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Sample records for bridged isocyanato complex

  1. Dimeric uranyl complexes with bridging perrhenates.

    PubMed

    John, Gordon H; May, Iain; Sarsfield, Mark J; Collison, David; Helliwell, Madeleine

    2007-04-28

    The reaction between [UO2(ReO4)2.H(2)O] and two equivalents of either tri-n-butyl phosphine oxide (TBPO) or tri-iso-butyl phosphate (TiBP) results in the formation of [UO2(mu2-ReO4)(ReO4)(TBPO)2]2 (1) and [UO2(mu2-ReO4)(ReO4)(TiBP)2]2 (2) respectively. Both complexes crystallise as two structurally similar centrosymmetric dimers, the cores containing two uranyl moieties linked by bridging perrhenates. Two P=O donor ligands and one monodenatate perrhenate complete the pentagonal bipyramidal coordination sphere at each metal centre. Both complexes have also been characterised in the solid state by vibrational and absorption spectroscopy. Solution spectroscopic characterisation indicates that both perrhenate and phosphine oxide (1) or phosphate (2) remain coordinated, although it is not possible to state conclusively that the dimeric species remain intact. A low resolution structural study of a minor product from the reaction that yielded revealed a monomeric complex with only monodentate perrhenate coordination, [UO2(ReO4)2(H2O)(TiBP)2] (2'). These results represent the first structural evidence for the bridging coordination mode of perrhenate on coordination to an actinide and yields further insight into the possible solvent phase pertechnetate complexes that may exist in PUREX process phosphate rich solvent.

  2. 40 CFR 721.2535 - Benzene, 1,1′-methylanebis[4-isocyanato-, homopolymer, Bu alc.-blocked.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Benzene, 1,1â²-methylanebis[4... Significant New Uses for Specific Chemical Substances § 721.2535 Benzene, 1,1′-methylanebis[4-isocyanato... chemical substance identified as benzene, 1,1′-methylanebis[4-isocyanato-, homopolymer, Bu...

  3. 40 CFR 721.2535 - Benzene, 1,1′-methylanebis[4-isocyanato-, homopolymer, Bu alc.-blocked.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Benzene, 1,1â²-methylanebis[4... Significant New Uses for Specific Chemical Substances § 721.2535 Benzene, 1,1′-methylanebis[4-isocyanato... chemical substance identified as benzene, 1,1′-methylanebis[4-isocyanato-, homopolymer, Bu...

  4. 40 CFR 721.2535 - Benzene, 1,1′-methylanebis[4-isocyanato-, homopolymer, Bu alc.-blocked.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Benzene, 1,1â²-methylanebis[4... Significant New Uses for Specific Chemical Substances § 721.2535 Benzene, 1,1′-methylanebis[4-isocyanato... chemical substance identified as benzene, 1,1′-methylanebis[4-isocyanato-, homopolymer, Bu...

  5. 40 CFR 721.2535 - Benzene, 1,1′-methylanebis[4-isocyanato-, homopolymer, Bu alc.-blocked.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Benzene, 1,1â²-methylanebis[4... Significant New Uses for Specific Chemical Substances § 721.2535 Benzene, 1,1′-methylanebis[4-isocyanato... chemical substance identified as benzene, 1,1′-methylanebis[4-isocyanato-, homopolymer, Bu...

  6. 40 CFR 721.2535 - Benzene, 1,1′-methylanebis[4-isocyanato-, homopolymer, Bu alc.-blocked.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Benzene, 1,1â²-methylanebis[4... Significant New Uses for Specific Chemical Substances § 721.2535 Benzene, 1,1′-methylanebis[4-isocyanato... chemical substance identified as benzene, 1,1′-methylanebis[4-isocyanato-, homopolymer, Bu...

  7. Preparation and Investigation of Monodentate and Bridging Pyrazole Complexes

    ERIC Educational Resources Information Center

    Evans, Wynne

    2004-01-01

    Complexes of pyrazole-derived ligands are very popular due to the ability of the pyrazolato anion to form bridged polymetallic compounds in which the metals are held close enough to react with small molecules or facilitate magnetic exchange. The preparation of monodentate pyrazole and 3,5-dimethylpyrazole (DMHpz) nickel species and the…

  8. 54. STEEL COMPLEX FROM CLARK AVENUE BRIDGE, LOOKING NORTHEAST. FOUNDRY ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    54. STEEL COMPLEX FROM CLARK AVENUE BRIDGE, LOOKING NORTHEAST. FOUNDRY IN FOREGROUND, INGOT MOLDS ON TRACK AT RIGHT, BASIC OXYGEN FURNACE ON TRACK AT RIGHT. - Corrigan, McKinney Steel Company, 3100 East Forty-fifth Street, Cleveland, Cuyahoga County, OH

  9. Bridging epigenomics and complex disease: the basics.

    PubMed

    Teperino, Raffaele; Lempradl, Adelheid; Pospisilik, J Andrew

    2013-05-01

    The DNA sequence largely defines gene expression and phenotype. However, it is becoming increasingly clear that an additional chromatin-based regulatory network imparts both stability and plasticity to genome output, modifying phenotype independently of the genetic blueprint. Indeed, alterations in this "epigenetic" control layer underlie, at least in part, the reason for monozygotic twins being discordant for disease. Functionally, this regulatory layer comprises post-translational modifications of DNA and histones, as well as small and large noncoding RNAs. Together these regulate gene expression by changing chromatin organization and DNA accessibility. Successive technological advances over the past decade have enabled researchers to map the chromatin state with increasing accuracy and comprehensiveness, catapulting genetic research into a genome-wide era. Here, aiming particularly at the genomics/epigenomics newcomer, we review the epigenetic basis that has helped drive the technological shift and how this progress is shaping our understanding of complex disease.

  10. Formation of a Bridging Phosphinidene Thorium Complex.

    PubMed

    Behrle, Andrew C; Castro, Ludovic; Maron, Laurent; Walensky, Justin R

    2015-12-01

    The synthesis and structural determination of the first thorium phosphinidene complex are reported. The reaction of 2 equiv of (C5Me5)2Th(CH3)2 with H2P(2,4,6-(i)Pr3C6H2) at 95 °C produces [(C5Me5)2Th]2(μ2-P[(2,6-CH2CHCH3)2-4-(i)PrC6H2] as well as 4 equiv of methane, 2 equiv from deprotonation of the phosphine and 2 equiv from C-H bond activation of one methyl group of each of the isopropyl groups at the 2- and 6-positions. Transition state calculations indicate that the steps in the mechanism are P-H, C-H, C-H, and then P-H bond activation to form the phosphinidene. PMID:26575219

  11. 9-Triptycenecarboxylate-Bridged Diiron(II) Complexes

    PubMed Central

    Friedle, Simone; Kodanko, Jeremy J.; Fornace, Kyrstin L.; Lippard, Stephen J.

    2008-01-01

    The synthesis and characterization of diiron(II) complexes supported by 9-triptycenecarboxylate ligands (-O2CTrp) is described. The interlocking nature of the triptycenecarboxylates facilitates formation of quadruply bridged diiron(II) complexes of the type [Fe2(μ-O2CTrp)4(L)2] (L = THF, pyridine or imidazole derivative) with a paddlewheel geometry. A systematic lengthening of the Fe-Fe distance occurs with the increase in steric bulk of the neutral donor L, resulting in values of up to 3 Å without disassembly of the paddlewheel structure. Reactions with an excess of water do not lead to decomposition of the diiron(II) core, indicating that these quadruply bridged complexes are of exceptional stability. The red-colored complexes [Fe2(μ-O2CTrp)4(4-AcPy)2] (10) and [Fe2(μ-O2CTrp)4(4-CNPy)2] (11) exhibit solvent-dependent thermochromism in coordinating solvents that was studied by variable temperature UV-vis spectroscopy. Reaction of [Fe2(μ-O2CTrp)4(THF)2] with N,N,N’,N’-tetramethylethylenediamine (TMEDA), tetra-n-butyl ammonium thiocyanate, or excess 2-methylimidazole resulted in the formation of mononuclear complexes [Fe(O2CTrp)2(TMEDA)] (13), (n-Bu4N)2[Fe(O2CTrp)2(SCN)2] (14), and [Fe(O2CTrp)2(2-MeIm)2] (15) having an O4/N2 coordination sphere composition. PMID:19915653

  12. 40 CFR 721.1068 - Benzenamine, 4-isocyanato-N,N-bis(4-isocyanatophenyl)-2,5-dimethoxy-.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... AGENCY (CONTINUED) TOXIC SUBSTANCES CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.1068 Benzenamine, 4-isocyanato-N,N-bis(4-isocyanatophenyl)-2,5-dimethoxy-. (a) Chemical substance and significant new uses subject to reporting. (1)...

  13. Tuning spin-spin coupling in quinonoid-bridged dicopper(II) complexes through rational bridge variation.

    PubMed

    Schweinfurth, David; Khusniyarov, Marat M; Bubrin, Denis; Hohloch, Stephan; Su, Cheng-Yong; Sarkar, Biprajit

    2013-09-16

    Bridged metal complexes [{Cu(tmpa)}2(μ-L(1)-2H)](ClO4)2 (1), [{Cu(tmpa)}2(μ-L(2)-2H)](ClO4)2 (2), [{Cu(tmpa)}2(μ-L(3)-2H)](BPh4)2 (3), and [{Cu(tmpa)}2(μ-L(4)-2H)](ClO4)2 (4) (tmpa = tris(2-pyridylmethyl)amine, L(1) = chloranilic acid, L(2) = 2,5-dihydroxy-1,4-benzoquinone, L(3) = (2,5-di-[2-(methoxy)-anilino]-1,4-benzoquinone, L(4) = azophenine) were synthesized from copper(II) salts, tmpa, and the bridging quinonoid ligands in the presence of a base. X-ray structural characterization of the complexes showed a distorted octahedral environment around the copper(II) centers for the complexes 1-3, the donors being the nitrogen atoms of tmpa, and the nitrogen or oxygen donors of the bridging quinones. In contrast, the copper(II) centers in 4 display a distorted square-pyramidal coordination, where one of the pyridine arms of each tmpa remains uncoordinated. Bond-length analyses within the bridging ligand exhibit localization of the double bonds inside the bridge for 1-3. In contrast, complete delocalization of double bonds within the bridging ligand is observed for 4. Temperature-dependent magnetic susceptibility measurements on the complexes reveal an antiferromagnetic coupling between the copper(II) ions. The strength of antiferromagnetic coupling was observed to depend on the energy of the HOMO of the bridging quinone ligands, with exchange coupling constants J in the range between -23.2 and -0.6 cm(-1) and the strength of antiferromagnetic coupling of 4 > 3 > 2 > 1. Broken-symmetry density functional theory calculations (DFT) revealed that the orientation of magnetic orbitals in 1 and 2 is different than that in 3 and 4, and this results in two different exchange pathways. These results demonstrate how bridge-mediated spin-spin coupling in quinone-bridged metal complexes can be strongly tuned by a rational design of the bridging ligand employing the [O] for [NR] isoelectronic analogy.

  14. Charge-transport-induced dissociation in donor-bridge-acceptor complexes.

    PubMed

    Brisker, Daria; Peskin, Uri

    2008-12-28

    Possible mechanisms for charge-transport-induced dissociation in donor-bridge-acceptor complexes are studied. Two mechanisms for dissociation at the molecular bridge are captured within a simple model of an anharmonic bridge vibration coupled nonlinearly to an electronic degree of freedom. A direct mechanism is associated with vibronic excitations to the nuclear continuum and an alternative dissociation mechanism involves intermediate quasibound vibrational states (Feshbach resonances). The two different mechanisms of charge-transport-induced dissociation are analyzed and their interplay as a function of the system parameters is examined. A parameter regime is suggested where the phenomenon should be experimentally accessible.

  15. A TACC3/ch-TOG/clathrin complex stabilises kinetochore fibres by inter-microtubule bridging

    PubMed Central

    Booth, Daniel G; Hood, Fiona E; Prior, Ian A; Royle, Stephen J

    2011-01-01

    Kinetochore fibres (K-fibres) of the spindle apparatus move chromosomes during mitosis. These fibres are discrete bundles of parallel microtubules (MTs) that are crosslinked by inter-MT ‘bridges' that are thought to improve fibre stability during chromosomal movement. The identity of these bridges is unknown. Clathrin is a multimeric protein that has been shown to stabilise K-fibres during early mitosis by a mechanism independent of its role in membrane trafficking. In this study, we show that clathrin at the mitotic spindle is in a transforming acidic colied-coil protein 3 (TACC3)/colonic, hepatic tumour overexpressed gene (ch-TOG)/clathrin complex. The complex is anchored to the spindle by TACC3 and ch-TOG. Ultrastructural analysis of clathrin-depleted K-fibres revealed a selective loss of a population of short inter-MT bridges and a general loss of MTs. A similar loss of short inter-MT bridges was observed in TACC3-depleted K-fibres. Finally, immunogold labelling confirmed that inter-MT bridges in K-fibres contain clathrin. Our results suggest that the TACC3/ch-TOG/clathrin complex is an inter-MT bridge that stabilises K-fibres by physical crosslinking and by reducing rates of MT catastrophe. PMID:21297582

  16. Significance of retinal laser lesion location and subretinal hemorrhage in bridging choroidal neovascular complexes

    NASA Astrophysics Data System (ADS)

    Schuschereba, Steven T.; Clarkson, Donna R.; Valo, Lynn M.; Brown, Jeremiah, Jr.; Stuck, Bruce E.

    2003-06-01

    Purpose: To determine funduscopic criteria that will help predict when bridging choroidal neovascular (CNV) complexes will develop after laser retinal trauma and to define early preventive treatment targets. Methods: Ten rhesus monkeys were used and retinal lesions were produced by Nd:YAG exposures (20ns, 1-2mJ, 1064nm, min. spot size) simulating human accidental laser trauma to the central fundus. Funduscopy and fluorescein/ICG angiography were conducted at day 1, 4, and 14, and at 2 and 4 months, and animals terminated for histologic evaluation. Predisposition for bridging fibrovascular complexes was evaluated for single lesions, two small lesions showing coalescing hemorrhages, and multiple lesions involved with large field subretinal and vitreous hemorrhages. Results: Elevated CNVs were present in all single lesions with confined subretinal hemorrhages. All lesion sets that showed initial and small coalescing subretinal hemorrhages formed bridging CNV scars. No bridging CNVs occurred in lesion sets involving a vitreous hemorrhage adjacent to a confined, but small subretinal hemorrhage. In large field subretinal hemorrhages involving multiple laser lesions, complex CNV formation occurred. Extensive secondary photoreceptor losses occurred in confined hemorrhage and CNV zones. Conclusion: Trauma presenting with evidence of coalescing and confined subretinal hemorrhages between two adjacent lesions has a high chance of forming choroidal neovascular bridge complexes between the involved lesions. CNV formation may be related to the long residence time, break down products, and clearance processes of extravasated blood. Removal of trapped blood and curtailing angiogenesis and cellular proliferation may be helpful treatment strategies.

  17. Mixed-valence dinitrogen-bridged Fe(0)/Fe(II) complex.

    PubMed

    Field, Leslie D; Guest, Ruth W; Turner, Peter

    2010-10-01

    The reactions of a dinitrogen-bridged Fe(II)/Fe(II) complex [(FeH(PP(3)))(2)(μ-N(2))](2+) (3) (PP(3) = P(CH(2)CH(2)PMe(2))(3)) with base were investigated using (15)N labeling techniques to enhance characterization. In the presence of base, 3 is initially deprotonated to the Fe(II)/Fe(0) dinitrogen-bridged complex [(FeH(PP(3)))(μ-N(2))(Fe(PP(3)))](+) (4) and then to the symmetrical Fe(0)/Fe(0) dinitrogen-bridged complex (Fe(PP(3)))(2)(μ-N(2)) (5). [(FeH(PP(3)))(μ-N(2))(Fe(PP(3)))](+) (4) exhibits unusual long-range (31)P-(31)P NMR coupling through the bridging dinitrogen ligand from the phosphines at the Fe(0) center and those at the Fe(II) center. Reaction of 4 with base under an atmosphere of argon resulted in the known dinitrogen Fe(0) complex Fe(N(2))(PP(3)) (6) and a solvent C-H activation product. Complexes 3, 4, and 5 were fully characterized by multinuclear NMR spectroscopy, and complexes 3 and 4 by X-ray crystallography.

  18. Phenoxy-bridged binuclear Zn(II) complex holding salen ligand: Synthesis and structural characterization

    NASA Astrophysics Data System (ADS)

    Azam, Mohammad; Al-Resayes, Saud I.

    2016-03-01

    A novel binuclear phenoxo-bridged zinc complex obtained from the interaction of ligand, 2,2-(1E,1E)-(2,2-dimethylpropane-1,3-diyl)bis(azanylylidene) bis(methanylylidene)diphenol with zinc chloride is reported. The synthesized and isolated zinc complex has been characterized by FT-IR, 1H- and 13C- NMR, ESI-MS, TGA/DTA and single crystal X-ray diffraction studies. The phenoxo-bridge in this binuclear Zn(II) complex is due to the phenolic oxygen of the salen liagnd. The complex crystallizes in monoclinic P-1 space group, and different geometry has been assigned for both zinc ions in the complex.

  19. Unique behaviour of dinitrogen-bridged dimolybdenum complexes bearing pincer ligand towards catalytic formation of ammonia

    PubMed Central

    Tanaka, Hiromasa; Arashiba, Kazuya; Kuriyama, Shogo; Sasada, Akira; Nakajima, Kazunari; Yoshizawa, Kazunari; Nishibayashi, Yoshiaki

    2014-01-01

    It is vital to design effective nitrogen fixation systems that operate under mild conditions, and to this end we recently reported an example of the catalytic formation of ammonia using a dinitrogen-bridged dimolybdenum complex bearing a pincer ligand, where up to twenty three equivalents of ammonia were produced based on the catalyst. Here we study the origin of the catalytic behaviour of the dinitrogen-bridged dimolybdenum complex bearing the pincer ligand with density functional theory calculations, based on stoichiometric and catalytic formation of ammonia from molecular dinitrogen under ambient conditions. Comparison of di- and mono-molybdenum systems shows that the dinitrogen-bridged dimolybdenum core structure plays a critical role in the protonation of the coordinated molecular dinitrogen in the catalytic cycle. PMID:24769530

  20. 40 CFR 721.10185 - 1,2-Propanediol, 3-(diethylamino)-, polymers with 5-isocyanato-1- (isocyanatomethyl)-1,3,3...

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false 1,2-Propanediol, 3-(diethylamino)-, polymers with 5-isocyanato-1- (isocyanatomethyl)-1,3,3-trimethylcyclohexane, propylene glycol and reduced Me esters of reduced polymd. oxidized tetrafluoroethylene, 2-ethyl-1-hexanol-blocked, acetates (salts). 721.10185 Section 721.10185 Protection...

  1. 40 CFR 721.10185 - 1,2-Propanediol, 3-(diethylamino)-, polymers with 5-isocyanato-1- (isocyanatomethyl)-1,3,3...

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false 1,2-Propanediol, 3-(diethylamino)-, polymers with 5-isocyanato-1- (isocyanatomethyl)-1,3,3-trimethylcyclohexane, propylene glycol and reduced Me esters of reduced polymd. oxidized tetrafluoroethylene, 2-ethyl-1-hexanol-blocked, acetates (salts). 721.10185 Section 721.10185 Protection...

  2. 40 CFR 721.10185 - 1,2-Propanediol, 3-(diethylamino)-, polymers with 5-isocyanato-1- (isocyanatomethyl)-1,3,3...

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false 1,2-Propanediol, 3-(diethylamino)-, polymers with 5-isocyanato-1- (isocyanatomethyl)-1,3,3-trimethylcyclohexane, propylene glycol and reduced Me esters of reduced polymd. oxidized tetrafluoroethylene, 2-ethyl-1-hexanol-blocked, acetates (salts). 721.10185 Section 721.10185 Protection...

  3. 40 CFR 721.10185 - 1,2-Propanediol, 3-(diethylamino)-, polymers with 5-isocyanato-1- (isocyanatomethyl)-1,3,3...

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false 1,2-Propanediol, 3-(diethylamino)-, polymers with 5-isocyanato-1- (isocyanatomethyl)-1,3,3-trimethylcyclohexane, propylene glycol and reduced Me esters of reduced polymd. oxidized tetrafluoroethylene, 2-ethyl-1-hexanol-blocked, acetates (salts). 721.10185 Section 721.10185 Protection...

  4. 40 CFR 721.10185 - 1,2-Propanediol, 3-(diethylamino)-, polymers with 5-isocyanato-1- (isocyanatomethyl)-1,3,3...

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ...)-, polymers with 5-isocyanato-1- (isocyanatomethyl)-1,3,3-trimethylcyclohexane, propylene glycol and reduced Me esters of reduced polymd. oxidized tetrafluoroethylene, 2-ethyl-1-hexanol-blocked, acetates (salts... Me esters of reduced polymd. oxidized tetrafluoroethylene, 2-ethyl-1-hexanol-blocked, acetates...

