-01 2011-10-01 false Operator requirements of the Bridge-to-Bridge... Requirements § 80.163 Operator requirements of the Bridge-to-Bridge Act. Each ship subject to the Bridge-to-Bridge Act must have on board a radio operator who holds a restricted radiotelephone operator permit or...
78 FR 45863 - Drawbridge Operation Regulation; Willamette River at Portland, OR
Federal Register 2010, 2011, 2012, 2013, 2014
2013-07-30
... operating schedule that govern four Multnomah County bridges: The Broadway Bridge, mile 11.7, the Burnside Bridge, mile 12.4, the Morrison Bridge, mile 12.8, and the Hawthorne Bridge, mile 13.1, all crossing the... the Broadway Bridge, mile 11.7, the Burnside Bridge, mile 12.4, the Morrison Bridge, mile 12.8, and...
77 FR 43164 - Drawbridge Operation Regulation; Willamette River, Portland, OR
Federal Register 2010, 2011, 2012, 2013, 2014
2012-07-24
... schedule that governs four Multnomah County bridges: The Broadway Bridge, mile 11.7, the Burnside Bridge, mile 12.4, the Morrison Bridge, mile 12.8, and the Hawthorne Bridge, mile 13.1, all crossing the..., mile 11.7, the Burnside Bridge, mile 12.4, the Morrison Bridge, mile 12.8, and the Hawthorne Bridge...
47 CFR 80.163 - Operator requirements of the Bridge-to-Bridge Act.
Code of Federal Regulations, 2010 CFR
2010-10-01
... 47 Telecommunication 5 2010-10-01 2010-10-01 false Operator requirements of the Bridge-to-Bridge... Requirements § 80.163 Operator requirements of the Bridge-to-Bridge Act. Each ship subject to the Bridge-to-Bridge Act must have on board a radio operator who holds a restricted radiotelephone operator permit or...
Simple model of cable-stayed bridge deck subjected to static wind loading
NASA Astrophysics Data System (ADS)
Kang, Yi-Lung; Wang, Yang Cheng
1997-05-01
Cable-stayed bridges have been known since 18th century with aesthetics design. The structural system and the structural behavior are significantly different from those of continuous bridges. Compared to continuous bridge, cable- stayed bridges have more flexure bridge deck than those of continuous bridges.On the other hand, cable-stayed bridges have less stiffness to resist wind loading especially for lateral loads. The first considering of bridge engineering is safety. In 1940's, Tacoma Narrows Suspension Bridge destroyed by wind loading is a good example even though it is not a cable-stayed bridge. After the bridge was destroyed, a lot of research articles have been published regarding cable supported bridge subjected to wind loading. In recent days, high strength materials have been served. The bridge engineers use the advantages to expand the span length of cable-stayed bridges. Due to the span length increased and the use of high strength materials, cable- stayed bridges have more significant nonlinear behavior subjected to wind loading. In this paper, a slice bridge deck of cable-stayed bridge connected to internal support cables is considered. The deck has been considered to be subjected to lateral static wind loading. Since cables can not take compressive force, the deck has strongly nonlinear behavior even though the materials are linear elastic. Several primary load combinations have ben considered in this paper such as the bridge deck supposed to be moved horizontally without rotation or the bridge deck supposed to be moved horizontally with rotational deformation. The mathematical formulas and the numerical solutions are found and represented in graphical forms. The results can be provided to bridge designers and researchers for further study of this type of structure subjected to wind loading.