  5. [Sorption and desorption of phenanthrene by organo-mineral complexes with different bridge cations].

    PubMed

    Ni, Jin-zhi; Luo, Yong-ming; Wei, Ran; Li, Xiu-hua; Qian, Wei

    2008-12-01

    Sorption and desorption of phenanthrene by organo-mineral complexes with Ca2+, Fe3+ and Al3+ as bridge cations were studied according to the association type between organic matter and minerals in natural soils. The results showed that the data of phenanthrene sorption and desorption by different cation saturated montmorillonite and their corresponding humic acid and mineral complexes could be fitted with Freundlich model, and the order of the sorption capacities (Kf) were Ca-Mont (0.184) > Fe-Mont (0.028) > Al-Mont (0.015) and Fe-Mont-HA (2.341) > Ca-Mont-HA (1.557) > Al-Mont-HA (1.136), respectively. The Kf values of humic acid and mineral complexes were far greater than those of minerals, which demonstrated that humic acid made great contributions to the sorption of phenanthrene in the organo-mineral complexes. However, the Kf values of the organo-mineral complexes with different bridge cations were not consistent with their organic carbon content, which indicated that both the organic carbon content and the combined types between organic matter and mineral could affect the sorption capacity of phenanthrene by the organo-mineral complexes. The desorption hysteresis of phenanthrene was significant for Ca2+ and Al3+ bridged organo-mineral complexes. Desorption hysteresis of phenanthrene was mainly from the sorption of phenanthrene by organic matter, and the contributions of mineral to the desorption hysteresis were not significant. PMID:19256397

  6. [Sorption and desorption of phenanthrene by organo-mineral complexes with different bridge cations].

    PubMed

    Ni, Jin-zhi; Luo, Yong-ming; Wei, Ran; Li, Xiu-hua; Qian, Wei

    2008-12-01

    Sorption and desorption of phenanthrene by organo-mineral complexes with Ca2+, Fe3+ and Al3+ as bridge cations were studied according to the association type between organic matter and minerals in natural soils. The results showed that the data of phenanthrene sorption and desorption by different cation saturated montmorillonite and their corresponding humic acid and mineral complexes could be fitted with Freundlich model, and the order of the sorption capacities (Kf) were Ca-Mont (0.184) > Fe-Mont (0.028) > Al-Mont (0.015) and Fe-Mont-HA (2.341) > Ca-Mont-HA (1.557) > Al-Mont-HA (1.136), respectively. The Kf values of humic acid and mineral complexes were far greater than those of minerals, which demonstrated that humic acid made great contributions to the sorption of phenanthrene in the organo-mineral complexes. However, the Kf values of the organo-mineral complexes with different bridge cations were not consistent with their organic carbon content, which indicated that both the organic carbon content and the combined types between organic matter and mineral could affect the sorption capacity of phenanthrene by the organo-mineral complexes. The desorption hysteresis of phenanthrene was significant for Ca2+ and Al3+ bridged organo-mineral complexes. Desorption hysteresis of phenanthrene was mainly from the sorption of phenanthrene by organic matter, and the contributions of mineral to the desorption hysteresis were not significant.

  7. Synthesis and DFT Study of a Diphenylsilanone-Bridged Dimolybdenum Complex.

    PubMed

    Alvarez, M Angeles; García, M Esther; García-Vivó, Daniel; Menéndez, Sonia; Ruiz, Miguel A

    2016-06-20

    Reaction of the 30-electron benzylidyne complex [Mo2 Cp2 (μ-CPh)(μ-PCy2 )(μ-CO)] with excess Ph2 SiH2 under visible-UV irradiation yields the silylene-bridged complex [Mo2 Cp2 (μ-CPh)(μ-PCy2 )(μ-SiPh2 )]. This compound undergoes selective oxidation with O2 to give the unsaturated complex [Mo2 Cp2 (μ-CPh)(μ-PCy2 )(μ-κ(1) :κ(1) -OSiPh2 )], which contains an unprecedented bridging diphenylsilanone ligand, as confirmed by X-ray diffraction analysis and DFT calculations. The bonding within the central Mo2 SiO ring of this complex approaches the extreme description of a dimetallacyclosiloxane according to the relevant solid-state bond lengths and theoretical calculations. PMID:27124667

  8. Synthesis and spectral and redox properties of three triply bridged complexes of ruthenium

    USGS Publications Warehouse

    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.

  9. Preparation, characterization and luminescent properties of lanthanide complexes with a new aryl amide bridging ligand

    NASA Astrophysics Data System (ADS)

    Li, Ya-Fei; Tang, Kuan-Zhen; Tang, Yu; Liu, Wei-Sheng; Tan, Min-Yu

    2008-12-01

    A new aryl amide type bridging ligand 1,4-bis{[(2'-benzylaminoformyl)phenoxyl]ethoxyl}benzene ( L) and its complexes with lanthanide ions (Ln = Pr, Nd, Sm, Eu, Gd, Tb, Dy, Er) were synthesized and characterized by elemental analysis, infrared spectra and electronic spectra. At the same time, the luminescent properties of the Sm, Eu, Tb and Dy complexes in solid state and the Tb complex in solvents were also investigated. At room temperature, these four complexes exhibited characteristic luminescence emissions of the central metal ions under UV light excitation and could be significant in the field of supramolecular photonic devices.

  10. Bridging Mechanistic and Phenomenological Models of Complex Biological Systems

    PubMed Central

    Transtrum, Mark K.; Qiu, Peng

    2016-01-01

    The inherent complexity of biological systems gives rise to complicated mechanistic models with a large number of parameters. On the other hand, the collective behavior of these systems can often be characterized by a relatively small number of phenomenological parameters. We use the Manifold Boundary Approximation Method (MBAM) as a tool for deriving simple phenomenological models from complicated mechanistic models. The resulting models are not black boxes, but remain expressed in terms of the microscopic parameters. In this way, we explicitly connect the macroscopic and microscopic descriptions, characterize the equivalence class of distinct systems exhibiting the same range of collective behavior, and identify the combinations of components that function as tunable control knobs for the behavior. We demonstrate the procedure for adaptation behavior exhibited by the EGFR pathway. From a 48 parameter mechanistic model, the system can be effectively described by a single adaptation parameter τ characterizing the ratio of time scales for the initial response and recovery time of the system which can in turn be expressed as a combination of microscopic reaction rates, Michaelis-Menten constants, and biochemical concentrations. The situation is not unlike modeling in physics in which microscopically complex processes can often be renormalized into simple phenomenological models with only a few effective parameters. The proposed method additionally provides a mechanistic explanation for non-universal features of the behavior. PMID:27187545

  11. Complex archaea that bridge the gap between prokaryotes and eukaryotes.

    PubMed

    Spang, Anja; Saw, Jimmy H; Jørgensen, Steffen L; Zaremba-Niedzwiedzka, Katarzyna; Martijn, Joran; Lind, Anders E; van Eijk, Roel; Schleper, Christa; Guy, Lionel; Ettema, Thijs J G

    2015-05-14

    The origin of the eukaryotic cell remains one of the most contentious puzzles in modern biology. Recent studies have provided support for the emergence of the eukaryotic host cell from within the archaeal domain of life, but the identity and nature of the putative archaeal ancestor remain a subject of debate. Here we describe the discovery of 'Lokiarchaeota', a novel candidate archaeal phylum, which forms a monophyletic group with eukaryotes in phylogenomic analyses, and whose genomes encode an expanded repertoire of eukaryotic signature proteins that are suggestive of sophisticated membrane remodelling capabilities. Our results provide strong support for hypotheses in which the eukaryotic host evolved from a bona fide archaeon, and demonstrate that many components that underpin eukaryote-specific features were already present in that ancestor. This provided the host with a rich genomic 'starter-kit' to support the increase in the cellular and genomic complexity that is characteristic of eukaryotes.

  12. Complex archaea that bridge the gap between prokaryotes and eukaryotes

    PubMed Central

    Martijn, Joran; Lind, Anders E.; van Eijk, Roel; Schleper, Christa; Guy, Lionel; Ettema, Thijs J. G.

    2015-01-01

    The origin of the eukaryotic cell remains one of the most contentious puzzles in modern biology. Recent studies have provided support for the emergence of the eukaryotic host cell from within the archaeal domain of life, but the identity and nature of the putative archaeal ancestor remain a subject of debate. Here we describe the discovery of ‘Lokiarchaeota’, a novel candidate archaeal phylum, which forms a monophyletic group with eukaryotes in phylogenomic analyses, and whose genomes encode an expanded repertoire of eukaryotic signature proteins that are suggestive of sophisticated membrane remodelling capabilities. Our results provide strong support for hypotheses in which the eukaryotic host evolved from a bona fide archaeon, and demonstrate that many components that underpin eukaryote-specific features were already present in that ancestor. This provided the host with a rich genomic ‘starter-kit’ to support the increase in the cellular and genomic complexity that is characteristic of eukaryotes. PMID:25945739

  13. Complex archaea that bridge the gap between prokaryotes and eukaryotes.

    PubMed

    Spang, Anja; Saw, Jimmy H; Jørgensen, Steffen L; Zaremba-Niedzwiedzka, Katarzyna; Martijn, Joran; Lind, Anders E; van Eijk, Roel; Schleper, Christa; Guy, Lionel; Ettema, Thijs J G

    2015-05-14

    The origin of the eukaryotic cell remains one of the most contentious puzzles in modern biology. Recent studies have provided support for the emergence of the eukaryotic host cell from within the archaeal domain of life, but the identity and nature of the putative archaeal ancestor remain a subject of debate. Here we describe the discovery of 'Lokiarchaeota', a novel candidate archaeal phylum, which forms a monophyletic group with eukaryotes in phylogenomic analyses, and whose genomes encode an expanded repertoire of eukaryotic signature proteins that are suggestive of sophisticated membrane remodelling capabilities. Our results provide strong support for hypotheses in which the eukaryotic host evolved from a bona fide archaeon, and demonstrate that many components that underpin eukaryote-specific features were already present in that ancestor. This provided the host with a rich genomic 'starter-kit' to support the increase in the cellular and genomic complexity that is characteristic of eukaryotes. PMID:25945739

  14. Liquid bridges in complex geometries: Equilibrium shape metamorphosis using electrowetting

    NASA Astrophysics Data System (ADS)

    Baratian, Davood; Cavalli, Andrea; van den Ende, Dirk; Mugele, Frieder

    2015-11-01

    The equilibrium morphology of liquid drops exposed to geometric constraints can be rather complex. Even for simple geometries, analytical solutions are scarce. We investigate the equilibrium shape and position of liquid drops confined in the wedge between two solid surfaces. Using electrowetting, we control the contact angle and thereby manipulate the shape and the equilibrium position of aqueous drops in ambient oil. In the absence of contact angle hysteresis and buoyancy, we find that the equilibrium shape is given by a truncated sphere, prior to filling the wedge corner, at a position that is determined by the drop volume and the contact angle. At this position, the net force between drop and the surfaces vanishes. The effect of buoyancy gives rise to substantial deviations from this equilibrium configuration which we discuss it as well. We elegantly show how the geometric constraint and electrowetting can be used to position droplets inside a wedge in a controlled way, without mechanical actuation. The Netherlands Organization for Scientific Research (NWO).

  15. Carbon bridged triphenolate lanthanide complexes: synthesis, characterization, DFT studies and catalytic activities for isoprene polymerization.

    PubMed

    Zhang, Min; Liang, Zhenhua; Ling, Jun; Ni, Xufeng; Shen, Zhiquan

    2015-06-28

    The dinuclear lanthanide complexes [Ln2(L)2(THF)n] (Ln = Nd (1) n = 4, Gd (2) n = 3, Lu (3) n = 2) supported by carbon bridged triphenolate ligands [LH3 = tris(3,5-di-tert-butyl-2-hydroxyphenyl)methane] were synthesized via a salt metathesis reaction between lanthanide trichlorides and LNa3 in THF. All complexes were characterized by elemental analysis and X-ray crystallography, and complex 3 was characterized by (1)H and (13)C NMR spectroscopy. Agostic interactions were found in these complexes and were further substantiated by DFT calculations of complex 3. These lanthanide complexes in combination with aluminum alkyls and [Ph3C](+)[B(C6F5)4](-) generated efficient homogeneous catalysts for the cis-1,4 polymerization of isoprene, with complex 1 having the best catalytic activity. PMID:26008592

  16. Cross-bridged Macrocyclic Chelators for Stable Complexation of Copper Radionuclides for PET Imaging

    PubMed Central

    Anderson, Carolyn J.; Wadas, Thaddeus J.; Wong, Edward H.; Weisman, Gary R.

    2015-01-01

    Copper-64 (t1/2 = 12.7 h, β+: 17.4%, Eβ+max = 656 keV; β−: 39%, Eβ-max = 573 keV) has emerged as an important non-standard positron-emitting radionuclide for PET imaging of diseased tissues. A significant challenge of working with copper radionuclides is that they must be delivered to the living system as a stable complex that is attached to a biological targeting molecule for effective imaging and therapy. Significant research has been devoted to the development of ligands that can stably chelate 64Cu, in particular, the cross-bridged macrocyclic chelators. This review describes the coordination chemistry and biological behavior of 64Cu-labeled cross-bridged complexes. PMID:18043536

  17. Synthesis and antimalarial activity of metal complexes of cross-bridged tetraazamacrocyclic ligands

    PubMed Central

    Hubin, Timothy J.; Amoyaw, Prince N. -A.; Roewe, Kimberly D.; Simpson, Natalie C.; Maples, Randall D.; Carder Freeman, TaRynn N.; Cain, Amy N.; Le, Justin G.; Archibald, Stephen J.; Khan, Shabana I.; Tekwani, Babu L.; Khan, M. O. Faruk

    2014-01-01

    Using transition metals such as manganese(II), iron(II), cobalt(II), nickel(II), copper(II), and zinc(II), several new metal complexes of cross-bridged tetraazamacrocyclic chelators namely, cyclen- and cyclam-analogs with benzyl groups, were synthesized and screened for in vitro antimalarial activity against chloroquine-resistant (W2) and chloroquine-sensitive (D6) strains of Plasmodium falciparum. The metal-free chelators tested showed little or no antimalarial activity. All the metal complexes of the dibenzyl cross-bridged cyclam ligand exhibited potent antimalarial activity. The Mn2+ complex of this ligand was the most potent with IC50s of 0.127 and 0.157 µM against the chloroquine-sensitive (D6) and chloroquine-resistant (W2) P. falciparum strains, respectively. In general, the dibenzyl hydrophobic ligands showed better antimalarial activity compared to the activity of monobenzyl ligands, potentially because of their higher lipophilicity and thus better cell penetration ability. The higher antimalarial activity displayed by the manganese complex for the cyclam ligand in comparison to that of the cyclen, correlates with the larger pocket of cyclam compared to that of cyclen which produces a more stable complex with the Mn2+. Few of the Cu2+ and Fe2+ complexes also showed improvement in activity but Ni2+, Co2+ and Zn2+ complexes did not show any improvement in activity upon the metal-free ligands for anti-malarial development. PMID:24857776

  18. A slipped multi-decker zirconium complex with an η7:η2-bridging cycloheptatrienyl ligand.

    PubMed

    Glöckner, Andreas; Daniliuc, Constantin G; Freytag, Matthias; Jones, Peter G; Tamm, Matthias

    2012-07-01

    The complex [(η(7)-C(7)H(7))Zr{N(SiMe(3))(2)}(thf)] (2) loses THF upon sublimation to afford a chain polymer consisting of [(η(7)-C(7)H(7))Zr{N(SiMe(3))(2)}] (3) units; they are connected by cycloheptatrienyl ligands in an unprecedented antifacial η(7):η(2)-bridging mode. The basicity of the bis(trimethylsilyl)amido ligand can also be used to introduce other ligands by acid-base reactions.

  19. First magnetostructural study on a heterodinuclear 2,2'-bipyrimidine-bridged complex.

    PubMed

    Martínez-Lillo, José; Armentano, Donatella; De Munno, Giovanni; Cano, Joan; Lloret, Francesc; Julve, Miguel; Faus, Juan

    2011-12-19

    The use of the [ReCl(4)(bpym)] precursor as a ligand toward the fully solvated nickel(II) metal ion affords the first example of a 2,2'-bipyrimidine-bridged Re(IV)-Ni(II) complex, [ReCl(4)(μ-bpym)NiBr(2)(H(2)O)(2)] (1), whose intramolecular ferromagnetic coupling has been substantiated from both experimental and theoretical studies.

  20. The Effect of 3-Isocyanato-1-Propene on Adhesive Properties of UV-Curing Urethane/Siloxane Acrylate Resin.

    PubMed

    Chun, J H; Cheon, J M; Jeong, B Y; Jo, N J

    2016-03-01

    We synthesized the urethane/siloxane acrylate oligomer from isophorone diisocyanate (IPDI), hydroxyl alkyl terminated polydimethylsiloxane and 2-hydroxyethyl acrylate (2-HEA). UV-curable resins were formulated from the synthesized oligomer, ethylene glycol phenyl ether acrylate (PHEA), 1,6-hexanediol diacrylate (HDDA), trimethylolpropane triacrylate (TMPTA) as a reactive diluent, 3-isocyanato-1-propene as an adhesion promoter and photoinitiators. The PET film was treated with plasma in order to introduce the functional group on the PET surface and the functional group was observed through X-ray photoelectron spectroscopy (XPS) and the Fourier transform infrared (FT-IR). The adhesion strength between the PET film and the UV-cured resin were increased by using the adhesion promoter. Also, the thermal stability, the modulus and surface hardness were increased, as the adhesion promoter was added.

  1. Ionothermal synthesis and crystal structure of a luminescent bipyridine bridged Zn(II) complex

    NASA Astrophysics Data System (ADS)

    Xiong, Wei; Xu, Wentao; Zhou, Youfu; Huang, Decai; Wang, Jinyun; Hong, Maochun; Xiong, Chunrong

    2014-02-01

    A luminescent complex, [Bmim]2[(ZnBr3)2(bpy)] (1) (bpy = 4,4‧-bipyridine, bmim = 1-butyl-3-methyl imidazolium), has been synthesized through ionothermal reaction and characterized systematically. Complex 1 exhibits isolated structure of bipyridine bridged zinc bromide units, stacked with 1-butyl-3-methyl imidazolium layers. The luminescent property of 1 has been investigated and supported by density functional theory (DFT) calculations, where the emissions are assigned to the halide-to-ligand charge transfer (XLCT) mixed with some metal-to-ligand charge transfer (MLCT) and intraligand-charge-transfer (ILCT).

  2. On the Silver Effect and the Formation of Chloride-Bridged Digold Complexes

    PubMed Central

    2013-01-01

    Abstraction of chloride anion from Au(I) complexes such as JohnPhosAuCl in noncoordinating solvents with 1 equiv of a silver salt, or even larger amounts, leads to the formation of chloride-bridged dinuclear gold(I) complexes, irrespective of the counteranion, which are substantially less reactive as catalysts. This incomplete removal of chloride ligand could lead to false negative results when using the in situ generation of the gold(I) active species by silver-promoted chloride abstraction. PMID:24195441

  3. Evolution and structural organization of the mitochondrial contact site (MICOS) complex and the mitochondrial intermembrane space bridging (MIB) complex.

    PubMed

    Huynen, Martijn A; Mühlmeister, Mareike; Gotthardt, Katherina; Guerrero-Castillo, Sergio; Brandt, Ulrich

    2016-01-01

    We have analyzed the distribution of mitochondrial contact site and cristae organizing system (MICOS) complex proteins and mitochondrial intermembrane space bridging complex (MIB) proteins over (sub)complexes and over species. The MICOS proteins are associated with the formation and maintenance of mitochondrial cristae. Indeed, the presence of MICOS genes in genomes correlates well with the presence of cristae: all cristae containing species have at least one MICOS gene and cristae-less species have none. Mic10 is the most widespread MICOS gene, while Mic60 appears be the oldest one, as it originates in the ancestors of mitochondria, the proteobacteria. In proteobacteria the gene occurs in clusters with genes involved in heme synthesis while the protein has been observed in intracellular membranes of the alphaproteobacterium Rhodobacter sphaeroides. In contrast, Mic23 and Mic27 appear to be the youngest MICOS proteins, as they only occur in opisthokonts. The remaining MICOS proteins, Mic10, Mic19, Mic25 and Mic12, the latter we show to be orthologous to human C19orf70/QIL1, trace back to the root of the eukaryotes. Of the remaining MIB proteins, also DNAJC11 shows a high correlation with the presence of cristae. In mitochondrial protein complexome profiles, the MIB complex occurs as a defined complex and as separate subcomplexes, potentially reflecting various assembly stages. We find three main forms of the complex: A) The MICOS complex, containing all the MICOS proteins, B) a membrane bridging subcomplex, containing in addition SAMM50, MTX2 and the previously uncharacterized MTX3, and C) the complete MIB complex containing in addition DNAJC11 and MTX1.

  4. Cytotoxic hydrogen bridged ruthenium quinaldamide complexes showing induced cancer cell death by apoptosis.

    PubMed

    Lord, Rianne M; Allison, Simon J; Rafferty, Karen; Ghandhi, Laura; Pask, Christopher M; McGowan, Patrick C

    2016-08-16

    This report presents the first known p-cymene ruthenium quinaldamide complexes which are stabilised by a hydrogen-bridging atom, [{(p-cym)Ru(II)X(N,N)}{H(+)}{(N,N)XRu(II)(p-cym)}][PF6] (N,N = functionalised quinaldamide and X = Cl or Br). These complexes are formed by a reaction of [p-cymRu(μ-X)2]2 with a functionalised quinaldamide ligand. When filtered over NH4PF6, and under aerobic conditions the equilibrium of NH4PF6 ⇔ NH3 + HPF6 enables incorporation of HPF6 and the stabilisation of two monomeric ruthenium complexes by a bridging H(+), which are counter-balanced by a PF6 counterion. X-ray crystallographic analysis is presented for six new structures with OO distances of 2.420(4)-2.448(15) Å, which is significant for strong hydrogen bonds. Chemosensitivity studies against HCT116, A2780 and cisplatin-resistant A2780cis human cancer cells showed the ruthenium complexes with a bromide ancillary ligand to be more potent than those with a chloride ligand. The 4'-fluoro compounds show a reduction in potency for both chloride and bromide complexes against all cell lines, but an increase in selectivity towards cancer cells compared to non-cancer ARPE-19 cells, with a selectivity index >1. Mechanistic studies showed a clear correlation between IC50 values and induction of cell death by apoptosis. PMID:27417660

  5. Simple structural differentiation of (μ-S,O) bridged sulfito complexes by vibrational spectrometry

    NASA Astrophysics Data System (ADS)

    Krieglstein, R.; Breitinger, D. K.

    1997-06-01

    Vibrational spectra of the newly prepared complexes [enM(SO 3) 2Men]·3H 2O (M = Pt ( 1) and Pd ( 2), en = 1,2-diaminoethane) indicate that in 1 the sulfite ligands link the two metal centers by two parallel μ-S,O bridges, whereas in 2 antiparallel bridges are realized, in accordance with the results of X-ray structure analyses for 1 and 2. Furthermore, the spectra allow a clear differentiation of the mononuclear educts K 2[M(SO 3) 2en]·2H 2O (M = Pt ( 3) and Pd ( 4)) with S-coordinated sulfite ligands and the binuclear products 1 and 2.

  6. Bridged transition-metal complexes and uses thereof for hydrogen separation, storage and hydrogenation

    DOEpatents

    Lilga, M.A.; Hallen, R.T.

    1991-10-15

    The present invention constitutes a class of organometallic complexes which reversibly react with hydrogen to form dihydrides and processes by which these compounds can be utilized. The class includes bimetallic complexes in which two cyclopentadienyl rings are bridged together and also separately [pi]-bonded to two transition metal atoms. The transition metals are believed to bond with the hydrogen in forming the dihydride. Transition metals such as Fe, Mn or Co may be employed in the complexes although Cr constitutes the preferred metal. A multiple number of ancillary ligands such as CO are bonded to the metal atoms in the complexes. Alkyl groups and the like may be substituted on the cyclopentadienyl rings. These organometallic compounds may be used in absorption/desorption systems and in facilitated transport membrane systems for storing and separating out H[sub 2] from mixed gas streams such as the product gas from coal gasification processes. 3 figures.

  7. Bridged transition-metal complexes and uses thereof for hydrogen separation, storage and hydrogenation

    DOEpatents

    Lilga, M.A.; Hallen, R.T.

    1990-08-28

    The present invention constitutes a class of organometallic complexes which reversibly react with hydrogen to form dihydrides and processes by which these compounds can be utilized. The class includes bimetallic complexes in which two cyclopentadienyl rings are bridged together and also separately [pi]-bonded to two transition metal atoms. The transition metals are believed to bond with the hydrogen in forming the dihydride. Transition metals such as Fe, Mn or Co may be employed in the complexes although Cr constitutes the preferred metal. A multiple number of ancillary ligands such as CO are bonded to the metal atoms in the complexes. Alkyl groups and the like may be substituted on the cyclopentadienyl rings. These organometallic compounds may be used in absorption/desorption systems and in facilitated transport membrane systems for storing and separating out H[sub 2] from mixed gas streams such as the producer gas from coal gasification processes. 3 figs.

  8. Bridged transition-metal complexes and uses thereof for hydrogen separation, storage and hydrogenation

    DOEpatents

    Lilga, Michael A.; Hallen, Richard T.

    1990-01-01

    The present invention constitutes a class of organometallic complexes which reversibly react with hydrogen to form dihydrides and processes by which these compounds can be utilized. The class includes bimetallic complexes in which two cyclopentadienyl rings are bridged together and also separately .pi.-bonded to two transition metal atoms. The transition metals are believed to bond with the hydrogen in forming the dihydride. Transition metals such as Fe, Mn or Co may be employed in the complexes although Cr constitutes the preferred metal. A multiple number of ancilliary ligands such as CO are bonded to the metal atoms in the complexes. Alkyl groups and the like may be substituted on the cyclopentadienyl rings. These organometallic compounds may be used in absorption/desorption systems and in facilitated transport membrane systems for storing and separating out H.sub.2 from mixed gas streams such as the produce gas from coal gasification processes.

  9. Bridged transition-metal complexes and uses thereof for hydrogen separation, storage and hydrogenation

    DOEpatents

    Lilga, Michael A.; Hallen, Richard T.

    1991-01-01

    The present invention constitutes a class of organometallic complexes which reversibly react with hydrogen to form dihydrides and processes by which these compounds can be utilized. The class includes bimetallic complexes in which two cyclopentadienyl rings are bridged together and also separately .pi.-bonded to two transition metal atoms. The transition metals are believed to bond with the hydrogen in forming the dihydride. Transition metals such as Fe, Mn or Co may be employed in the complexes although Cr constitutes the preferred metal. A multiple number of ancilliary ligands such as CO are bonded to the metal atoms in the complexes. Alkyl groups and the like may be substituted on the cyclopentadienyl rings. These organometallic compounds may be used in absorption/desorption systems and in facilitated transport membrane systems for storing and separating out H.sub.2 from mixed gas streams such as the product gas from coal gasification processes.

  10. Study of the influence of the bridge on the magnetic coupling in cobalt(II) complexes.

    PubMed

    Fabelo, Oscar; Cañadillas-Delgado, Laura; Pasán, Jorge; Delgado, Fernando S; Lloret, Francesc; Cano, Joan; Julve, Miguel; Ruiz-Pérez, Catalina

    2009-12-01

    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

  11. Alkoxy bridged binuclear rhenium (I) complexes as a potential sensor for β-amyloid aggregation.

    PubMed

    Sathish, Veerasamy; Babu, Eththilu; Ramdass, Arumugam; Lu, Zong-Zhan; Velayudham, Murugesan; Thanasekaran, Pounraj; Lu, Kuang-Lieh; Rajagopal, Seenivasan

    2014-12-01

    Alkoxy bridged binuclear rhenium(I) complexes are used as a probe for the selective and sensitive detection of aggregation of β-amyloid fibrils that are consorted with Alzheimer's disease (AD). The strong binding of the complexes is affirmed by the fluorescence enhancement and calculated binding constant value in the order of 10(5)M(-1) is obtained from the Scatchard plots. The binding of β-amyloid can be attributed to π-π stacking interaction of naphthalene moiety present in rhenium(I) complexes, and it is supported by docking studies. The selectivity is quite high towards other proteins and the formation of fibrils can be observed in the range of 30-40 nm through the AFM and TEM techniques.

  12. Ammonia formation by a thiolate-bridged diiron amide complex as a nitrogenase mimic

    NASA Astrophysics Data System (ADS)

    Li, Yang; Li, Ying; Wang, Baomin; Luo, Yi; Yang, Dawei; Tong, Peng; Zhao, Jinfeng; Luo, Lun; Zhou, Yuhan; Chen, Si; Cheng, Fang; Qu, Jingping

    2013-04-01

    Although nitrogenase enzymes routinely convert molecular nitrogen into ammonia under ambient temperature and pressure, this reaction is currently carried out industrially using the Haber-Bosch process, which requires extreme temperatures and pressures to activate dinitrogen. Biological fixation occurs through dinitrogen and reduced NxHy species at multi-iron centres of compounds bearing sulfur ligands, but it is difficult to elucidate the mechanistic details and to obtain stable model intermediate complexes for further investigation. Metal-based synthetic models have been applied to reveal partial details, although most models involve a mononuclear system. Here, we report a diiron complex bridged by a bidentate thiolate ligand that can accommodate HN=NH. Following reductions and protonations, HN=NH is converted to NH3 through pivotal intermediate complexes bridged by N2H3- and NH2- species. Notably, the final ammonia release was effected with water as the proton source. Density functional theory calculations were carried out, and a pathway of biological nitrogen fixation is proposed.

  13. Facile formation and redox of benzoxazole-2-thiolate-bridged dinuclear Pt(II/III) complexes.

    PubMed

    Wang, Zhe; Jiang, Lu; Liu, Zhi-Pan; Gan, C R Raymond; Liu, Zhaolin; Zhang, Xin-Hai; Zhao, Jin; Hor, T S Andy

    2012-10-28

    Reaction of [Pt(L)(μ-Cl)](2) (L = ppy (2-phenylpyridine) or bzq (benzo[h]quinoline)) with 2-mercaptobenzoxazole (NOSH) and NaOAc in THF at r.t. yields the dinuclear Pt(II) d(8)-d(8) complexes [Pt(2)L(2)(μ-NOS-κN,S)(2)] (L = ppy, 1; L = bzq, 2) and the Pt(III) d(7)-d(7) complexes [Pt(2)(ppy)(2)(μ-NOS-κN,S)(2)(NOS-κS)(2)] (L = ppy, 3; L = bzq, 4) in one pot. The C,N-cyclometalated ligand is chelating whereas the N,S-donating benzoxazole-2-thiolates doubly bridge the two metal centers. The Pt···Pt separations of 3.0204(3) and 2.9726(8) Å in 1 and 2 contract to 2.685(1) Å in 3 and 2.6923(3) Å in 4, respectively, when two S-bound thiolate ligands coordinate trans- to the Pt···Pt axis. However, cyclometalation is preserved and there is minimum perturbation of the bridging ligands. Complexes 3 and 4 can be also obtained by oxidative addition of the thiolate ligand. In the presence of NaBH(4), 3 and 4 can be reduced to 1 and 2, respectively. At r.t., 1 and 2 exhibit intense orange-red luminescence at 625 nm and 631 nm, respectively. The electrochemical properties of 1-4 have been also discussed.

  14. Stealth fast photoswitching of negative photochromic naphthalene-bridged phenoxyl-imidazolyl radical complexes.

    PubMed

    Mutoh, Katsuya; Kobayashi, Yoichi; Hirao, Yasukazu; Kubo, Takashi; Abe, Jiro

    2016-05-21

    Naphthalene-bridged phenoxyl-imidazolyl radical complex (Np-PIC) is a novel fast switchable negative photochromic compound, which shows the thermal back reaction in the millisecond time scale. Upon UV light irradiation, Np-PIC shows the hypochromic effect in the UVA region due to there being less conjugation in the transient isomer. By replacing the phenoxyl unit with a naphthoxyl unit, the molecular structure has an asymmetric carbon, leading to fast chiroptical switching. This simple molecular design will be a good candidate for the future development of negative photochromic compounds.

  15. Coinage metal complexes with bridging hybrid phosphine-NHC ligands: synthesis of di- and tetra-nuclear complexes.

    PubMed

    Simler, Thomas; Braunstein, Pierre; Danopoulos, Andreas A

    2016-03-28

    A series of P-NHC-type hybrid ligands containing both PR2 and N-heterocyclic carbene (NHC) donors on meta-bis-substituted phenylene backbones, L(Cy), L(tBu) and L(Ph) (R = Cy, tBu, Ph, respectively), was accessed through a modular synthesis from a common precursor, and their coordination chemistry with coinage metals was explored and compared. Metallation of L(Ph)·n(HBr) (n = 1, 2) with Ag2O gave the pseudo-cubane [Ag4Br4(L(Ph))2], isostructural to [Ag4Br4(L(R))2] (R = Cy, tBu) (T. Simler, P. Braunstein and A. A. Danopoulos, Angew. Chem., Int. Ed., 2015, 54, 13691), whereas metallation of ·HBF4 (R = Ph, tBu) led to the dinuclear complexes [Ag2(L(R))2](BF4)2 which, in the solid state, feature heteroleptic Ag centres and a 'head-to-tail' (HT) arrangement of the bridging ligands. In solution, interconversion with the homoleptic 'head-to-head' (HH) isomers is facilitated by ligand fluxionality. 'Head-to-tail' [Cu2Br2(L(R))2] (R = Cy, tBu) dinuclear complexes were obtained from L(R)·HBr and [Cu5(Mes)5], Mes = 2,4,6-trimethylphenyl, which also feature bridging ligands and heteroleptic Cu centres. Although the various ligands L(R)l ed to structurally analogous complexes for R = Cy, tBu and Ph, the rates of dynamic processes occurring in solution are dependent on R, with faster rates for R = Ph. Transmetallation of both NHC and P donor groups from [Ag4Br4(L(tBu))2] to AuI by reaction with [AuCl(THT)] (THT = tetrahydrothiophene) led to L(tBu) transfer and to the dinuclear complex [Au2Cl2L(tBu)] with one L(tBu) ligand bridging the two Au centres. Except for the silver pseudo-cubanes, all other complexes do not exhibit metallophilic interactions. PMID:26886084

  16. Cu(I) complexes of 3,3'-polymethylene bridged derivatives of 2,2'-bi-1,10-phenanthroline.

    PubMed

    Riesgo, Elvira C; Hu, Yi-Zhen; Thummel, Randolph P

    2003-10-20

    A series of 3,3'-polymethylene-2,2'-bi-1,10-phenanthrolines coordinate with Cu(I) to form dinuclear complexes [(CuL)(2)](2+). As the 3,3'-bridge is lengthened from two to four carbons, the ligand becomes more twisted about the 2,2'-bond, favoring dinuclear coordination. The distance between the two copper atoms varies from 2.92 A for the dimethylene-bridged system to 3.59 A for the tetramethylene bridge. Favorable pi-stacking interactions occur between opposing ligands and promote complex formation. Competition experiments indicate that self-recognition is important and only homoleptic complexes are observed. Under equilibrium conditions, formation of the tetramethylene-bridged complex appears to be the most favored while the dimethylene-bridged system is least favored. The intensity of the long wavelength metal-ligand charge-transfer absorption band decreases as the 3,3'-bridge is shortened. Interaction between the two copper centers is evidenced by a splitting of the oxidation wave, and this splitting increases as the Cu-Cu distance is decreased.

  17. Salt Bridge Rearrangement (SaBRe) Explains the Dissociation Behavior of Noncovalent Complexes.

    PubMed

    Loo, Rachel R Ogorzalek; Loo, Joseph A

    2016-06-01

    Native electrospray ionization-mass spectrometry, with gas-phase activation and solution compositions that partially release subcomplexes, can elucidate topologies of macromolecular assemblies. That so much complexity can be preserved in gas-phase assemblies is remarkable, although a long-standing conundrum has been the differences between their gas- and solution-phase decompositions. Collision-induced dissociation of multimeric noncovalent complexes typically distributes products asymmetrically (i.e., by ejecting a single subunit bearing a large percentage of the excess charge). That unexpected behavior has been rationalized as one subunit "unfolding" to depart with more charge. We present an alternative explanation based on heterolytic ion-pair scission and rearrangement, a mechanism that inherently partitions charge asymmetrically. Excessive barriers to dissociation are circumvented in this manner, when local charge rearrangements access a lower-barrier surface. An implication of this ion pair consideration is that stability differences between high- and low-charge state ions usually attributed to Coulomb repulsion may, alternatively, be conveyed by attractive forces from ion pairs (salt bridges) stabilizing low-charge state ions. Should the number of ion pairs be roughly inversely related to charge, symmetric dissociations would be favored from highly charged complexes, as observed. Correlations between a gas-phase protein's size and charge reflect the quantity of restraining ion pairs. Collisionally-facilitated salt bridge rearrangement (SaBRe) may explain unusual size "contractions" seen for some activated, low charge state complexes. That some low-charged multimers preferentially cleave covalent bonds or shed small ions to disrupting noncovalent associations is also explained by greater ion pairing in low charge state complexes. Graphical Abstract ᅟ. PMID:27052739

  18. Salt Bridge Rearrangement (SaBRe) Explains the Dissociation Behavior of Noncovalent Complexes

    NASA Astrophysics Data System (ADS)

    Loo, Rachel R. Ogorzalek; Loo, Joseph A.

    2016-06-01

    Native electrospray ionization-mass spectrometry, with gas-phase activation and solution compositions that partially release subcomplexes, can elucidate topologies of macromolecular assemblies. That so much complexity can be preserved in gas-phase assemblies is remarkable, although a long-standing conundrum has been the differences between their gas- and solution-phase decompositions. Collision-induced dissociation of multimeric noncovalent complexes typically distributes products asymmetrically (i.e., by ejecting a single subunit bearing a large percentage of the excess charge). That unexpected behavior has been rationalized as one subunit "unfolding" to depart with more charge. We present an alternative explanation based on heterolytic ion-pair scission and rearrangement, a mechanism that inherently partitions charge asymmetrically. Excessive barriers to dissociation are circumvented in this manner, when local charge rearrangements access a lower-barrier surface. An implication of this ion pair consideration is that stability differences between high- and low-charge state ions usually attributed to Coulomb repulsion may, alternatively, be conveyed by attractive forces from ion pairs (salt bridges) stabilizing low-charge state ions. Should the number of ion pairs be roughly inversely related to charge, symmetric dissociations would be favored from highly charged complexes, as observed. Correlations between a gas-phase protein's size and charge reflect the quantity of restraining ion pairs. Collisionally-facilitated salt bridge rearrangement (SaBRe) may explain unusual size "contractions" seen for some activated, low charge state complexes. That some low-charged multimers preferentially cleave covalent bonds or shed small ions to disrupting noncovalent associations is also explained by greater ion pairing in low charge state complexes.

  19. Magnetic and structural properties of dinuclear singly bridged-phenoxido metal(II) complexes.

    PubMed

    Massoud, Salah S; Spell, Mark; Ledet, Catherine C; Junk, Thomas; Herchel, Radovan; Fischer, Roland C; Trávníček, Zdeněk; Mautner, Franz A

    2015-02-01

    The reaction of a methanolic solution containing the bi-compartmental phenolic ligand 2,6-bis[bis(2-pyridylmethyl)aminomethyl]-4-chlorophenol (L(Cl)-OH) with MCl2·nH2O in the presence of NH4PF6 or NaClO4 afforded the dinuclear bridged-phenoxido dichlorido-metal(ii) complexes [Co2(μ-L(Cl)O)(H2O)2Cl2][Co2(μ-L(Cl)O)(MeOH)2Cl2](PF6)2 (), [Ni2(μ-L(Cl)O)(MeOH)2Cl2]PF6 (), [Ni2(μ-L(Cl)O)(MeOH)(H2O)Cl2]ClO4·1.25H2O (), [Cu2(μ-L(Cl)O)Cl2]PF6·1/2MeOH () and [Zn2(μ-L(Cl)O)Cl2]PF6·MeOH (). The complexes were characterized by elemental microanalyses, conductivity measurements, IR and UV-Vis spectroscopy, mass spectrometry and single crystal X-ray crystallography. Each M(ii) center within the dinuclear complex cations is octahedrally coordinated in complexes , and five-coordinated distorted square pyramidal in and . Magnetic susceptibility measurements at variable temperature of the complexes revealed weak to moderate antiferromagnetic coupling with |J| values = 8.38, 39.0, 30.2 and 0.79 cm(-1), respectively. The results of DFT calculations correlate well with the experimentally determined antiferromagnetic coupling and show that the magnetic exchange coupling occurs mainly through the phenoxido bridge M-O-M. Implications of geometry around the central metal ion, MM distance, M-O-M bond angle and overlapping of magnetic orbitals on the magnetic exchange coupling are discussed. PMID:25502556

  20. Protein adsorption induced bridging flocculation: the dominant entropic pathway for nano-bio complexation

    NASA Astrophysics Data System (ADS)

    Eren, Necla Mine; Narsimhan, Ganesan; Campanella, Osvaldo H.