Novel highly luminescent amine-functionalized bridged silsesquioxanes
NASA Astrophysics Data System (ADS)
Pereira, Rui F. P.; Nunes, Sílvia C.; Toquer, Guillaume; Cardoso, Marita A.; Valente, Artur J. M.; Ferro, Marta C.; Silva, Maria M.; Carlos, Luís D.; Ferreira, Rute A. S.; de Zea Bermudez, Verónica
2017-12-01
Amine-functionalized bridged silsesquioxanes were synthesized from bis[(3-trimethoxysilyl)propyl] amine via a solvent-mediated route. BS-1 and BS-2 were obtained with neutral pH with sub- and stoichiometric amounts of water, respectively, and high tetrahydrofuran content. BS-3 was prepared with hyperstoichiometric water concentration, high tetrahydrofuran content and hydrochloric acid. BS-4 was synthesized with hyperstoichiometric water concentration, high ethanol content and sodium hydroxide. BS-1 and BS-2 were produced as transparent films, whereas BS-3 and BS-4 formed white powders. Face-to-face stacking of flat or folded lamellae yielded quasi-hydrophobic platelets with emission quantum yields of 0.05±0.01 (BS-1 and BS-2) or superhydrophilic onion-like nanoparticles with exciting emission quantum yields of 0.38±0.03 (BS-3) and 0.33±0.04 (BS-4), respectively. The latter two values are the largest ever reported for amine-functionalized siloxane-based hybrids lacking aromatic groups. Fast Grotthus proton hopping between =NH2+/=NH groups (BS-3) and =N-/=NH groups (BS-4), promoted by H+ and OH- ions, respectively, and aided by short amine-amine contacts provided by the onion-like morphology, account for this unique optical behavior.
Shimozu, Yuuki; Kuroda, Teruo; Tsuchiya, Tomofusa; Hatano, Tsutomu
2017-10-27
Three new ellagitannin oligomers, isorugosins H (1), I (2), and J (3), together with 11 known hydrolyzable tannins were isolated from an aqueous acetone extract of the fresh leaves of Liquidambar formosana. Their chemical structures were elucidated based on spectroscopic data and chemical conversion into known hydrolyzable tannins. The bridging mode of the valoneoyl groups between their sugar moieties has been identified only in this plant species. Additionally, the effects of the isorugosins isolated from this species on drug-resistant bacteria were evaluated and showed that isorugosin A (4) exhibited the most potent antibacterial activity against methicillin-resistant Staphylococcus aureus (MRSA). The isorugosins also had a suppressing effect on pigment formation in Pseudomonas aeruginosa. The isorugosin-protein complexes were analyzed using size-exclusion chromatography and polyacrylamide gel electrophoresis to clarify the relationship of their antibacterial properties with their protein interaction potency as hydrolyzable tannins. The results suggested that the antibacterial properties of hydrolyzable tannins are not simply a result of their binding activity to proteins, but are due to other factors such as the accessibility of polyphenolic acyl groups to bacterial membranes.
Rollin-Genetet, Françoise; Seidel, Caroline; Artells, Ester; Auffan, Mélanie; Thiéry, Alain; Vidaud, Claude
2015-12-21
The redox state of disulfide bonds is implicated in many redox control systems, such as the cysteine-cystine couple. Among proteins, ubiquitous cysteine-rich metallothioneins possess thiolate metal binding groups susceptible to metal exchange in detoxification processes. CeO2 NPs are commonly used in various industrial applications due to their redox properties. These redox properties that enable dual oxidation states (Ce(IV)/Ce(III)) to exist at their surface may act as oxidants for biomolecules. The interaction among metallothioneins, cysteine, and CeO2 NPs was investigated through various biophysical approaches to shed light on the potential effects of the Ce(4+)/Ce(3+) redox system on the thiol groups of these biomolecules. The possible reaction mechanisms include the formation of a disulfide bridge/Ce(III) complex resulting from the interaction between Ce(IV) and the thiol groups, leading to metal unloading from the MTs, depending on their metal content and cluster type. The formation of stable Ce(3+) disulfide complexes has been demonstrated via their fluorescence properties. This work provides the first evidence of thiol concentration-dependent catalytic oxidation mechanisms between pristine CeO2 NPs and thiol-containing biomolecules.
Dynamic response for structural health monitoring of the Penang (I) cable-stayed bridge
NASA Astrophysics Data System (ADS)
Mohammed, M. I.; Sulaeman, E.; Mustapha, F.
2017-03-01
The paper discusses the dynamic response of the Penang (I) cable stayed bridge structure under various moving load representing typical traffic load of the bridge. The bridge has a total span of 440 m excluding the transition bridge that assumed to be not connected structurally to the main bridge structure. The bridge that links the fast growing Pinang Island and the Malaysian Mainland Peninsula has been known to be fully utilized which leads to the construction of Penang (II) bridge and now the third one. Due to highly traffic use of the bridge that may lead to reduction of the bridge design life, the dynamic response of the bridge becomes important to predict critical part of the bridge structure elements including the main girder and the 144 stay cables. The present study reveals that, due to flexible nature of the cable stayed bridge, the moving load that interacts with the natural dynamic characteristics of the bridge, gives significant stress increment compare to proportional static load especially when the moving load is un-symmetric. For this reason, several classes of typical vehicle passing the bridge with various vehicle speeds are investigated to demonstrate their effect on the bridge displacement, internal forces and stresses. The results can be used for further fatigue assessment of the bridge.