    2016-02-01

    Lysozyme-silica interactions and the resulting complexation were investigated through adsorption isotherms, dynamic and electrophoretic light scattering, circular dichroism (CD), and isothermal titration calorimetry (ITC). A thermodynamic analysis of ITC data revealed the existence of two binding modes during protein-nanoparticle complexation. Both binding modes are driven by the cooperation of a favorable enthalpy in the presence of a dominating entropy gain. The first binding mode has a higher binding affinity, a lower equilibrium stoichiometry and is driven by a higher entropic contribution compared to the second type. The observed favorable enthalpy gain in both modes is attributed to non-covalent complexation whereas the entropy gain is associated with the re-organization of the silica surface including not only the solvent and counter ion release, but also the protein's conformational changes. Possible mechanisms are proposed to explain non-covalent complexations for each binding mode by relating the changes in the zeta potential and hydrodynamic radius to the obtained adsorption isotherms and calorimetry profile. Based on all these findings, it is proposed that lysozyme adsorption on nano-silica is the result of protein-nanoparticle and protein-protein interactions that further leads to spontaneous, non-directional and random complexation of silica through bridging flocculation.Lysozyme-silica interactions and the resulting complexation were investigated through adsorption isotherms, dynamic and electrophoretic light scattering, circular dichroism (CD), and isothermal titration calorimetry (ITC). A thermodynamic analysis of ITC data revealed the existence of two binding modes during protein-nanoparticle complexation. Both binding modes are driven by the cooperation of a favorable enthalpy in the presence of a dominating entropy gain. The first binding mode has a higher binding affinity, a lower equilibrium stoichiometry and is driven by a higher entropic

  1. A one-dimensional azido-bridged manganese(III) complex with bidentate Schiff base: Crystal structure and magnetic properties

    SciTech Connect

    Li Wei; Li Zongwei; Li Licun Liao Daizheng; Jiang Zonghui

    2007-10-15

    The synthesis, structural characterization, and magnetic behavior of a novel one-dimensional azido-bridged manganese(III) complex of formula [Mn(L){sub 2}N{sub 3}] (1) is reported, where HL is the bidentate Schiff base obtained from the condensation of salicylaldehyde with 4-methoxy aniline. Complex 1 crystallizes in the monoclinic system, space group P2{sub 1}/n, with a=11.743(4) A, b=24.986(9) A, c=13.081(5) A, {beta}=95.387(7){sup o} and Z=2. The complex is of one-dimensional chain structure with single end-to-end azido bridges and the manganese(III) ion has an elongated octahedral geometry. Magnetic studies show that the weak antiferromagnetic interaction is mediated by the single end-to-end azido bridge with the exchange parameter J=-5.84 cm{sup -1}. - Graphical abstract: A novel azido-bridged manganese(III) complex with bidentate Schiff base ligands has been prepared and characterized structurally and magnetically. The complex is of one-dimensional chain structure with single end-to-end azido bridges in axial positions. Two bidentate Schiff base ligands coordinate in the equatorial mode. The magnetic measurements show that the complex exhibits weak antiferromagnetic interaction.

  2. Influence of salt bridge interactions on the gas-phase stability of DNA/peptide complexes

    NASA Astrophysics Data System (ADS)

    Alves, Sandra; Woods, Amina; Delvolvé, Alice; Tabet, Jean Claude

    2008-12-01

    Negative ion mode electrospray ionization mass spectrometry was used to study DNA duplexes-peptide interaction. In the present study, we show that peptides that contain two adjacent basic residues interact noncovalently with DNA single strand or duplex. Fragmentation of the complexes between peptides containing basic residues and DNA were studied under collisions and showed unexpected dissociation pathways, as previously reported for peptide-peptide interactions. The binary complexes are dissociated either along fragmentation of the covalent bonds of the peptide backbone and/or along the single DNA strand backbone cleavage without disruption of noncovalent interaction, which demonstrates the strong binding of peptide to the DNA strand. Sequential MS/MS and MSn were further performed on ternary complexes formed between duplexes and peptides to investigate the nature of interaction. The CID spectra showed as major pathway the disruption of the noncovalent interactions and the formation of binary complexes and single-strand ions, directed by the nucleic acid gas-phase acidity. Indeed, a preferential formation of complexes with thymidine containing single strands is observed. An alternative pathway is also detected, in which complexes are dissociated along the covalent bond of the peptide and/or DNA according to the basicity. Our experimental data suggest the presence of strong salt bridge interactions between DNA and peptides containing basic residues.

  3. Versatile deprotonated NHC: C,N-bridged dinuclear iridium and rhodium complexes

    PubMed Central

    2016-01-01

    Summary Bearing the versatility of N-heterocyclic carbene (NHC) ligands, here density functional theory (DFT) calculations unravel the capacity of coordination of a deprotonated NHC ligand (pNHC) to generate a doubly C2,N3-bridged dinuclear complex. Here, in particular the discussion is based on the combination of the deprotonated 1-arylimidazol (aryl = mesityl (Mes)) with [M(cod)(μ-Cl)] (M = Ir, Rh) generated two geometrical isomers of complex [M(cod){µ-C3H2N2(Mes)-κC2,κN3}]2). The latter two isomers display conformations head-to-head (H-H) and head-to-tail (H-T) of C S and C 2 symmetry, respectively. The isomerization from the H-H to the H-T conformation is feasible, whereas next substitutions of the cod ligand by CO first, and PMe3 later confirm the H-T coordination as the thermodynamically preferred. It is envisaged the exchange of the metal, from iridium to rhodium, confirming here the innocence of the nature of the metal for such arrangements of the bridging ligands. PMID:26877814

  4. Single-molecule magnet behavior in 2,2'-bipyrimidine-bridged dilanthanide complexes.

    PubMed

    Yu, Wen; Schramm, Frank; Pineda, Eufemio Moreno; Lan, Yanhua; Fuhr, Olaf; Chen, Jinjie; Isshiki, Hironari; Wernsdorfer, Wolfgang; Wulfhekel, Wulf; Ruben, Mario

    2016-01-01

    A series of 2,2'-bipyrimidine-bridged dinuclear lanthanide complexes with the general formula [Ln(tmhd)3]2bpm (tmhd = 2,2,6,6-tetramethyl-3,5-heptanedionate, bpm = 2,2'-bipyrimidine, Ln = Gd(III), 1; Tb(III), 2; Dy(III), 3; Ho(III), 4 and Er(III), 5) has been synthesized and characterized. Sublimation of [Tb(tmhd)3]2bpm onto a Au(111) surface leads to the formation of a homogeneous film with hexagonal pattern, which was studied by scanning tunneling microscopy (STM). The bulk magnetic properties of all complexes have been studied comprehensively. The dynamic magnetic behavior of the Dy(III) and Er(III) compounds clearly exhibits single molecule magnet (SMM) characteristics with an energy barrier of 97 and 25 K, respectively. Moreover, micro-SQUID measurements on single crystals confirm their SMM behavior with the presence of hysteresis loops. PMID:26925361

  5. Single-molecule magnet behavior in 2,2'-bipyrimidine-bridged dilanthanide complexes.

    PubMed

    Yu, Wen; Schramm, Frank; Pineda, Eufemio Moreno; Lan, Yanhua; Fuhr, Olaf; Chen, Jinjie; Isshiki, Hironari; Wernsdorfer, Wolfgang; Wulfhekel, Wulf; Ruben, Mario

    2016-01-01

    A series of 2,2'-bipyrimidine-bridged dinuclear lanthanide complexes with the general formula [Ln(tmhd)3]2bpm (tmhd = 2,2,6,6-tetramethyl-3,5-heptanedionate, bpm = 2,2'-bipyrimidine, Ln = Gd(III), 1; Tb(III), 2; Dy(III), 3; Ho(III), 4 and Er(III), 5) has been synthesized and characterized. Sublimation of [Tb(tmhd)3]2bpm onto a Au(111) surface leads to the formation of a homogeneous film with hexagonal pattern, which was studied by scanning tunneling microscopy (STM). The bulk magnetic properties of all complexes have been studied comprehensively. The dynamic magnetic behavior of the Dy(III) and Er(III) compounds clearly exhibits single molecule magnet (SMM) characteristics with an energy barrier of 97 and 25 K, respectively. Moreover, micro-SQUID measurements on single crystals confirm their SMM behavior with the presence of hysteresis loops.

  6. Dihydrogen activation by sulfido-bridged dinuclear Ru/Ge complexes: insight into the [NiFe] hydrogenase unready state.

    PubMed

    Matsumoto, Tsuyoshi; Itakura, Naohisa; Nakaya, Yukiko; Tatsumi, Kazuyuki

    2011-01-21

    A S/SH bridged hetero-dinuclear Ru/Ge complex cation reacted with H(2) to afford the μ-S/μ-H complex. The reaction was considerably slower compared to that of the μ-S/μ-OH complex. Thus, the μ-S/μ-SH and μ-S/μ-OH complexes might provide models for the unready and ready states, respectively, of [NiFe] hydrogenase. PMID:21072402

  7. Oxoiron(IV) Complex of the Ethylene-Bridged Dialkylcyclam Ligand Me2EBC.

    PubMed

    England, Jason; Prakash, Jai; Cranswick, Matthew A; Mandal, Debasish; Guo, Yisong; Münck, Eckard; Shaik, Sason; Que, Lawrence

    2015-08-17

    We report herein the first example of an oxoiron(IV) complex of an ethylene-bridged dialkylcyclam ligand, [Fe(IV)(O)(Me2EBC)(NCMe)](2+) (2; Me2EBC = 4,11-dimethyl-1,4,8,11-tetraazabicyclo[6.6.2]hexadecane). Complex 2 has been characterized by UV-vis, (1)H NMR, resonance Raman, Mössbauer, and X-ray absorption spectroscopy as well as electrospray ionization mass spectrometry, and its properties have been compared with those of the closely related [Fe(IV)(O)(TMC)(NCMe)](2+) (3; TMC = 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane), the intensively studied prototypical oxoiron(IV) complex of the macrocyclic tetramethylcyclam ligand. Me2EBC has an N4 donor set nearly identical with that of TMC but possesses an ethylene bridge in place of the 1- and 8-methyl groups of TMC. As a consequence, Me2EBC is forced to deviate from the trans-I configuration typically found for Fe(IV)(O)(TMC) complexes and instead adopts a folded cis-V stereochemistry that requires the MeCN ligand to coordinate cis to the Fe(IV)═O unit in 2 rather than in the trans arrangement found in 3. However, switching from the trans geometry of 3 to the cis geometry of 2 did not significantly affect their ground-state electronic structures, although a decrease in ν(Fe═O) was observed for 2. Remarkably, despite having comparable Fe(IV/III) reduction potentials, 2 was found to be significantly more reactive than 3 in both oxygen-atom-transfer (OAT) and hydrogen-atom-transfer (HAT) reactions. A careful analysis of density functional theory calculations on the HAT reactivity of 2 and 3 revealed the root cause to be the higher oxyl character of 2, leading to a stronger O---H bond specifically in the quintet transition state. PMID:26244657

  8. Oxoiron(IV) Complex of the Ethylene-Bridged Dialkylcyclam Ligand Me2EBC.

    PubMed

    England, Jason; Prakash, Jai; Cranswick, Matthew A; Mandal, Debasish; Guo, Yisong; Münck, Eckard; Shaik, Sason; Que, Lawrence

    2015-08-17

    We report herein the first example of an oxoiron(IV) complex of an ethylene-bridged dialkylcyclam ligand, [Fe(IV)(O)(Me2EBC)(NCMe)](2+) (2; Me2EBC = 4,11-dimethyl-1,4,8,11-tetraazabicyclo[6.6.2]hexadecane). Complex 2 has been characterized by UV-vis, (1)H NMR, resonance Raman, Mössbauer, and X-ray absorption spectroscopy as well as electrospray ionization mass spectrometry, and its properties have been compared with those of the closely related [Fe(IV)(O)(TMC)(NCMe)](2+) (3; TMC = 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane), the intensively studied prototypical oxoiron(IV) complex of the macrocyclic tetramethylcyclam ligand. Me2EBC has an N4 donor set nearly identical with that of TMC but possesses an ethylene bridge in place of the 1- and 8-methyl groups of TMC. As a consequence, Me2EBC is forced to deviate from the trans-I configuration typically found for Fe(IV)(O)(TMC) complexes and instead adopts a folded cis-V stereochemistry that requires the MeCN ligand to coordinate cis to the Fe(IV)═O unit in 2 rather than in the trans arrangement found in 3. However, switching from the trans geometry of 3 to the cis geometry of 2 did not significantly affect their ground-state electronic structures, although a decrease in ν(Fe═O) was observed for 2. Remarkably, despite having comparable Fe(IV/III) reduction potentials, 2 was found to be significantly more reactive than 3 in both oxygen-atom-transfer (OAT) and hydrogen-atom-transfer (HAT) reactions. A careful analysis of density functional theory calculations on the HAT reactivity of 2 and 3 revealed the root cause to be the higher oxyl character of 2, leading to a stronger O---H bond specifically in the quintet transition state.

  9. Red-shifted cyanide stretching frequencies in cyanide-bridged transition metal donor-acceptor complexes. Support for vibronic coupling

    SciTech Connect

    Watzky, M.A.; Endicott, J.F.; Song, X.

    1996-06-05

    Patterns in the cyanide stretching frequencies have been examined in several series of monometal- and CN{sup {minus}} bridged transition metal complexes. Metal-to-cyanide back-bonding can be identified as a major factor contributing to red shifts of v{sub CN} in monometal complexes. This effect is complicated in cyanide-bridged complexes in two ways: (a) when both metals can back-bond to cyanide, the net interaction is repulsive and results in a blue shift of v{sub CN}: and (b) when a donor and acceptor are bridged, V{sub CN} undergoes a substantial red shift (sometimes more than 60 cm{sup {minus}1} lower in energy than the parent monometal complex). These effects can be described by simple perturbational models for the electronic interactions. Monometal cyanide complexes and CN{sup {minus}}-bridged backbonding metals can be treated in terms of their perturbations of the CN{sup {minus}} {pi} and {pi}* orbitals by using a simple, Hueckel-like, three-center perturbational treatment of electronic interactions. However, bridged donor-acceptor pairs are best described by a vibronic model in which it is assumed that the extent of electronic delocalization is in equilibrium with variations of some nuclear coordinates. Consistent with this approach, it is found that (a) the oscillator strength of the donor-acceptor charge transfer (DACT) absorption is roughly proportional to the red shift of v{sub CN} and (b) there are strong symmetry constraints on the coupling.

  10. Rodlike bimetallic ruthenium and osmium complexes bridged by phenylene spacers. Synthesis, electrochemistry, and photophysics.

    PubMed

    Welter, Steve; Salluce, Nunzio; Benetti, Arianna; Rot, Nicolette; Belser, Peter; Sonar, Prashant; Grimsdale, Andrew C; Müllen, Klaus; Lutz, Martin; Spek, Anthony L; De Cola, Luisa

    2005-06-27

    In the search for light-addressable nanosized compounds we have synthesized 10 dinuclear homometallic trisbipyridyl complexes of linear structure with the general formula [M(bpy)3-BL-M(bpy)3]4+ [M = Ru(II) or Os(II); BL = polyphenylenes (2, 3, 4, or 5 units) or indenofluorene; bpy = 2,2'-bipyridine]. By using a "chemistry on the complex" approach, different sizes of rodlike systems have been obtained with a length of 19.8 and 32.5 A for the shortest and longest complex, respectively. For one of the ruthenium precursors, [Rubpy-ph2-Si(CH3)3][PF6]2, single crystals were obtained by recrystallization from methanol. Their photophysical and electrochemical properties are reported. All the compounds are luminescent both at room and low temperature with long excited-state lifetimes due to an extended delocalization. Nanosecond transient absorption showed that the lowest excited state involves the chelating unit attached to the bridging ligand. Electrochemical data indicated that the first reduction is at a slightly more positive potential than for the reference complexes [M(bpy)3]2+ (M = Ru, Os). This result confirms that the best acceptor is the bipyridine moiety connected to the conjugated spacers. The role of the tilt angle between the phenylene units, in the two series of complexes, for the ground and excited states is discussed.

  11. Facile formation and redox of benzoxazole-2-thiolate-bridged dinuclear Pt(II/III) complexes.

    PubMed

    Wang, Zhe; Jiang, Lu; Liu, Zhi-Pan; Gan, C R Raymond; Liu, Zhaolin; Zhang, Xin-Hai; Zhao, Jin; Hor, T S Andy

    2012-10-28

    Reaction of [Pt(L)(μ-Cl)](2) (L = ppy (2-phenylpyridine) or bzq (benzo[h]quinoline)) with 2-mercaptobenzoxazole (NOSH) and NaOAc in THF at r.t. yields the dinuclear Pt(II) d(8)-d(8) complexes [Pt(2)L(2)(μ-NOS-κN,S)(2)] (L = ppy, 1; L = bzq, 2) and the Pt(III) d(7)-d(7) complexes [Pt(2)(ppy)(2)(μ-NOS-κN,S)(2)(NOS-κS)(2)] (L = ppy, 3; L = bzq, 4) in one pot. The C,N-cyclometalated ligand is chelating whereas the N,S-donating benzoxazole-2-thiolates doubly bridge the two metal centers. The Pt···Pt separations of 3.0204(3) and 2.9726(8) Å in 1 and 2 contract to 2.685(1) Å in 3 and 2.6923(3) Å in 4, respectively, when two S-bound thiolate ligands coordinate trans- to the Pt···Pt axis. However, cyclometalation is preserved and there is minimum perturbation of the bridging ligands. Complexes 3 and 4 can be also obtained by oxidative addition of the thiolate ligand. In the presence of NaBH(4), 3 and 4 can be reduced to 1 and 2, respectively. At r.t., 1 and 2 exhibit intense orange-red luminescence at 625 nm and 631 nm, respectively. The electrochemical properties of 1-4 have been also discussed. PMID:22960665

  12. Sulfate-bridged dimeric trinuclear copper(II)–pyrazolate complex with three different terminal ligands

    PubMed Central

    Mezei, Gellert

    2016-01-01

    The reaction of CuSO4·5H2O, 4-chloro­pyrazole (4-Cl-pzH) and tri­ethyl­amine (Et3N) in di­methyl­formamide (DMF) produced crystals of di­aqua­hexa­kis­(μ-4-chloro­pyrazolato-κ2 N:N′)bis­(N,N-di­methyl­formamide)di-μ3-hydroxido-bis­(μ4-sulfato-κ4 O:O′:O′′:O′′)hexa­copper(II) N,N-di­methyl­formamide tetra­solvate dihydrate, [Cu3(OH)(SO4)(C3H2ClN2)3(C3H7NO)(H2O)]2·4C3H7NO·2H2O. The centrosymmetric dimeric molecule consists of two trinuclear copper–pyrazolate units bridged by two sulfate ions. The title compound provides the first example of a trinuclear copper–pyrazolate complex with three different terminal ligands on the Cu atoms, and also the first example of such complex with a strongly binding basal sulfate ion. Within each trinuclear unit, the CuII atoms are bridged by μ-pyrazolate groups and a central μ3-OH group, and are coordinated by terminal sulfate, H2O and DMF ligands, respectively. Moreover, the sulfate O atoms coordinate at the apical position to the Cu atoms of the symmetry-related unit, providing square–pyramidal coordination geometry around each copper cation. The metal complex and solvent mol­ecules are involved in O—H⋯O hydrogen bonds, leading to a two-dimensional network parallel to (10-1). PMID:27536383

  13. Triptycene-based Bis(benzimidazole) Carboxylate-Bridged Biomimetic Diiron(II) Complexes.

    PubMed

    Li, Yang; Myae Soe, Chan Myae; Wilson, Justin J; Tuang, Suan Lian; Apfel, Ulf-Peter; Lippard, Stephen J

    2013-04-01

    A triptycene-based bis(benzimidazole) ester ligand, L3, was designed to enhance the electron donating ability of the heterocyclic nitrogen atoms relative to those of the first generation bis(benzoxazole) analogs, L1 and L2. A convergent synthesis of L3 was designed and executed. Three-component titration experiments using UV-visible spectroscopy revealed that the desired diiron(II) complex could be obtained with a 1:2:1 ratio of L3:Fe(OTf)2(MeCN)2:external carboxylate reactants. X-ray crystallographic studies of two diiron complexes derived in this manner from L3 revealed their formulas to be [Fe2 L3(μ-OH)(μ-O2CR)(OTf)2], where R = 2,6-bis(p-tolyl)benzoate (7) or triphenylacetate (8). The structures are similar to that of a diiron complex derived from L1, [Fe2 L1(μ-OH)(μ-O2CAr(Tol))(OTf)2] (9) with a notable difference being that, in 7 and 8, the geometry at iron more closely resembles square-pyramidal than trigonal-bipyramidal. Mössbauer spectroscopic analyses of 7 and 8 indicate the presence of high-spin diiron(II) cores. These results demonstrate the importance of substituting benzimidazole for benzoxazole for assembling biomimetic diiron complexes with syn disposition of two N-donor ligands, as found in O2-activating carboxylate-bridged diiron centers in biology. PMID:23585728

  14. Triptycene-based Bis(benzimidazole) Carboxylate-Bridged Biomimetic Diiron(II) Complexes

    PubMed Central

    Li, Yang; Myae Soe, Chan Myae; Wilson, Justin J.; Tuang, Suan Lian; Apfel, Ulf-Peter

    2013-01-01

    A triptycene-based bis(benzimidazole) ester ligand, L3, was designed to enhance the electron donating ability of the heterocyclic nitrogen atoms relative to those of the first generation bis(benzoxazole) analogs, L1 and L2. A convergent synthesis of L3 was designed and executed. Three-component titration experiments using UV-visible spectroscopy revealed that the desired diiron(II) complex could be obtained with a 1:2:1 ratio of L3:Fe(OTf)2(MeCN)2:external carboxylate reactants. X-ray crystallographic studies of two diiron complexes derived in this manner from L3 revealed their formulas to be [Fe2L3(μ-OH)(μ-O2CR)(OTf)2], where R = 2,6-bis(p-tolyl)benzoate (7) or triphenylacetate (8). The structures are similar to that of a diiron complex derived from L1, [Fe2L1(μ-OH)(μ-O2CArTol)(OTf)2] (9) with a notable difference being that, in 7 and 8, the geometry at iron more closely resembles square-pyramidal than trigonal-bipyramidal. Mössbauer spectroscopic analyses of 7 and 8 indicate the presence of high-spin diiron(II) cores. These results demonstrate the importance of substituting benzimidazole for benzoxazole for assembling biomimetic diiron complexes with syn disposition of two N-donor ligands, as found in O2-activating carboxylate-bridged diiron centers in biology. PMID:23585728

  15. Redox-Active-Ligand-Mediated Formation of an Acyclic Trinuclear Ruthenium Complex with Bridging Nitrido Ligands.

    PubMed

    Bagh, Bidraha; Broere, Daniël L J; Siegler, Maxime A; van der Vlugt, Jarl Ivar

    2016-07-11

    Coordination of a redox-active pyridine aminophenol ligand to Ru(II) followed by aerobic oxidation generates two diamagnetic Ru(III) species [1 a (cis) and 1 b (trans)] with ligand-centered radicals. The reaction of 1 a/1 b with excess NaN3 under inert atmosphere resulted in the formation of a rare bis(nitrido)-bridged trinuclear ruthenium complex with two nonlinear asymmetrical Ru-N-Ru fragments. The spontaneous reduction of the ligand centered radical in the parent 1 a/1 b supports the oxidation of a nitride (N(3-) ) to half an equivalent of N2 . The trinuclear omplex is reactive toward TEMPO-H, tin hydrides, thiols, and dihydrogen. PMID:27321547

  16. Nucleophilic ring opening of bridging thietanes in open triosmium cluster complexes

    SciTech Connect

    Adams, R.D.; Belinski, J.A.

    1992-07-01

    The complexes Os{sub 3}(CO){sub 9}({mu}{sub 3}-S)[{mu}-SCH{sub 2}CMe{sub 2}CMe{sub 2}CH{sub 2}] (1) and Os{sub 3}(CO){sub 9}({mu}{sub 3}-S)[{mu}-SCH{sub 2}CH{sub 2}CH{sub 2}] (2) were obtained from the reactions of Os{sub 3}(CO){sub 10}({mu}{sub 3}-S) with 3,3-dimethylthietane (DMT) and thietane, respectively, at -42 {degree}C in the presence of Me{sub 3}NO. Compound 1 was characterized by a single-crystal X-ray diffraction analysis and was found to contain a DMT group bridging two of the nonbonded metal atoms in the open cluster of three metal atoms by using both lone pairs of electrons on the sulfur atom. Compound 1 reacted with bis(triphenylphosphine)nitrogen(1+) chloride ([PPN]Cl) at 25 {degrees}C to yield the salt [PPN][Os{sub 3}-(CO){sub 9}({mu}-SCH{sub 2}CMe{sub 2}CH{sub 2}Cl)({mu}{sub 3}-S)] (3; 76%), in which the chloride ion was added to one of the methylene groups of the DMT ring in a process that caused the ring to open by cleavage of one of the carbon-sulfur bonds. A 4-chloro-3,3-dimethylpropanethiolate ligand bridges the open edge of the anionic triosmium cluster. Compound 3 was converted to the neutral complex Os{sub 3}(CO){sub 9}[{mu}-SCH{sub 2}CMe{sub 2}CMe{sub 2}CH{sub 2}Cl]({mu}{sub 3}-S)({mu}-H) (4) by reaction with HCl at 25 {degrees}C. Compound 4 is structurally similar to 3, except that is contains a hydride ligand bridging one of the two metal-metal bonds. Compounds 1 and 2 react with HCl in CH{sub 2}Cl{sub 2} solvent to yield the neutral compounds 4 and Os{sub 3}(CO){sub 9}[{mu}-SCH{sub 2}CH{sub 2}CH{sub 2}Cl]({mu}{sub 3}-S)({mu}-H) (5) in 89% and 90% yields, respectively, in one step. 11 refs., 3 figs., 10 tabs.

  17. Copper(I) Complexes of Pyridine-Bridged Phosphaalkene-Oxazoline Pincer Ligands.

    PubMed

    Serin, Spencer C; Pick, Fraser S; Dake, Gregory R; Gates, Derek P

    2016-07-01

    The synthesis of enantiomerically pure pyridine-bridged phosphaalkene-oxazolines ArP═C(Ph)(2,6-C5H3NOx) (1, Ar = Mes/Mes*, Ox = CNOCH(i-Pr)CH2/CNOCH(CH2Ph)CH2) is reported. This new ligand forms a κ(P), κ(2)(NN) dimeric complex with copper(I) (7) that dissociates into a cationic κ(3)(PNN) monomeric complex upon addition of a neutral ligand {[1a·CuL]OTf (8a-e): L = PPh3 (a), P(OPh)3 (b), 2,6-lutidine (c), 4-DMAP (d), 1-methylimidazole (e)}. The P-Cu bond lengths in 8 are influenced by the π-accepting/σ-donating properties of L, and this can be observed by changes in the δ(31)PP═C NMR shift. The donor-acceptor properties in complexes of type 8 have also been investigated by UV/vis spectroscopy and density functional theory calculations.

  18. Experimental and theoretical studies on arene-bridged metal-metal-bonded dimolybdenum complexes.

    PubMed

    Carrasco, Mario; Curado, Natalia; Álvarez, Eleuterio; Maya, Celia; Peloso, Riccardo; Poveda, Manuel L; Rodríguez, Amor; Ruiz, Eliseo; Álvarez, Santiago; Carmona, Ernesto

    2014-05-12

    The bis(hydride) dimolybdenum complex, [Mo2(H)2{HC(N-2,6-iPr2C6H3)2}2(thf)2], 2, which possesses a quadruply bonded Mo2(II) core, undergoes light-induced (365 nm) reductive elimination of H2 and arene coordination in benzene and toluene solutions, with formation of the Mo(I)2 complexes [Mo2{HC(N-2,6-iPr2C6H3)2}2(arene)], 3⋅C6H6 and 3⋅C6H5Me, respectively. The analogous C6H5OMe, p-C6H4Me2, C6H5F, and p-C6H4F2 derivatives have also been prepared by thermal or photochemical methods, which nevertheless employ different Mo2 complex precursors. X-ray crystallography and solution NMR studies demonstrate that the molecule of the arene bridges the molybdenum atoms of the Mo(I)2 core, coordinating to each in an η(2) fashion. In solution, the arene rotates fast on the NMR timescale around the Mo2-arene axis. For the substituted aromatic hydrocarbons, the NMR data are consistent with the existence of a major rotamer in which the metal atoms are coordinated to the more electron-rich C-C bonds.

  19. Copper(I) Complexes of Pyridine-Bridged Phosphaalkene-Oxazoline Pincer Ligands.

    PubMed

    Serin, Spencer C; Pick, Fraser S; Dake, Gregory R; Gates, Derek P

    2016-07-01

    The synthesis of enantiomerically pure pyridine-bridged phosphaalkene-oxazolines ArP═C(Ph)(2,6-C5H3NOx) (1, Ar = Mes/Mes*, Ox = CNOCH(i-Pr)CH2/CNOCH(CH2Ph)CH2) is reported. This new ligand forms a κ(P), κ(2)(NN) dimeric complex with copper(I) (7) that dissociates into a cationic κ(3)(PNN) monomeric complex upon addition of a neutral ligand {[1a·CuL]OTf (8a-e): L = PPh3 (a), P(OPh)3 (b), 2,6-lutidine (c), 4-DMAP (d), 1-methylimidazole (e)}. The P-Cu bond lengths in 8 are influenced by the π-accepting/σ-donating properties of L, and this can be observed by changes in the δ(31)PP═C NMR shift. The donor-acceptor properties in complexes of type 8 have also been investigated by UV/vis spectroscopy and density functional theory calculations. PMID:27315353

  20. Intramolecular ferro- and antiferromagnetic interactions in oxo-carboxylate bridged digadolinium(III) complexes.

    PubMed

    Cañadillas-Delgado, Laura; Fabelo, Oscar; Pasán, Jorge; Delgado, Fernando S; Lloret, Francesc; Julve, Miguel; Ruiz-Pérez, Catalina

    2010-08-21

    Two new digadolinium(III) complexes with monocarboxylate ligands, [Gd2(pac)6(H2O)4] (1) and [Gd2(tpac)6(H2O)4] (2) (Hpac = pentanoic acid and Htpac = 3-thiopheneacetic acid), have been prepared and their structures determined by X-ray diffraction on single crystals. Their structures consist of neutral and isolated digadolinium(III) units, containing six monocarboxylate ligands and four coordinated water molecules, the bridging skeleton being built by a muO(1):kappa2O(1)O(2) framework. This structural pattern has already been observed in the parent acetate-containing compound [Gd2(ac)6(H2O)4] x 4 H2O (3) whose structure and magnetic properties were reported elsewhere (L. Cañadillas-Delgado, O. Fabelo, J. Cano, J. Pasán, F. S. Delgado, M. Julve, F. Lloret and C. Ruiz-Pérez, CrystEngComm, 2009, 11, 2131). Each gadolinium(III) ion in 1 and 2 is nine-coordinated with seven carboxylate-oxygen atoms from four pac (1)/tpac (2) ligands and two water molecules (1 and 2) building a distorted monocapped square antiprism. The values of the intramolecular gadolinium-gadolinium separation are 4.1215(5) (1), 4.1255(6) (2) and 4.1589(3) A (3) and those of the angle at the oxo-carboxylate bridge (theta) are 113.16(13) (1), 112.5(2) (2) and 115.47(7) degrees (3). Magnetic susceptibility measurements in the temperature range 1.9-300 K reveal the occurrence of a weak intramolecular antiferromagnetic interaction [J = -0.032(1) (1) and -0.012(1) cm(-1) (2), the Hamiltonian being defined as H = -JS(A) x S(B)] in contrast with the intramolecular ferromagnetic coupling which occurs in 3 (J = +0.031(1) cm(-1)). The magneto-structural data of 1-3 show the relevance of the geometrical parameters at the muO(1):kappa2O(1)O(2) bridge on the nature of the magnetic coupling between two gadolinium(III) ions.

  1. Synthesis, crystal structure and magnetic properties of an oxalato-bridged Re(IV)Mo(VI) heterobimetallic complex.

    PubMed

    Martínez-Lillo, José; Armentano, Donatella; De Munno, Giovanni; Lloret, Francesc; Julve, Miguel; Faus, Juan

    2011-05-14

    The Re(IV)-Mo(VI) compound of formula (PPh(4))(2)[ReCl(4)(μ-ox)MoO(2)Cl(2)] (1) constitutes the first example of a heterodinuclear oxalato-bridged complex in the coordination chemistry of molybdenum.

  2. Dinuclear Spin-Crossover Complexes Based on Tetradentate and Bridging Cyanocarbanion Ligands.

    PubMed

    Milin, Eric; Belaïd, Sabrina; Patinec, Véronique; Triki, Smail; Chastanet, Guillaume; Marchivie, Mathieu

    2016-09-01

    Spin-crossover (SCO) Fe(II) dinuclear complexes of formula [Fe2(tmpa)2(μ2-tcpd)2]·0.8(CH3OH) (1·MeOH) and [Fe2(andmpa)2(μ2-tcpd)2]·2CH3OH (2·MeOH) (tmpa = tris(2-pyridylmethyl)amine, andmpa = bis(2-pyridylmethyl)aminomethyl)aniline, (tcpd)(2-) = 2-dicyanomethylene-1,1,3,3-tetracyanopropanediide) have been synthesized and characterized by infrared spectroscopy, X-ray diffraction, and magnetic measurements. The crystal structure determinations of the two complexes (1·MeOH and 2·MeOH) and the desolvated complex 1 (from 1·MeOH) revealed a neutral centrosymmetrical dinuclear structure in which the (tcpd)(2-) cyanocarbanion acts as a double μ2-bridging ligand between two [FeL](2+) (L = tmpa (1), andmpa (2)) units involving two free coordination sites in the cis configuration. Examination of the shortest intermolecular contacts in 1·MeOH and 1 reveals no significant hydrogen bonding between the dinuclear units, while in 2·MeOH these units are held together by significant hydrogen bonds between one of the uncoordinated nitrile groups and the anilate function, giving rise to 1D supramolecular structure. The three dinuclear complexes 1, 2·MeOH, and 2 exhibit SCO behaviors which have been evidenced by the thermal evolutions of the χmT product and by the average values of the six Fe-N distances for 1 and 2·MeOH, that reveal a gradual conversion with transition temperatures (T1/2) at ca. 352 K (1), 196 K (2), and 180 K (2·MeOH). For the solvated 1·MeOH, the sharp SCO transition observed around 365 K was induced by the desolvatation process above 330 K during the magnetic measurements. PMID:27526047

  3. Stereocontrol in dinuclear triple lithium-bridged titanium(IV) complexes: solving some stereochemical mysteries.

    PubMed

    Albrecht, Markus; Isaak, Elisabeth; Moha, Verena; Raabe, Gerhard; Fröhlich, Roland

    2014-05-26

    Compounds 1 a-f-H2 form "monomeric" triscatecholate titanium(IV) complexes [Ti(1 a-f)3](2-), which in the presence of Li cations are in equilibrium with the triple lithium-bridged "dimers" [Li3(Ti(1 a-f)3)2](-). The equilibrium strongly depends on the donor ability of the solvent. Usually, in solvents with high donor ability, the stereochemically labile monomer is preferred, whereas in nondonor solvents, the dimer is the major species. In the latter, the stereochemistry at the complex units is "locked". The configuration at the titanium(IV) triscatecholates is influenced by addition of chiral ammonium countercations. In this case, the induced stereochemical information at the monomer is transferred to the dimer. Alternatively, the configuration at the metal complexes can be controlled by enantiomerically pure ester side chains. Due to the different orientation of the ester groups in the monomer or dimer, opposite configurations of the triscatecholates were observed by circular dichroism (CD) spectroscopy for [Ti(1 c-e)3](2-) or [Li3(Ti(1 c-e)3)2](-). A surprising exception was found for the dimer [Li3(Ti(1 f)3)2](-). Herein, the dimer is the dominating species in weak donor (methanol), as well as strong donor (DMSO), solvents. This is due to the bulkiness of the ester substituent destabilizing the monomer. Due to the size of the substituent in [Li3(Ti(1 f)3)2](-) the esters have to adopt an unusual conformation in the dimer resulting in a stereocontrol of the small methyl group. Following this, opposite stereocontrol mechanisms were observed for the central metal-complex units of [Li3(Ti(1 c-e)3)2](-) or [Li3(Ti(1 f)3)2](-).

  4. Redox-Active Tetraruthenium Macrocycles Built from 1,4-Divinylphenylene-Bridged Diruthenium Complexes.

    PubMed

    Scheerer, Stefan; Linseis, Michael; Wuttke, Evelyn; Weickert, Sabrina; Drescher, Malte; Tröppner, Oliver; Ivanović-Burmazović, Ivana; Irmler, Andreas; Pauly, Fabian; Winter, Rainer F

    2016-07-01

    Metallamacrocylic tetraruthenium complexes were generated by treatment of 1,4-divinylphenylene-bridged diruthenium complexes with functionalized 1,3-benzene dicarboxylic acids and characterized by HR ESI-MS and multinuclear NMR spectroscopy. Every divinylphenylene diruthenium subunit is oxidized in two consecutive one-electron steps with half-wave potential splittings in the range of 250 to 330 mV. Additional, smaller redox-splittings between the +/2+ and 0/+ and the 3+/4+ and 2+/3+ redox processes, corresponding to the first and the second oxidations of every divinylphenylene diruthenium entity, are due to electrostatic effects. The lack of electronic coupling through bond or through space is explained by the nodal properties of the relevant molecular orbitals and the lateral side-by-side arrangement of the divinylphenylene linkers. The polyelectrochromic behavior of the divinylphenylene diruthenium precursors is retained and even amplified in these metallamacrocyclic structures. EPR studies down to T=4 K indicate that the dications 1-H(2+) and 1-OBu(2+) are paramagnetic. The dications and the tetracation of macrocycle 3-H display intense (dications) or weak (3-H(4+) ) EPR signals. Quantum chemical calculations indicate that the four most stable conformers of the macrocycles are largely devoid of strain. Bond parameters, energies as well as charge and spin density distributions of model macrocycle 5-H(Me) were calculated for the different charge and spin states.

  5. Oxo-Centered Triruthenium-Acetate Cluster Complexes Derived from Axial or Bridging Ligand Substitution

    NASA Astrophysics Data System (ADS)

    Chen, Zhong-Ning; Dai, Feng-Rong

    The oxo-centered triruthenium-acetate cluster complexes with general formula [Ru3(μ3-O)(μ-OAc)6 (L)2 L']n+ (L and L' = axial ligand, n = 0, 1, 2) show attractive ligand substitution reactivity, multiple redox behavior and rich mixed-valence chemistry. The axial ligands L and L' are comparatively labile and readily substitutable. Although the Ru3(μ3-O)(μ-OAc)6 cluster core possesses high stability, displacement of one of the bridging acetates has been achieved by using π-delocalized N-hetrocyclic ligands with low π* energy levels. Ligand substitution not only affords an excellent means of tuning the redox levels of electron transfer processes, but also provides a feasible approach to design ligand-linked triruthenium cluster oligomers with desired properties. This article reviews the recent progress in the ligand substitution chemistry of oxo-centered triruthenium-acetate complexes with parent Ru3(μ3-O)(μ-OAc)6 cores. The syntheses, redox and spectroscopic properties, and mixed valence chemistry of these oxo-centered triruthenium cluster derivatives are summarized to correlate structures with properties.

  6. Single-molecule magnet behavior in 2,2’-bipyrimidine-bridged dilanthanide complexes

    PubMed Central

    Schramm, Frank; Pineda, Eufemio Moreno; Lan, Yanhua; Fuhr, Olaf; Chen, Jinjie; Isshiki, Hironari; Wernsdorfer, Wolfgang; Wulfhekel, Wulf

    2016-01-01

    Summary A series of 2,2’-bipyrimidine-bridged dinuclear lanthanide complexes with the general formula [Ln(tmhd)3]2bpm (tmhd = 2,2,6,6-tetramethyl-3,5-heptanedionate, bpm = 2,2’-bipyrimidine, Ln = Gd(III), 1; Tb(III), 2; Dy(III), 3; Ho(III), 4 and Er(III), 5) has been synthesized and characterized. Sublimation of [Tb(tmhd)3]2bpm onto a Au(111) surface leads to the formation of a homogeneous film with hexagonal pattern, which was studied by scanning tunneling microscopy (STM). The bulk magnetic properties of all complexes have been studied comprehensively. The dynamic magnetic behavior of the Dy(III) and Er(III) compounds clearly exhibits single molecule magnet (SMM) characteristics with an energy barrier of 97 and 25 K, respectively. Moreover, micro-SQUID measurements on single crystals confirm their SMM behavior with the presence of hysteresis loops. PMID:26925361

  7. Propylene cross-bridged macrocyclic bifunctional chelator: a new design for facile bioconjugation and robust (64)Cu complex stability.

    PubMed

    Pandya, Darpan N; Bhatt, Nikunj; An, Gwang Il; Ha, Yeong Su; Soni, Nisarg; Lee, Hochun; Lee, Yong Jin; Kim, Jung Young; Lee, Woonghee; Ahn, Heesu; Yoo, Jeongsoo

    2014-09-11

    The first macrocyclic bifunctional chelator incorporating propylene cross-bridge was efficiently synthesized from cyclam in seven steps. After the introduction of an extra functional group for facile conjugation onto the propylene cross-bridge, the two carboxylic acid pendants could contribute to strong coordination of Cu(II) ions, leading to a robust Cu complex. The cyclic RGD peptide conjugate of PCB-TE2A-NCS was prepared and successfully radiolabeled with (64)Cu ion. The radiolabeled peptide conjugate was evaluated in vivo through a biodistribution study and animal PET imaging to demonstrate high tumor uptake with low background.