47 CFR 80.309 - Watch required by the Bridge-to-Bridge Act.
Code of Federal Regulations, 2011 CFR
2011-10-01
... 47 Telecommunication 5 2011-10-01 2011-10-01 false Watch required by the Bridge-to-Bridge Act. 80... Safety Watches § 80.309 Watch required by the Bridge-to-Bridge Act. In addition to the watch requirement contained in § 80.148, all vessels subject to the Bridge-to-Bridge Act must keep a watch on the designated...
47 CFR 80.309 - Watch required by the Bridge-to-Bridge Act.
Code of Federal Regulations, 2010 CFR
2010-10-01
... 47 Telecommunication 5 2010-10-01 2010-10-01 false Watch required by the Bridge-to-Bridge Act. 80... Safety Watches § 80.309 Watch required by the Bridge-to-Bridge Act. In addition to the watch requirement contained in § 80.148, all vessels subject to the Bridge-to-Bridge Act must keep a watch on the designated...
Kavanagh, Dara O; Nolan, Blathnaid; Judge, Ciaran; Hyland, John M P; Mulcahy, Hugh E; O'Connell, P Ronan; Winter, Des C; Doherty, Glen A
2013-04-01
The use of self-expanding metal stents as a bridge to surgery in the setting of malignant colorectal obstruction has been advocated as an acceptable alternative to emergency surgery. However, concerns about the safety of stenting have been raised following recent randomized studies. The aim of the current study was to compare outcomes. This was an observational, comparative study. This study was conducted at a tertiary referral center and university teaching hospital. Patients with malignant colonic obstruction (n = 49) treated by either emergency surgery (n = 26) or with stent placement (n = 23) as a bridge to surgery were identified and followed. Short-term outcomes including stoma rates and postoperative morbidity and medium-term oncological outcomes were compared based on an "intention-to-treat" analysis. Patients in both groups were well matched on clinicopathological parameters. Technical and clinical successful stent deployment was achieved in 91% and 83%. This did not adversely impact cancer-specific and overall survival (log rank = nonsignificant). No difference was observed in stoma rates, primary anastomosis rates, perioperative mortality rates, or reoperation rates between the 2 groups. Significantly fewer patients underwent total colectomy in the stent group in comparison with the emergency surgery group (1/23 vs 6/26: p = 0.027). There was no difference in postoperative morbidity (59% vs 66%: p = 0.09). There was a significant reduction in readmission rates in the stent group (5/26 vs 0/23: p = 0.038). The small sample size of this study could lead to type II error. In addition, the study was nonrandomized and demonstrated a limited length of follow-up. Despite a high rate of technical and clinical success in selected patients with colonic obstruction, stenting has no impact on stoma rates. Despite concerns about the rate of stent-associated perforation, stenting does not adversely impact disease progression or survival. Future comparative trials are essential to better define the role of stenting in this setting and to ensure that we are not using costly technology to create an elective operative situation without concomitant patient benefits.