  8. Fully delocalized (ethynyl)(vinyl)phenylene bridged triruthenium complexes in up to five different oxidation states.

    PubMed

    Wuttke, Evelyn; Pevny, Florian; Hervault, Yves-Marie; Norel, Lucie; Drescher, Malte; Winter, Rainer F; Rigaut, Stéphane

    2012-02-01

    Triruthenium [(dppe)(2)Ru{-C≡C-1,4-C(6)H(2)-2,5-R(2)-CH═CH-RuCl(CO)(P(i)Pr(3))(2)}(2)](n+) (4a, R = H; 4b, R = OMe) containing unsymmetrical (ethynyl)(vinyl)phenylene bridging ligands and displaying five well-separated redox states (n = 0-4) are compared to their bis(alkynyl)ruthenium precursors (dppe)(2)Ru{-C≡C-1,4-C(6)H(2)-2,5-R(2)-C≡CR'} (2a,b: R' = TMS; 3a,b: R' = H) and their symmetrically substituted bimetallic congeners, complexes {Cl(dppe)(2)Ru}(2){μ-C≡C-1,4-C(6)H(2)-2,5-R(2)-C≡C} (A(a), R = H; A(b), R = OMe) and {RuCl(CO)(P(i)Pr(3))(2)}(2){μ-CH═CH-1,4-C(6)H(2)-2,5-R(2)-CH═CH} (V(a), R = H; V(b), R = OMe) as well as the mixed (ethynyl)(vinyl)phenylene bridged [Cl(dppe)(2)Ru-C≡C-1,4-C(6)H(4)-CH═CH-RuCl(CO)(P(i)Pr(3))(2)] (M(a)). Successive one-electron transfer steps were studied by means of cyclic voltammetry, EPR and UV-vis-NIR-IR spectroelectrochemistry. These studies show that the first oxidation mainly involves the central bis(alkynyl) ruthenium moiety with only limited effects on the appended vinyl ruthenium moieties. The second to fourth oxidations (n = 2, 3, 4) involve the entire carbon-rich conjugated path of the molecule with an increased charge uniformly distributed between the two arms of the molecules, including the terminal vinyl ruthenium sites. In order to assess the charge distribution, we judiciously use (13)CO labeled analogues to distinguish stretching vibrations due to the acetylide triple bonds and the intense and charge-sensitive Ru(CO) IR probe in different oxidation states. The comparison between complex pairs 4a,b(n+) (n = 0-3), A(a,b)(n+) and V(a,b)(n+) (n = 0-2) serves to elucidate the effect of the methoxy donor substituents on the redox and spectroscopic properties of these systems in their various oxidation states and on the metal/ligand contributions to their frontier orbitals.

  9. Nucleophilic ring opening of bridging thietane ligands in trirhenium carbonyl cluster complexes

    SciTech Connect

    Adams, R.D.; Cortopassi, J.E.; Falloon, S.B.

    1992-11-01

    The reactions of 3,3-dimethylthietane, SCH{sub 2}CMe{sub 2}CH{sub 2} (3,3-DMT), and thietane, SCH{sub 2}CH{sub 2}CH{sub 2}, with Re{sub 3}(CO){sub 10}[{mu}-SCH{sub 2}CH{sub 2}CH{sub 2}]({mu}-H){sub 3}, 2b. Compound 2a was characterized crystallographically and was found to consist of a trirhenium cluster with three bridging hydride ligands and a bridging thietane ligand coordinated through its sulfur atom. 2a and 2b react with halide ions by ring-opening additions to the 3,3-DMT ligand to yield the complex anions [Re{sub 3}(CO){sub 10}({mu}-SCH{sub 2}CMe{sub 2}CH{sub 2}x)({mu}-h){sub 3}]{sup -} 3A-6A, X = F (71%), Cl(71%), Br(84%), I(87%) and [Re{sub 3}(CO){sub 10}({mu}-SCH{sub 2}CH{sub 2}CH{sub 2}Cl)({mu}-H){sub 3}]{sup -}, 4b (67%). Similarly, addition of NMe{sub 3} to 2a and 2b yielded the ring-opened zwitterions Re{sub 3}(CO){sub 10}({mu}-SCH{sub 2}CMe{sub 2}CH{sub 2}NMe{sub 3})({mu}-H){sub 3}, 7 a crystographically. They are zwitterions positively charged at the nitrogen atoms and negatively charged on the trirhenium clusters. Complex 7b was also obtained in a 48% yield from the reaction of Re{sub 3}(C){sub 12}({mu}-H){sub 3} with Me{sub 3}NO in the presence of thietane, but the corresponding reaction using 3,3-DMT yielded only 2a and Re{sub 3}(CO){sub 11}(SCH{sub 2}CMe{sub 2}CH{sub 2})({mu}-H){sub 3}, 8. Attempts to obtain a ring-opening addition to 2a by reaction with PMe{sub 2}Ph yielded only Re{sub 3}(CO){sub 10}(PMe{sub 2}PH){sub 2}({mu}-H){sub 3} by ligand substitution. Attempts to obtain ring opening addition to 8 by reaction with I{sup -} yielded only [Re{sub 3}(CO){sub 11}I({mu}-H){sub 3}]{sup -} by ligand substitution. 20 refs., 3 figs., 10 tabs.

  10. Pre-Elsonian mafic magmatism in the Nain Igneous Complex, Labrador: the bridges layered intrusion

    USGS Publications Warehouse

    Ashwal, L.D.; Wiebe, R.A.; Wooden, J.L.; Whitehouse, M.J.; Snyder, Diane

    1992-01-01

    Decades of work on the pristine, unmetamorphosed, and well exposed anorthositic, mafic and granitic rocks of the Nain igneous complex, Labrador, have led to the conclusion that all plutonic rocks in that area were emplaced in a short time intercal at about 1300 ?? 10 Ma). We report here new isotopic data for mafic intrusive rocks that appear to have crystallized several hundred Ma earlier than the bulk of the plutonic activity in the Nain complex. The Bridges layered intrusion (BLI) is a small (15-20 km2) lens of layered mafic rocks about 1.5 km thick, surrounded and intruded by anorthositic, leuconoritic and leucotroctolitic plutons in the middle of the coastal section of the Nain igneous complex. BLI shows very well developed magmatic structures, including channel scours, slump structures, and ubiquitous modally graded layering. Most rocks, however, show granular textures indicative of recrystallization, presumably caused by emplacement of younger anorthositic rocks. BLI contains cumulate rocks with slightly more primitive mineral compositions (An60-83, Fo66-71) than those of other mafic intrusions in the Nain igneous complex, including Kiglapait. SmNd isotopic data for 7 BLI whole-rocks ranging in composition between olivine melagabbro and olivine leucogabbro yield an age of 1667 ?? 75 Ma, which we interpret as the time of primary crystallization. The internal isotopic systematics of the BLI have been reset, probably by intrusion of adjacent anorthositic plutons. A SmNd mineral isochron (plag, whole-rock, mafics) for a BLI olivine melagabbro gives an age of 1283 ?? 22 Ma, equivalent within error of a mineral array (plag, whole-rock, opx, cpx) for an adjacent, igneous-textured, leuconorite vein (1266 ?? 152 Ma). The initial Nd ratio for BLI corresponds to ??{lunate}Nd = -3.18 ?? 0.44. Other whole-rock samples, however, some with vein-like alteration (Chlorite, serpentine, amphiboles), show ??{lunate}Nd values as low as -9.1, suggesting variable contamination by

  11. Synthesis and spectral characterization of trinuclear, oxo-centered, carboxylate-bridged, mixed-valence iron complexes with Schiff bases.

    PubMed

    Singh, Atresh Kumar; Singh, Alok Kumar

    2012-10-01

    Some novel trinuclear, oxo-centered, carboxylate-bridged, mixed-valence iron complexes of the general formula [Fe(3)O(OOCR)(3)(SB)(3)L(3)] (where R=C(13)H(27), C(15)H(31) or C(17)H(35,) HSB=Schiff bases and L=Ethanol) have been synthesized by the stepwise substitutions of acetate ions from μ(3)-oxo-hexa(acetato)tri(aqua)iron(II)diiron(III), first with straight chain carboxylic acids and then with Schiff bases. The complexes were characterized by elemental analyses, molecular weight determinations and spectral (electronic, infrared, FAB mass, Mössbauer and powder XRD) studies. Molar conductance measurements indicated the complexes to be non-electrolytes in nitrobenzene. Bridging nature of carboxylate and Schiff base anions in the complexes was established by their infrared spectra. Mössbauer spectroscopic studies indicated two quadrupole-split doublets due to Fe(II) and Fe(III) ions at 80, 200 and 295K, confirming the complexes are mixed-valence species. This was also supported by the observed electronic spectra of the complexes. Magnetic susceptibility measurements displayed octahedral geometry around iron in mixed-valence state and a net antiferromagnetic exchange coupling via μ-oxo atom. Trinuclear nature of the complexes was confirmed by their molecular weight determination and FAB mass spectra. A plausible structure for these complexes has been established on the basis of spectral and magnetic moment data.

  12. Synthesis and spectral characterization of trinuclear, oxo-centered, carboxylate-bridged, mixed-valence iron complexes with Schiff bases

    NASA Astrophysics Data System (ADS)

    Singh, Atresh Kumar; Singh, Alok Kumar

    2012-10-01

    Some novel trinuclear, oxo-centered, carboxylate-bridged, mixed-valence iron complexes of the general formula [Fe3O(OOCR)3(SB)3L3] (where R = C13H27, C15H31 or C17H35, HSB = Schiff bases and L = Ethanol) have been synthesized by the stepwise substitutions of acetate ions from μ3-oxo-hexa(acetato)tri(aqua)iron(II)diiron(III), first with straight chain carboxylic acids and then with Schiff bases. The complexes were characterized by elemental analyses, molecular weight determinations and spectral (electronic, infrared, FAB mass, Mössbauer and powder XRD) studies. Molar conductance measurements indicated the complexes to be non-electrolytes in nitrobenzene. Bridging nature of carboxylate and Schiff base anions in the complexes was established by their infrared spectra. Mössbauer spectroscopic studies indicated two quadrupole-split doublets due to Fe(II) and Fe(III) ions at 80, 200 and 295 K, confirming the complexes are mixed-valence species. This was also supported by the observed electronic spectra of the complexes. Magnetic susceptibility measurements displayed octahedral geometry around iron in mixed-valence state and a net antiferromagnetic exchange coupling via μ-oxo atom. Trinuclear nature of the complexes was confirmed by their molecular weight determination and FAB mass spectra. A plausible structure for these complexes has been established on the basis of spectral and magnetic moment data.

  13. Heterobimetallic oxalato-bridged Cu(II)Re(IV) complexes. Synthesis, crystal structure and magnetic properties.

    PubMed

    Chiozzone, R; González, R; Kremer, C; De Munno, G; Armentano, D; Cano, J; Lloret, F; Julve, M; Faus, J

    2001-08-13

    Three copper(II)-rhenium(IV) bimetallic complexes of formula [ReCl(4)(mu-ox)Cu(phen)(2)] (1), [ReCl(4)(mu-ox)Cu(phen)(2)].CH(3)CN (2), and [ReCl(4)(mu-ox)Cu(terpy) (H(2)O)][ReCl(4)(mu-ox)Cu(terpy)(CH(3)CN)] (3) (ox = oxalate anion, phen = 1,10-phenanthroline, and terpy = 2,2':6,2"- terpyridine) have been synthesized and their crystal structures determined by single-crystal X-ray diffraction. Complex 1 crystallizes in the triclinic system, space group P(-1), with a = 9.776(2), b = 11.744(3), c = 14.183(3) A, alpha =102.09(2) degrees, beta = 109.42(2) degrees, gamma = 107.11(2) degrees, and Z = 2, whereas 2 and 3 crystallize in the monoclinic system, space groups P2(1)/n and P2(1)/c, respectively, with a = 12.837(3), b = 17.761(4), c = 12.914(3) A, beta = 91.32(2) degrees, and Z = 4 for 2, and a = 8.930(2), b = 18.543(4), c = 27.503(6) A, beta = 94.67(2) degrees, and Z = 4 for 3. The structures of 1 and 2 are made up of neutral [ReCl(4)(mu-ox)Cu(phen)(2)] bimetallic units. Re(IV) and Cu(II) metal ions exhibit distorted octahedral coordination geometries, being bridged by a bis(bidentate) oxalato ligand. The presence of acetonitrile molecules of crystallization in 2 causes a somewhat greater separation between the bimetallic complexes and a different packing of these units in the crystal structure with respect to 1. The copper-rhenium separation across oxalato is 5.628(2) in 1 and 5.649(3) A in 2. The structure of 3 is made up of two different and neutral bimetallic units, [ReCl(4)(mu-ox)Cu(terpy)(H(2)O)] and [ReCl(4)(mu-ox)Cu(terpy)(CH(3)CN)]. In the first one, the oxalate group behaves as a bis(bidentate) ligand occupying one equatorial and one axial position in the elongated octahedral environment of Cu(II). The water molecule is axially coordinated. In the second one, the oxalate group behaves as a bidentate/monodentate ligand occupying the axial position in the square pyramidal environment of Cu(II). The acetonitrile molecule occupies a basal coordination

  14. Versatile lanthanide-azide complexes with azide/carboxylate/hydroxy mixed bridged chain exhibiting magnetic and luminescent properties

    SciTech Connect

    Wang Haichao; Xue Min; Guo Qian; Zhao Jiongpeng; Liu Fuchen; Ribas, Joan

    2012-03-15

    Two new lanthanide-azide complexes, [Ln{sub 2}(N{sub 3})(isonic){sub 2}(OH){sub 3}(Hisonic)(H{sub 2}O)]{sub n} (Ln=Yb for 1 and Tb for 2, isonic=isonicotinate), were obtained in hydrothermal condition. X-ray diffraction analysis indicated the two complexes are isomorphic chain structure in which the Ln{sup III} ions are mixed bridged by the azide anions, hydroxyl anions and carboxylate groups of the isonicotinate ligands. Further studies indicated weak antiferromagnetic interactions between the Ln{sup III} ions in 1 and 2, and complex 2 exhibit green sensitized Luminescent character of Tb{sup III} ion. - Graphical abstract: Two new 1D lanthanide-azide complexes, [Ln{sub 2}(N{sub 3})(isonic){sub 2}(OH){sub 3}(Hisonic)(H{sub 2}O)]{sub n} (Ln=Yb{sup III} for 1 and Tb{sup III} for 2, isonic=isonicotinate), were synthesized by hydrothermal reaction and exhibit interesting magnetism and fluorescence properties. Highlights: Black-Right-Pointing-Pointer The research provided a new method for synthesizing lanthanide-azide complexes. Black-Right-Pointing-Pointer The complexes have an interesting azide/hydroxyl/carboxylate mixed bridged1D chain structure. Black-Right-Pointing-Pointer The antiferromagnetic coupling between the complexes and 2 displays green luminescence.

  15. Synthesis, spectral and redox switchable cubic NLO properties of chiral dinuclear iron cyanide/isocyanide-bridged complexes.

    PubMed

    Ma, Xiao; Lin, Chen-Sheng; Zhang, Hui; Lin, Yi-Ji; Hu, Sheng-Min; Sheng, Tian-Lu; Wu, Xin-Tao

    2013-09-14

    Two chiral dinuclear cyanide/isocyanide-bridged complexes (R)-[Cp(dppe)Fe-CN-Fe(dppp)Cp]PF6 (1[PF6]) and (R)-[Cp(dppe)Fe-NC-Fe(dppp)Cp]PF6 (2[PF6]), and their mono-oxidation products (R)-[Cp(dppe)Fe(II)-CN-Fe(III)(dppp)Cp] [PF6]2 (1[PF6]2) and (R)-[Cp(dppe)Fe(III)-NC-Fe(II)(dppp)Cp][PF6]2 (2[PF6]2) were synthesized and fully characterized. The electronic spectra of both the mixed-valence complexes 1[PF6]2 and 2[PF6]2 exhibit a strong and broad absorption band with two discernable peaks in the NIR region, which are attributed to Fe(II)-Fe(III) IVCT transitions. The attributions are supported by the DFT calculations. Under irradiation with a nanosecond laser at 1064 nm, the measured third-order NLO results of all four cyanide-bridged complexes showed that complexes 1(+) and 2(+) do not exhibit an NLO response, but their one-electron oxidation complexes 1(2+) and 2(2+) exhibit a strong NLO response due to a resonance enhanced effect. In addition, both complexes 1(2+) and 2(2+) display RSA and self-defocusing effects and show good optical limiting behavior in a broadband range.

  16. Pyrazole bridged dinuclear Cu(II) and Zn(II) complexes as phosphatase models: Synthesis and activity

    NASA Astrophysics Data System (ADS)

    Naik, Krishna; Nevrekar, Anupama; Kokare, Dhoolesh Gangaram; Kotian, Avinash; Kamat, Vinayak; Revankar, Vidyanand K.

    2016-12-01

    Present work describes synthesis of dibridged dinuclear [Cu2L2(μ2-NN pyr)(NO3)2(H2O)2] and [Zn2L(μ-OH)(μ-NNpyr)(H2O)2] complexes derived from a pyrazole based ligand bis(2-hydroxy-3-methoxybenzylidene)-1H-pyrazole-3,5-dicarbohydrazide. The ligand shows dimeric chelate behaviour towards copper against monomeric for zinc counterpart. Spectroscopic evidences affirm octahedral environment around the metal ions in solution state and non-electrolytic nature of the complexes. Both the complexes are active catalysts towards phosphomonoester hydrolysis with first order kcat values in the range of 2 × 10-3s-1. Zinc complex exhibited promising catalytic efficiency for the hydrolysis. The dinuclear complexes hydrolyse via Lewis acid activation, whereby the phosphate esters are preferentially bound in a bidentate bridging fashion and subsequent nucleophilic attack to release phosphate group.

  17. Multinuclear oxo-bridged manganese complexes with a bulky substituted benzoate ligand: novel species obtained by using steric control.

    PubMed

    Mukhopadhyay, Sumitra; Armstrong, William H

    2003-10-29

    A sterically hindered carboxylate ligand is used to synthesize the first transition metal complex containing both bis-mu-oxo and bis-mu-carboxylato groups, [Mn2(mu-O)2(mu-ArtolCO2)2(bpy)2]+. However, methyl substitution on the chelating bipyridine ligand results in the formation of a strikingly different and novel hexanuclear species, [Mn6(mu-O)4(mu3-O)4(mu-ArtolCO2)2(dmb)6]4+. Steric interactions between the bridging carboxylates and chelating pyridine-based ligands determine the nuclearity of the complexes formed.

  18. 4,4'-dithiodipyridine as a bridging ligand in osmium and ruthenium complexes: the electron conductor ability of the -S-S- bridge.

    PubMed

    Silva, Welter C; Lima, Joacy B; Moreira, Icaro S; Neto, Antônio M; Gandra, Flávio C G; Ferreira, Antônio G; McGarvey, Bruce R; Franco, Douglas W

    2003-10-20

    The compounds [Ru(NH(3))(5)(dtdp)](TFMS)(3), [Os(NH(3))(5)(dtdp)](TFMS)(3), [(NH(3))(5)Os(dtdp)Os(NH(3))(5)](TFMS)(6), [(NH(3))(5)Os(dtdp)Ru(NH(3))(5)](TFMS)(3)(PF(6))(2), and [(NH(3))(5)Os(dtdp)Fe(CN)(5)] (dtdp = 4,4'-dithiodipyridine, TFMS = trifluoromethanesulfonate) have been synthesized and characterized by elemental analysis, cyclic voltammetry, electronic, vibrational, EPR, and (1)H NMR spectroscopies. Changes in the electronic and voltammetric spectra of the ion complex [Os(NH(3))(5)(dtdp)](3+) as a function of the solution pH enable us to calculate the pK(a) for the [Os(NH(3))(5)(dtdpH)](4+) and [Os(NH(3))(5)(dtdpH)](3+) acids as 3.5 and 5.5, respectively. The comparison of the above pK(a) data with that for the free ligand (pK(1) = 4.8) provides evidence for the -S-S- bridge efficiency as an electron conductor between the two pyridine rings. The symmetric complex, [(NH(3))(5)Os(dtdp)Os(NH(3))(5)](6+), is found to exist in two geometric forms, and the most abundant form (most probably trans) has a strong conductivity through the -S-S- bridge, as is shown by EPR, which finds it to have an S = 1 spin state with a spin-spin interaction parameter of 150-200 G both in the solid sate and in frozen solution. Further the NMR of the same complex shows a large displacement of unpaired spin into the pi orbitals of the dttp ligand relative to that found in [Os(NH(3))(5)(dtdp)](3+). The comproportionation constant, K(c) = 2.0 x 10(5), for the equilibrium equation [Os(II)Os(II)] + [Os(III)Os(III)] right harpoon over left harpoon 2[Os(II)Os(III)] and the near-infrared band energy for the mixed-valence species (MMCT), [(NH(3))(5)Os(dtdp)Os(NH(3))(5)](5+) (lambda(MMCT) = 1665 nm, epsilon = 3.5 x 10(3) M(-)(1) cm(-)(1), deltanu(1/2) = 3.7 x 10(3) cm(-)(1), alpha = 0.13, and H(AB) = 7.8 x 10(2) cm(-)(1)), are quite indicative of strong electron delocalization between the two osmium centers. The electrochemical and spectroscopic data for the unsymmetrical binuclear complexes

  19. Methyl-, Ethenyl-, and Ethynyl-Bridged Cationic Digold Complexes Stabilized by Coordination to a Bulky Terphenylphosphine Ligand.

    PubMed

    Espada, María F; Campos, Jesús; López-Serrano, Joaquín; Poveda, Manuel L; Carmona, Ernesto

    2015-12-14

    Reactions of the gold(I) triflimide complex [Au(NTf2 )(PMe2 Ar${{^{{\\rm Dipp}{_{2}}}}}$)] (1) with the gold(I) hydrocarbyl species [AuR(PMe2 Ar${{^{{\\rm Dipp}{_{2}}}}}$)] (2 a-2 c) enable the isolation of hydrocarbyl-bridged cationic digold complexes with the general composition [Au2 (μ-R)(PMe2 Ar${{^{{\\rm Dipp}{_{2}}}}}$)2 ][NTf2 ], where Ar${{^{{\\rm Dipp}{_{2}}}}}$=C6 H3 -2,6-(C6 H3 -2,6-iPr2 )2 and R=Me (3), CHCH2 (4), or CCH (5). Compound 3 is the first alkyl-bridged digold complex to be reported and features a symmetric [Au(μ-CH3 )Au](+) core. Complexes 4 and 5 are the first species of their kind that contain simple, unsubstituted vinyl and acetylide units, respectively. In the series of complexes 3-5, the bridging carbon atom systematically changes its hybridization from sp(3) to sp(2) and sp. Concomitant with this change, and owing to variations in the nature of the bonding within the [Au(μ-R)Au](+) unit, there is a gradual decrease in aurophilicity, that is, the strength of the Au⋅⋅⋅Au bonding interaction decreases. This change is illustrated by a monotonic increase in the Au-Au distance by approximately 0.3 Å from R=CH3 (2.71 Å) to CHCH2 (3.07 Å) and CCH (3.31 Å).

  20. A family of acetato-diphenoxo triply bridged dimetallic Zn(II)Ln(III) complexes: SMM behavior and luminescent properties.

    PubMed

    Oyarzabal, Itziar; Artetxe, Beñat; Rodríguez-Diéguez, Antonio; García, JoséÁngel; Seco, José Manuel; Colacio, Enrique

    2016-06-21

    Eleven dimetallic Zn(II)-Ln(III) complexes of the general formula [Zn(µ-L)(µ-OAc)Ln(NO3)2]·CH3CN (Ln(III) = Pr (1), Nd (2), Sm (3), Eu (4), Gd (5), Tb (6), Dy (7), Ho (8), Er (9), Tm (10), Yb (11)) have been prepared in a one-pot reaction from the compartmental ligand N,N'-dimethyl-N,N'-bis(2-hydroxy-3-formyl-5-bromo-benzyl)ethylenediamine (H2L). In all these complexes, the Zn(II) ions occupy the internal N2O2 site whereas the Ln(III) ions show preference for the O4 external site. Both metallic ions are bridged by an acetate bridge, giving rise to triple mixed diphenoxido/acetate bridged Zn(II)Ln(III) compounds. The Nd, Dy, Er and Yb complexes exhibit field induced single-ion magnet (SIM) behaviour, with Ueff values ranging from 14.12 to 41.55 K. The Er complex shows two relaxation processes, but only the second relaxation process with an energy barrier of 21.0 K has been characterized. The chromophoric L(2-) ligand is able to act as an "antenna" group, sensitizing the near-infrared (NIR) Nd(III) and Yb(III)-based luminescence in complexes 2 and 11 and therefore, both compounds can be considered as magneto-luminescent materials. In addition, the Sm(III), Eu(III) and Tb(III) derivatives exhibit characteristic emissions in the visible region. PMID:27230817

  1. A new biotinylated tris bipyridinyl iron(II) complex as redox biotin-bridge for the construction of supramolecular biosensing architectures.

    PubMed

    Haddour, Naoufel; Gondran, Chantal; Cosnier, Serge

    2004-02-01

    The bioaffine immobilization of several avidin layers on an electrode modified by a biotinylated polymer was accomplished by the first biotinylated redox bridge consisted of a tris(bipyridyl)iron(II) complex bearing six pre-oriented biotin groups.

  2. A metal-bridged tricyclic aromatic system: synthesis of osmium polycyclic aromatic complexes.

    PubMed

    Zhu, Congqing; Zhu, Qin; Fan, Jinglan; Zhu, Jun; He, Xumin; Cao, Xiao-Yu; Xia, Haiping

    2014-06-10

    Aromaticity is one of the most important concepts in organic chemistry. A variety of metalla-aromatic compounds have been recently prepared and in most of those examples, the metal participates only in a monocyclic ring. In contrast, metal-bridged bicyclic aromatic molecules, in which a metal is shared between two aromatic rings, have been less developed. Herein, we report the first metal-bridged tricyclic aromatic system, in which the metal center is shared by three aromatic five-membered rings. These metalla-aromatics are formed by reaction between osmapentalyne and arene nucleophiles. Experimental results and theoretical calculations reveal that the three five-membered rings around the osmium center are aromatic. In addition, the broad absorption bands in the UV/Vis absorption spectra of these novel aromatic systems cover almost the entire visible region. This straightforward synthetic strategy may be extended to the synthesis of other metal-bridged polycyclic aromatics. PMID:24782397

  3. Interfacial charge-transfer transitions and reorganization energies in sulfur-bridged TiO2-x-benzenedithiol complexes (x: o, m, p).

    PubMed

    Fujisawa, Jun-Ichi; Muroga, Ryuki; Hanaya, Minoru

    2016-08-10

    Surface complexes formed between TiO2 nanoparticles and enediol compounds such as 1,2-benzenediol (o-BDO) via Ti-O-C linkages show absorption of visible light due to interfacial charge-transfer (ICT) transitions. The ICT transitions take place from the π-conjugated systems to TiO2. Recently, we reported a surface complex formed between TiO2 and 1,2-benzenedithiol (o-BDT) via Ti-S-C linkages. This sulfur-bridged complex shows ICT transitions from the sulfur bridging atoms to TiO2. Interestingly, it was demonstrated that the ICT transitions in the sulfur-bridged TiO2-o-BDT complex induce photoelectric conversion more efficiently than those in the oxygen-bridged TiO2-o-BDO complex. This result suggests that carrier recombination is suppressed with the sulfur bridging atoms. In this paper, we examine ICT transitions and reorganization energies in the sulfur-bridged TiO2-x-BDT complexes (x: o, m, p) and compare them with those in the oxygen-bridged TiO2-x-BDO complexes. The estimated reorganization energies for the sulfur-bridged TiO2-x-BDT complexes (x: o, m, p) are much smaller than those for the oxygen-bridged TiO2-x-BDO ones. Based on the Marcus theory, the small reorganization energy calculated for the TiO2-o-BDT complex, which is less than half of that for the TiO2-o-BDO complex, increases the activation energy of carrier recombination. The small reorganization energy is attributed to the characteristic distribution of the highest occupied molecular orbital (HOMO) on the sulfur-bridging atoms in the TiO2-o-BDT complex, which inhibits structural changes in the benzene ring in the ICT excited state. Our work reveals the important role of the sulfur bridging atoms in the suppression of carrier recombination. PMID:27456170

  4. Electronic communication in phosphine substituted bridged dirhenium complexes - clarifying ambiguities raised by the redox non-innocence of the C4H2- and C4-bridges.

    PubMed

    Li, Yan; Blacque, Olivier; Fox, Thomas; Luber, Sandra; Polit, Walther; Winter, Rainer F; Venkatesan, Koushik; Berke, Heinz

    2016-04-01

    The mononuclear rhenium carbyne complex trans-[Re(C[triple bond, length as m-dash]CSiMe3)([triple bond, length as m-dash]C-Me)(PMe3)4][PF6] (2) was prepared in 90% yield by heating a mixture of the dinitrogen complex trans-[ReCl(N2)(PMe3)4] (1), TlPF6, and an excess of HC[triple bond, length as m-dash]CSiMe3. 2 could be deprotonated with KOtBu to the vinylidene complex trans-[Re(C[triple bond, length as m-dash]CSiMe3)([double bond, length as m-dash]C[double bond, length as m-dash]CH2)(PMe3)4] (3) in 98% yield. Oxidation of 3 with 1.2 equiv. of [Cp2Fe][PF6] at -78 °C gave the Cβ-C'β coupled dinuclear rhenium biscarbyne complex trans-[(Me3SiC[triple bond, length as m-dash]C)(PMe3)4Re[triple bond, length as m-dash]C-CH2-CH2-C[triple bond, length as m-dash]Re(PMe3)4(C[triple bond, length as m-dash]CSiMe3)][PF6]2 (5) in 92% yield. Deprotonation of 5 with an excess of KOtBu in THF produced the diamagnetic trans-[(Me3SiC[triple bond, length as m-dash]C)(PMe3)4Re[double bond, length as m-dash]C[double bond, length as m-dash]CH-CH[double bond, length as m-dash]C[double bond, length as m-dash]Re(PMe3)4(C[triple bond, length as m-dash]CSiMe3)] complex (E-6(S)) in 87% yield with an E-butadienediylidene bridge. Density functional theory (DFT) calculations of E-6(S) confirmed its singlet ground state. The Z-form of 6 (Z-6(S)) could not be observed, which is in accord with its DFT calculated 17.8 kJ mol(-1) higher energy. Oxidation of E-6 with 2 equiv. of [Cp2Fe][PF6] resulted in the stable diamagnetic dicationic trans-[(Me3SiC[triple bond, length as m-dash]C)(PMe3)4Re[triple bond, length as m-dash]C-CH[double bond, length as m-dash]CH-C[triple bond, length as m-dash]Re(PMe3)4(C[triple bond, length as m-dash]CSiMe3)][PF6]2 complex (E-6[PF6]2) with an ethylenylidene dicarbyne structure of the bridge. The paramagnetic mixed-valence (MV) complex E-6[PF6] was obtained by comproportionation of E-6(S) and E-6[PF6]2 or by oxidation of E-6(S) with 1 equiv. of [Cp2Fe][PF6]. The

  5. LOOKING WNW, CHEVROLET AVENUE BRIDGE CROSSING FLINT RIVER. BRIDGE CONNECTED ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    LOOKING WNW, CHEVROLET AVENUE BRIDGE CROSSING FLINT RIVER. BRIDGE CONNECTED NORTH AND SOUTH PORTIONS OF FACTORY COMPLEX. DANIEL LUTEN DESIGNED THE BRIDGE, AND ILLINOIS BRIDGE COMPANY BUILT IT IN 1918. THE BRIDGE WAS THE SITE OF THE BATTLE OF RUNNING BULLS IN THE 1936-1937 GM SIT DOWN STRIKE. - Delphi Flint West, 300 Chevrolet Avenue, Flint, Genesee County, MI

  6. Chloride-Bridged Dinuclear Rhodium(III) Complexes Bearing Chiral Diphosphine Ligands: Catalyst Precursors for Asymmetric Hydrogenation of Simple Olefins.

    PubMed

    Kita, Yusuke; Hida, Shoji; Higashihara, Kenya; Jena, Himanshu Sekhar; Higashida, Kosuke; Mashima, Kazushi

    2016-07-11

    Efficient rhodium(III) catalysts were developed for asymmetric hydrogenation of simple olefins. A new series of chloride-bridged dinuclear rhodium(III) complexes 1 were synthesized from the rhodium(I) precursor [RhCl(cod)]2 , chiral diphosphine ligands, and hydrochloric acid. Complexes from the series acted as efficient catalysts for asymmetric hydrogenation of (E)-prop-1-ene-1,2-diyldibenzene and its derivatives without any directing groups, in sharp contrast to widely used rhodium(I) catalytic systems that require a directing group for high enantioselectivity. The catalytic system was applied to asymmetric hydrogenation of allylic alcohols, alkenylboranes, and unsaturated cyclic sulfones. Control experiments support the superiority of dinuclear rhodium(III) complexes 1 over typical rhodium(I) catalytic systems. PMID:27088539

  7. Di-, tri-, and tetranuclear nickel(II) complexes with oximato bridges: magnetism and catecholase-like activity of two tetranuclear complexes possessing rhombic topology.

    PubMed

    Das, Lakshmi Kanta; Biswas, Apurba; Kinyon, Jared S; Dalal, Naresh S; Zhou, Haidong; Ghosh, Ashutosh

    2013-10-21

    Oxime-based tridentate Schiff base ligands 3-[2-(diethylamino)ethylimino]butan-2-one oxime (HL(1)) and 3-[3-(dimethylamino)propylimino]butan-2-one oxime (HL(2)) produced the dinuclear complex [Ni2L(1)2](ClO4)2 (1) and trinuclear complex [Ni3(HL(2))3(μ3-O)](ClO4)4·CH3CN (2), respectively, upon reaction with Ni(ClO4)2·6H2O. However, in a slightly alkaline medium, both of the ligands underwent hydrolysis and resulted in tetranuclear complexes [{Ni(deen)(H2O)}2(μ3-OH)2{Ni2(moda)4}](ClO4)2·2CH3CN (3) and [{Ni(dmpn)(CH3CN)2}2(μ3-OH)2{Ni2(moda)4}](ClO4)2·CH3CN (4), where deen = 2-(diethylamino)ethylamine, dmpn = 3-(dimethylamino)-1-propylamine, and modaH = diacetyl monoxime. All four complexes have been structurally characterized. Complex 1 is a centrosymmetric dimer where the square planar nickel(II) atoms are joined solely by the oximato bridges. In complex 2, three square planar nickel atoms form a triangular core through a central oxido (μ3-O) and peripheral oximato bridges. Tetranuclear complexes 3 and 4 consist of four distorted octahedral nickel(II) ions held together in a rhombic chair arrangement by two central μ3-OH and four peripheral oximato bridges. Magnetic susceptibility measurements indicated that dinuclear 1 and trinuclear 2 exhibited diamagnetic behavior, while tetranuclear complexes 3 and 4 were found to have dominant antiferromagnetic intramolecular coupling with concomitant ferromagnetic interactions. Despite its singlet ground state, both 3 and 4 serve as useful examples of Kahn's model for competing spin interactions. High-frequency EPR studies were also attempted, but no signal was detected, likely due to the large energy gap between the ground and first excited state. Complexes 3 and 4 exhibited excellent catecholase-like activity in the aerial oxidation of 3,5-di-tert-butylcatechol to the corresponding o-quinone, whereas 1 and 2 did not show such catalytic activity. Kinetic data analyses of this oxidation reaction in acetonitrile

  8. Neuroarchitecture and neuroanatomy of the Drosophila central complex: A GAL4-based dissection of protocerebral bridge neurons and circuits

    PubMed Central

    Wolff, Tanya; Iyer, Nirmala A; Rubin, Gerald M

    2015-01-01

    Insects exhibit an elaborate repertoire of behaviors in response to environmental stimuli. The central complex plays a key role in combining various modalities of sensory information with an insect's internal state and past experience to select appropriate responses. Progress has been made in understanding the broad spectrum of outputs from the central complex neuropils and circuits involved in numerous behaviors. Many resident neurons have also been identified. However, the specific roles of these intricate structures and the functional connections between them remain largely obscure. Significant gains rely on obtaining a comprehensive catalog of the neurons and associated GAL4 lines that arborize within these brain regions, and on mapping neuronal pathways connecting these structures. To this end, small populations of neurons in the Drosophila melanogaster central complex were stochastically labeled using the multicolor flip-out technique and a catalog was created of the neurons, their morphologies, trajectories, relative arrangements, and corresponding GAL4 lines. This report focuses on one structure of the central complex, the protocerebral bridge, and identifies just 17 morphologically distinct cell types that arborize in this structure. This work also provides new insights into the anatomical structure of the four components of the central complex and its accessory neuropils. Most strikingly, we found that the protocerebral bridge contains 18 glomeruli, not 16, as previously believed. Revised wiring diagrams that take into account this updated architectural design are presented. This updated map of the Drosophila central complex will facilitate a deeper behavioral and physiological dissection of this sophisticated set of structures. J. Comp. Neurol. 523:997–1037, 2015. © 2014 Wiley Periodicals, Inc. PMID:25380328

  9. Investigating vibrational anharmonic couplings in cyanide-bridged transition metal mixed valence complexes using two-dimensional infrared spectroscopy

    NASA Astrophysics Data System (ADS)

    Slenkamp, Karla M.; Lynch, Michael S.; Van Kuiken, Benjamin E.; Brookes, Jennifer F.; Bannan, Caitlin C.; Daifuku, Stephanie L.; Khalil, Munira

    2014-02-01

    Using polarization-selective two-dimensional infrared (2D IR) spectroscopy, we measure anharmonic couplings and angles between the transition dipole moments of the four cyanide stretching (νCN) vibrations found in [(NH3)5RuIIINCFeII(CN)5]- (FeRu) dissolved in D2O and formamide and [(NC)5FeIICNPtIV(NH3)4NCFeII(CN)5]4- (FePtFe) dissolved in D2O. These cyanide-bridged transition metal complexes serve as model systems for studying the role of high frequency vibrational modes in ultrafast photoinduced charge transfer reactions. Here, we focus on the spectroscopy of the νCN modes in the electronic ground state. The FTIR spectra of the νCN modes of the bimetallic and trimetallic systems are strikingly different in terms of frequencies, amplitudes, and lineshapes. The experimental 2D IR spectra of FeRu and FePtFe and their fits reveal a set of weakly coupled anharmonic νCN modes. The vibrational mode anharmonicities of the individual νCN modes range from 14 to 28 cm-1. The mixed-mode anharmonicities range from 2 to 14 cm-1. In general, the bridging νCN mode is most weakly coupled to the radial νCN mode, which involves the terminal CN ligands. Measurement of the relative transition dipole moments of the four νCN modes reveal that the FeRu molecule is almost linear in solution when dissolved in formamide, but it assumes a bent geometry when dissolved in D2O. The νCN modes are modelled as bilinearly coupled anharmonic oscillators with an average coupling constant of 6 cm-1. This study elucidates the role of the solvent in modulating the molecular geometry and the anharmonic vibrational couplings between the νCN modes in cyanide-bridged transition metal mixed valence complexes.

  10. Touching the upper limit for ferromagnetic interactions in hetero-bridged dinuclear [Cu2(II)] complexes using a novel N5-dinucleating ligand bearing an endogenous monoatomic amido(R-NH(-))-bridging group.

    PubMed

    Colacio, Enrique; Perea-Buceta, Jesús E; Mota, Antonio J; Brechin, Euan K; Prescimone, Alessandro; Hänninen, Mikko; Seppälä, Petri; Sillanpää, Reijo

    2012-01-21

    A novel N(5)-dinucleating ligand 4-amino-3,5-bis(bipyridine-2-yl)-1,2,4-triazole allows the preparation for the first time, and under mild conditions, of single and mixed amido(R-NH(-))-bridged copper(II) complexes, the latter exhibiting very strong ferromagnetic coupling.

  11. Novel lanthanide(II) complexes supported by carbon-bridged biphenolate ligands: synthesis, structure and catalytic activity.

    PubMed

    Deng, Mingyu; Yao, Yingming; Shen, Qi; Zhang, Yong; Sun, Jin

    2004-03-21

    [Ln[N(SiMe3)2]2(THF)2](Ln = Sm, Yb) reacts with 1 equiv. of carbon-bridged biphenols, 2,2'-methylene-bis(6-tert-butyl-4-methylphenol)(L1H2) or 2,2'-ethylidene-bis(4,6-di-tert-butylphenol)(L2H2), in toluene to give the novel aryloxide lanthanide(II) complexes [[LnL1(THF)n]2](Ln = Sm, n = 3 (1); Ln = Yb, n = 2 (2)) and [[LnL2(THF)3]2](Ln = Sm (5); Ln = Yb (6)) in quantitative yield, respectively. Addition of 2 equiv. of hexamethylphosphoric triamide (HMPA) to a tetrahydrofuran (THF) solution of 1, 2 and 5 affords the corresponding HMPA-coordinated complexes, [[LnL1(THF)m(HMPA)n]2(THF)y](Ln = Sm, n = 2, m = 0, y = 2 (3); Ln = Yb, m = 1, n = 1, y = 6 (4)) and [[SmL2(HMPA)2]2](7) in excellent yields. The single-crystal structural analyses of 3, 4 and 7 revealed that these aryloxide lanthanide(II) complexes are dimeric with two Ln-O bridges. The coordination geometry of each lanthanide metal can be best described as a distorted trigonal bipyramid. Complexes 1-3, 5 and 7 can catalyze the ring-opening polymerization of epsilon-caprolactone (epsilon-CL), and 1-3, along with 5 show moderate activity for the ring-opening polymerization of 2,2-dimethyltrimethylene carbonate (DTC) and the copolymerization of epsilon-CL and DTC to give random copolymers with high molecular weights and relatively narrow molecular weight distributions.. PMID:15252483

  12. μ-η6,η6-Arene-bridged diuranium hexakisketimide complexes isolable in two states of charge.