Mericli, Alexander F; Garvey, Patrick B; Giordano, Salvatore; Liu, Jun; Baumann, Donald P; Butler, Charles E
2017-03-01
The optimal strategy for abdominal wall reconstruction in the presence of a stomal-site hernia is unclear. We hypothesized that the rate of ventral hernia recurrence in patients undergoing a combined ventral hernia repair and stomal-site herniorraphy would not differ clinically from the ventral hernia recurrence rate in patients undergoing an isolated ventral hernia repair. We also hypothesized that bridged ventral hernia repairs result in worse outcomes compared with reinforced repairs, regardless of stomal hernia. We retrospectively reviewed prospectively collected data from consecutive abdominal wall reconstructions performed with acellular dermal matrix (ADM) at a single center between 2000 and 2015. We compared patients who underwent a ventral hernia repair alone (AWR) and those who underwent both a ventral hernia repair and ostomy-associated herniorraphy (AWR+O). We conducted a propensity score matched analysis to compare the outcomes between the 2 groups. Multivariable Cox proportional hazards and logistic regression models were used to study associations between potential predictive or protective reconstructive strategies and surgical outcomes. We included 499 patients (median follow-up 27.2 months; interquartile range [IQR] 12.4 to 46.6 months), 118 AWR+O and 381 AWR. After propensity score matching, 91 pairs were obtained. Ventral hernia recurrence was not statistically associated with ostomy-associated herniorraphy (adjusted hazard ratio [HR] 0.7; 95% CI 0.3 to 1.5; p = 0.34). However, the AWR+O group experienced a significantly higher percentage of surgical site occurrences (34.1%) than the AWR group (18.7%; adjusted odds ratio 2.3; 95% CI 1.4 to 3.7; p < 0.001). In the AWR group, there were significantly fewer ventral hernia recurrences when the repair was reinforced compared with bridged (5.3% vs 38.5%; p < 0.001). There was no statistically significant difference in ventral hernia recurrence between the AWR and AWR+O groups. Bridging was associated with an increased rate of hernia recurrence and should be avoided if possible. Copyright © 2016 American College of Surgeons. Published by Elsevier Inc. All rights reserved.
Vibration analysis of the Second Saikai Bridge—a concrete filled tubular (CFT) arch bridge
NASA Astrophysics Data System (ADS)
Yoshimura, Mistuhiro; Wu, Qingxiong; Takahashi, Kazuo; Nakamura, Shozo; Furukawa, Kazuyoshi
2006-02-01
Concrete-filled steel tubular (CFT) arch bridges have been rapidly developing in China since 1990. Research has focused on the static behavior, thermal stress and erection technique, however, and there has been very little research of natural vibrations and dynamic responses of these bridges. Japan's first CFT arch bridge in highway bridges, the Second Saikai Bridge, is now under construction in Nagasaki Prefecture. Furthermore, this bridge has a pedestrian bridge that is suspended under the girder, which is rare. Therefore, the natural vibration properties are examined, and the influence of pedestrian bridge structure on the natural vibration of main bridge is discussed first. Response analysis under a moving vehicle and pedestrian is carried out, and the response characteristics and response level are clarified. The natural vibrations and responses are compared to those of CFT arch bridges that have been constructed in China. Results show the fine performance of both main bridge and pedestrian bridge of the Second Saikai Bridge.
49 CFR 237.111 - Review of bridge inspection reports.
Code of Federal Regulations, 2011 CFR
2011-10-01
... 49 Transportation 4 2011-10-01 2011-10-01 false Review of bridge inspection reports. 237.111... ADMINISTRATION, DEPARTMENT OF TRANSPORTATION BRIDGE SAFETY STANDARDS Bridge Inspection § 237.111 Review of bridge inspection reports. Bridge inspection reports shall be reviewed by railroad bridge supervisors and railroad...
49 CFR 237.111 - Review of bridge inspection reports.
Code of Federal Regulations, 2010 CFR
2010-10-01
... 49 Transportation 4 2010-10-01 2010-10-01 false Review of bridge inspection reports. 237.111... ADMINISTRATION, DEPARTMENT OF TRANSPORTATION BRIDGE SAFETY STANDARDS Bridge Inspection § 237.111 Review of bridge inspection reports. Bridge inspection reports shall be reviewed by railroad bridge supervisors and railroad...
2011-03-01
Mumbai), providing terrorists with countless entry points to avoid police at bridge and tunnel crossings; limited roadways connecting the boroughs...phones, and Blackberries to communicate with themselves and their leadership during the three-day, multi-site rampage (Rabasa, Blackwill, Chalk
43 CFR 26.3 - Program purpose and objectives.
Code of Federal Regulations, 2014 CFR
2014-10-01
... sufficient size (not less than 10 enrollees) that will permit social interaction and group learning. The...- through 18-year-old males and females from all social, economic, and racial backgrounds. (3) Develop an... lasting cultural bridges between youth from various social, ethnic, racial and economic backgrounds. (c...
43 CFR 26.3 - Program purpose and objectives.
Code of Federal Regulations, 2013 CFR
2013-10-01
... sufficient size (not less than 10 enrollees) that will permit social interaction and group learning. The...- through 18-year-old males and females from all social, economic, and racial backgrounds. (3) Develop an... lasting cultural bridges between youth from various social, ethnic, racial and economic backgrounds. (c...