    PubMed

    Diaconescu, Paula L; Cummins, Christopher C

    2012-03-01

    Diuranium μ-η(6),η(6)-arene complexes supported by ketimide ligands were synthesized and characterized. Disodium or dipotassium salts of the formula M(2)(μ-η(6),η(6)-arene)[U(NC(t)BuMes)(3)](2) (M = Na or K, Mes = 2,4,6-C(6)H(2)Me(3)) and monopotassium salts of the formula K(μ-η(6),η(6)-arene)[U(NC(t)BuMes)(3)](2) (arene = naphthalene, biphenyl, trans-stilbene, or p-terphenyl) were both observed. Two different salts of the monoanionic, toluene-bridged complexes are also described. Density functional theory calculations have been employed to illuminate the electronic structure of the μ-η(6),η(6)-arene diuranium complexes and to facilitate the comparison with related transition-metal systems, in particular (μ-η(6),η(6)-C(6)H(6))[VCp](2). It was found that the μ-η(6),η(6)-arene diuranium complexes were isolobal with (μ-η(6),η(6)-C(6)H(6))[VCp](2) and that the principal arene-binding interaction was a pair of δ bonds (total of 4e) involving both metals and the arene lowest unoccupied molecular orbital. Reactivity studies have been carried out with the mono- and dianionic μ-η(6),η(6)-arene diuranium complexes, revealing contrasting modes of redox chemistry as a function of the system's state of charge.

  13. Efficient Energy Transfer and Metal Coupling in Cyanide-Bridged Heterodinuclear Complexes Based on (Bipyridine)(terpyridine)ruthenium(II) and (Phenylpyridine)iridium(III) Complexes.

    PubMed

    Barthelmes, Kevin; Jäger, Michael; Kübel, Joachim; Friebe, Christian; Winter, Andreas; Wächtler, Maria; Dietzek, Benjamin; Schubert, Ulrich S

    2016-06-01

    We report a series of cyanide-bridged, heterodinuclear iridium(III)-ruthenium(II) complexes with the generalized formula [Ir((R2)2-ppy)2(CN)(μ-CN)Ru(bpy)(tpy-R1)]PF6 (ppy = 2-phenylpyridine, bpy = 2,2'-bipyridine, and tpy = 2,2':6',2″-terpyridine). The structural, spectroscopic, and electrochemical properties were analyzed in the context of variation of the electron-withdrawing (e.g., -F, -Br, -CHO) and -donating (e.g., -Me) and extended π-conjugated groups at several positions. In total, ten dinuclear complexes and the appropriate model complexes have been prepared. The iridium(III)-based emission is almost fully quenched in these complexes, and only the ruthenium(II)-based emission is observed, which indicates an efficient energy transfer toward the Ru center. Upon oxidation of the Ru center, the fluorinated complexes 2 exhibit a broad intervalence charge-transfer transition in the near-infrared region. The complexes are assigned to a weakly coupled class II system according to the Robin-Day classification. The electronic structure was evaluated by density functional theory (DFT) and time-dependent DFT calculations to corroborate the experimental data. PMID:27214264

  14. Substituent effects of N4 Schiff base ligands on the formation of fluoride-bridged dicobalt(ii) complexes via B-F abstraction: structures and magnetism.

    PubMed

    Cho, Yae In; Ward, Meredith L; Rose, Michael J

    2016-09-14

    We report the synthesis of two fluoride bridged cobalt(ii) dimers - [Co(μ-F)(pnN4-PhCl)2(OH2)(MeCN)](BF4)3 (1) and [Co(μ-F)2(pnN4-PhCl)2](BF4)2 (2) - and related complexes derived from propyl-bridged N4 Schiff base plus pyridine ligands. Notably, the bridging fluoride ion(s) emanate from B-F abstraction processes on the BF4 anions in the starting salt, [Co(H2O)6](BF4)2. Two types of bridging motifs are generated - mono-bridged (μ-F) or di-bridged (μ-F)2- synthetically differentiated by the absence or presence of pyridine, respectively, during metalation. The synergistic roles of pyridine and the (ClPh)N4 ligand in promoting B-F abstraction were clarified by the isolation and crystallization of the simple tetrakis-pyridine monomeric complex [Co(py)4(MeCN)2](BF4)2 (4) [no B-F abstraction]; subsequent addition of the (ClPh)N4 ligand to 4 resulted in formation of the dimeric, di-bridged complex 2. Omission of pyridine during metalation resulted in formation of the mono-bridged dimer 1. The bulky chlorophenyl substituents were obligate for B-F abstraction, as metalation of the unsubstituted N4 ligand resulted in the non-fluoride-bridged dimer, [Co(pnN4)3](BF4)4 (3). In magnetic studies, complexes 1 (μeff = 6.24μB, 298 K) and 2 (μeff = 7.70μB, 298 K) both exhibit antiferromagnetic (AFM) coupling, but to different extents. Temperature-dependent magnetic susceptibility measurements (SQUID, 2 → 300 K) reveal that the linearity of the mono-fluoride bridge in 1 [∠Co-F-Co = 159.47(11)°] results in very strong AFM coupling (J = -14.9 cm(-1)). In contrast, the more acute Co2F2 diamond core [∠Co-F-Co = 98.8(2)°, 99.1(2)°] results in a smaller extent of AFM coupling (J = -2.97 cm(-1)). Overall, the results indicate the 'non-innocence' of the BF4 counterion in cobalt(ii) chemistry, and dimers 1 and 2 affirm the effect of the geometry of the bridging fluoride ion(s) in determining the extent of AFM coupling. PMID:27491352

  15. Substituent effects of N4 Schiff base ligands on the formation of fluoride-bridged dicobalt(ii) complexes via B-F abstraction: structures and magnetism.

    PubMed

    Cho, Yae In; Ward, Meredith L; Rose, Michael J

    2016-09-14

    We report the synthesis of two fluoride bridged cobalt(ii) dimers - [Co(μ-F)(pnN4-PhCl)2(OH2)(MeCN)](BF4)3 (1) and [Co(μ-F)2(pnN4-PhCl)2](BF4)2 (2) - and related complexes derived from propyl-bridged N4 Schiff base plus pyridine ligands. Notably, the bridging fluoride ion(s) emanate from B-F abstraction processes on the BF4 anions in the starting salt, [Co(H2O)6](BF4)2. Two types of bridging motifs are generated - mono-bridged (μ-F) or di-bridged (μ-F)2- synthetically differentiated by the absence or presence of pyridine, respectively, during metalation. The synergistic roles of pyridine and the (ClPh)N4 ligand in promoting B-F abstraction were clarified by the isolation and crystallization of the simple tetrakis-pyridine monomeric complex [Co(py)4(MeCN)2](BF4)2 (4) [no B-F abstraction]; subsequent addition of the (ClPh)N4 ligand to 4 resulted in formation of the dimeric, di-bridged complex 2. Omission of pyridine during metalation resulted in formation of the mono-bridged dimer 1. The bulky chlorophenyl substituents were obligate for B-F abstraction, as metalation of the unsubstituted N4 ligand resulted in the non-fluoride-bridged dimer, [Co(pnN4)3](BF4)4 (3). In magnetic studies, complexes 1 (μeff = 6.24μB, 298 K) and 2 (μeff = 7.70μB, 298 K) both exhibit antiferromagnetic (AFM) coupling, but to different extents. Temperature-dependent magnetic susceptibility measurements (SQUID, 2 → 300 K) reveal that the linearity of the mono-fluoride bridge in 1 [∠Co-F-Co = 159.47(11)°] results in very strong AFM coupling (J = -14.9 cm(-1)). In contrast, the more acute Co2F2 diamond core [∠Co-F-Co = 98.8(2)°, 99.1(2)°] results in a smaller extent of AFM coupling (J = -2.97 cm(-1)). Overall, the results indicate the 'non-innocence' of the BF4 counterion in cobalt(ii) chemistry, and dimers 1 and 2 affirm the effect of the geometry of the bridging fluoride ion(s) in determining the extent of AFM coupling.

  16. Single molecule magnet behaviour in a rare trinuclear {Cr(III)Dy} methoxo-bridged complex.

    PubMed

    Car, Pierre-Emmanuel; Favre, Annaïck; Caneschi, Andrea; Sessoli, Roberta

    2015-09-28

    The reaction of the chromium(iii) chloride tetrahydrofuran complex with the dipivaloylmethane ligand, the lanthanide alcoholic salt DyCl3·CH3OH and the 1,1,1-tris(hydroxymethyl)-ethane ligand resulted in the formation of a new trinuclear chromium-dysprosium complex. Magnetic investigations revealed that the new 3d-4f complex exhibits single molecule magnet behaviour. PMID:26282265

  17. The conformation effect of the diamine bridge on the stability of dinuclear platinum(II) complexes and their hydrolysis.

    PubMed

    Esteves, Lucas F; Dos Santos, Hélio F; Costa, Luiz Antônio S

    2015-09-01

    In this paper, the hydrolysis process of a bisplatinum complex containing the flexible chain 1,6-hexanediamine between the two metal centers was investigated through the use of density functional theory (DFT) with the analysis of the role of the spacing group arrangement on the values of free energy activation barrier. All structures were fully optimized in aqueous solution using implicit model for solvent at DFT level. The energy profiles for the hydrolysis reaction were determined by using the supermolecule approach. Five transition states were proposed differing by the conformation of the bridge group, and the activation free energy calculated as a weighted average within the selected forms. The Gibbs population for reactant was used as a statistical weight leading to the predicted value of 23.1kcalmol(-1), in good accordance with experiment, 23.8kcalmol(-1). Our results suggests that for 1,6-hexanediamine bridge ligand, the extend forms with average torsional angle over the carbon chain larger than 130° have the greatest contribution to the hydrolysis kinetics. The results presented here point out that the hydrolysis mechanism might follow different paths for each conformation and each of these contributes to the observed energy barrier.

  18. Akirin2 is critical for inducing inflammatory genes by bridging IκB-ζ and the SWI/SNF complex

    PubMed Central

    Tartey, Sarang; Matsushita, Kazufumi; Vandenbon, Alexis; Ori, Daisuke; Imamura, Tomoko; Mino, Takashi; Standley, Daron M; Hoffmann, Jules A; Reichhart, Jean-Marc; Akira, Shizuo; Takeuchi, Osamu

    2014-01-01

    Transcription of inflammatory genes in innate immune cells is coordinately regulated by transcription factors, including NF-κB, and chromatin modifiers. However, it remains unclear how microbial sensing initiates chromatin remodeling. Here, we show that Akirin2, an evolutionarily conserved nuclear protein, bridges NF-κB and the chromatin remodeling SWI/SNF complex by interacting with BRG1-Associated Factor 60 (BAF60) proteins as well as IκB-ζ, which forms a complex with the NF-κB p50 subunit. These interactions are essential for Toll-like receptor-, RIG-I-, and Listeria-mediated expression of proinflammatory genes including Il6 and Il12b in macrophages. Consistently, effective clearance of Listeria infection required Akirin2. Furthermore, Akirin2 and IκB-ζ recruitment to the Il6 promoter depend upon the presence of IκB-ζ and Akirin2, respectively, for regulation of chromatin remodeling. BAF60 proteins were also essential for the induction of Il6 in response to LPS stimulation. Collectively, the IκB-ζ–Akirin2–BAF60 complex physically links the NF-κB and SWI/SNF complexes in innate immune cell activation. By recruiting SWI/SNF chromatin remodellers to IκB-ζ, transcriptional coactivator for NF-κB, the conserved nuclear protein Akirin2 stimulates pro-inflammatory gene promoters in mouse macrophages during innate immune responses to viral or bacterial infection. PMID:25107474

  19. Mixed-ligand MnII and CuII complexes with alternating 2,2'-bipyrimidine and terephthalate bridges.

    PubMed

    Poleti, Dejan; Rogan, Jelena; Rodić, Marko V; Radovanović, Lidija

    2015-02-01

    The novel polymeric complexes catena-poly[[diaquamanganese(II)]-μ-2,2'-bipyrimidine-κ(4)N(1),N(1'):N(3),N(3')-[diaquamanganese(II)]-bis(μ-terephthalato-κ(2)O(1):O(4))], [Mn2(C8H4O4)2(C8H6N4)(H2O)4]n, (I), and catena-poly[[[aquacopper(II)]-μ-aqua-μ-hydroxido-μ-terephthalato-κ(2)O(1):O(1')-copper(II)-μ-aqua-μ-hydroxido-μ-terephthalato-κ(2)O(1):O(1')-[aquacopper(II)]-μ-2,2'-bipyrimidine-κ(4)N(1),N(1'):N(3),N(3')] tetrahydrate], {[Cu3(C8H4O4)2(OH)2(C8H6N4)(H2O)4]·4H2O}n, (II), containing bridging 2,2'-bipyrimidine (bpym) ligands coordinated as bis-chelates, have been prepared via a ligand-exchange reaction. In both cases, quite unusual coordination modes of the terephthalate (tpht(2-)) anions were found. In (I), two tpht(2-) anions acting as bis-monodentate ligands bridge the Mn(II) centres in a parallel fashion. In (II), the tpht(2-) anions act as endo-bridges and connect two Cu(II) centres in combination with additional aqua and hydroxide bridges. In this way, the binuclear [Mn2(tpht)2(bpym)(H2O)4] entity in (I) and the trinuclear [Cu3(tpht)2(OH)2(bpym)(H2O)4]·4H2O coordination entity in (II) build up one-dimensional polymeric chains along the b axis. In (I), the Mn(II) cation lies on a twofold axis, whereas the four central C atoms of the bpym ligand are located on a mirror plane. In (II), the central Cu(II) cation is also on a special position (site symmetry -1). In the crystal structures, the packing of the chains is further strengthened by a system of hydrogen bonds [in both (I) and (II)] and weak face-to-face π-π interactions [in (I)], forming three-dimensional metal-organic frameworks. The Mn(II) cation in (I) has a trigonally deformed octahedral geometry, whereas the Cu(II) cations in (II) are in distorted octahedral environments. The Cu(II) polyhedra are inclined relative to each other and share common edges. PMID:25652277

  20. Synthesis, crystal structures, magnetic and luminescent properties of unique 1D p-ferrocenylbenzoate-bridged lanthanide complexes

    SciTech Connect

    Yan, P.F.; Zhang, F.M.; Li, G.M.; Zhang, J.W.; Sun, W.B.; Suda, M.; Einaga, Y.

    2009-07-15

    Treatments of p-ferrocenylbenzoate [p-NaOOCH{sub 4}C{sub 6}Fc, Fc=(eta{sup 5}-C{sub 5}H{sub 5})Fe(eta{sup 5}-C{sub 5}H{sub 4})] with Ln(NO{sub 3}){sub 3}.nH{sub 2}O afford seven p-ferrocenylbenzoate lanthanide complexes {l_brace}[Ln(OOCH{sub 4}C{sub 6}Fc){sub 2}(mu{sub 2}-OOCH{sub 4}C{sub 6}Fc){sub 2}(H{sub 2}O){sub 2}](H{sub 3}O){r_brace}{sub n} [Ln=Ce (1), Pr (2), Sm (3), Eu (4), Gd (5), Tb (6) and Dy (7)]. X-ray crystallographic analysis reveals that the isomorphous complexes {l_brace}[Ce(OOCH{sub 4}C{sub 6}Fc){sub 2}(mu{sub 2}-OOCH{sub 4}C{sub 6}Fc){sub 2}(H{sub 2}O){sub 2}](H{sub 3}O){r_brace}{sub n} (1) and {l_brace}[Pr(OOCH{sub 4}C{sub 6}Fc){sub 2}(mu{sub 2}-OOCH{sub 4}C{sub 6}Fc){sub 2}(H{sub 2}O){sub 2}](H{sub 3}O){r_brace}{sub n} (2) form a unique 1D double-bridged infinite chain structure bridged by mu{sub 2}-OOCH{sub 4}C{sub 6}Fc groups. Each Ln(III) ion adopts a dodecahedron coordination environment with eight coordinated oxygen atoms from two terminal monodentate coordinated FcC{sub 6}H{sub 4}COO{sup -} units, two terminal monodentate coordinated H{sub 2}O molecules and four mu{sub 2}-{sup -}OOCH{sub 4}C{sub 6}Fc units. The luminescent spectra reveal that only 4 and 6 exhibit characteristic emissions of lanthanide ions, Eu(III) and Tb(III) ions, respectively. The variable-temperature magnetic properties of 5 and 7 suggest that a ferromagnetic coupling between spin carriers may exist in 5. - Graphical abstract: Seven p-ferrocenylbenzoate lanthanide coordination polymers were synthesized. Given is the perspective view of a unique 1D double-bridged infinite chain structure of 1, excitation and emission spectra of 6 and plots of chi{sub m}T vs. T and chi{sub m}{sup -1} vs. T of 5.

  1. Investigating vibrational anharmonic couplings in cyanide-bridged transition metal mixed valence complexes using two-dimensional infrared spectroscopy

    SciTech Connect

    Slenkamp, Karla M.; Lynch, Michael S.; Van Kuiken, Benjamin E.; Brookes, Jennifer F.; Bannan, Caitlin C.; Daifuku, Stephanie L.; Khalil, Munira

    2014-02-28

    Using polarization-selective two-dimensional infrared (2D IR) spectroscopy, we measure anharmonic couplings and angles between the transition dipole moments of the four cyanide stretching (ν{sub CN}) vibrations found in [(NH{sub 3}){sub 5}Ru{sup III}NCFe{sup II}(CN){sub 5}]{sup −} (FeRu) dissolved in D{sub 2}O and formamide and [(NC){sub 5}Fe{sup II}CNPt{sup IV}(NH{sub 3}){sub 4}NCFe{sup II}(CN){sub 5}]{sup 4−} (FePtFe) dissolved in D{sub 2}O. These cyanide-bridged transition metal complexes serve as model systems for studying the role of high frequency vibrational modes in ultrafast photoinduced charge transfer reactions. Here, we focus on the spectroscopy of the ν{sub CN} modes in the electronic ground state. The FTIR spectra of the ν{sub CN} modes of the bimetallic and trimetallic systems are strikingly different in terms of frequencies, amplitudes, and lineshapes. The experimental 2D IR spectra of FeRu and FePtFe and their fits reveal a set of weakly coupled anharmonic ν{sub CN} modes. The vibrational mode anharmonicities of the individual ν{sub CN} modes range from 14 to 28 cm{sup −1}. The mixed-mode anharmonicities range from 2 to 14 cm{sup −1}. In general, the bridging ν{sub CN} mode is most weakly coupled to the radial ν{sub CN} mode, which involves the terminal CN ligands. Measurement of the relative transition dipole moments of the four ν{sub CN} modes reveal that the FeRu molecule is almost linear in solution when dissolved in formamide, but it assumes a bent geometry when dissolved in D{sub 2}O. The ν{sub CN} modes are modelled as bilinearly coupled anharmonic oscillators with an average coupling constant of 6 cm{sup −1}. This study elucidates the role of the solvent in modulating the molecular geometry and the anharmonic vibrational couplings between the ν{sub CN} modes in cyanide-bridged transition metal mixed valence complexes.

  2. Synthesis and reactivity of NHC-supported Ni2(μ(2)-η(2),η(2)-S2)-bridging disulfide and Ni2(μ-S)2-bridging sulfide complexes.

    PubMed

    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. PMID:25742125

  3. Synthesis, structural characterization, and ligand replacement reactions of gem-dithiolato-bridged rhodium and iridium complexes.

    PubMed

    Rivas, Angel B; Gascón, José M; Lahoz, Fernando J; Balana, Ana I; Pardey, Alvaro J; Oro, Luis A; Pérez-Torrente, Jesús J

    2008-07-01

    The reaction of gem-dithiol compounds R 2C(SH) 2 (R = Bn (benzyl), (i) Pr; R 2 = -(CH 2) 4-) with dinuclear rhodium or iridium complexes containing basic ligands such as [M(mu-OH)(cod)] 2 and [M(mu-OMe)(cod)] 2, or the mononuclear [M(acac)(cod)] (M = Rh, Ir, cod = 1,5-cyclooctadiene) in the presence of a external base, afforded the dinuclear complexes [M 2(mu-S 2CR 2)(cod) 2] ( 1- 4). The monodeprotonation of 1,1-dimercaptocyclopentane gave the mononuclear complex [Rh(HS 2Cptn)(cod)] ( 5) that is a precursor for the dinuclear compound [Rh 2(mu-S 2Cptn)(cod) 2] ( 6). Carbonylation of the diolefin compounds gave the complexes [Rh 2(mu-S 2CR 2)(CO) 4] ( 7- 9), which reacted with P-donor ligands to stereoselectively produce the trans isomer of the disubstituted complexes [Rh 2(mu-S 2CR 2)(CO) 2(PR' 3) 2] (R' = Ph, Cy (cyclohexyl)) ( 10- 13) and [Rh 2(mu-S 2CBn 2)(CO) 2{P(OR') 3} 2] (R' = Me, Ph) ( 14- 15). The substitution process in [Rh 2(mu-S 2CBn 2)(CO) 4] ( 7) by P(OMe) 3 has been studied by spectroscopic means and the full series of substituted complexes [Rh 2(mu-S 2CBn 2)(CO) 4- n {P(OR) 3} n ] ( n = 1, 4) has been identified in solution. The cis complex [Rh 2(mu-S 2CBn 2)(CO) 2(mu-dppb)] ( 16) was obtained by reaction of 7 with the diphosphine dppb (1,4-bis(diphenylphosphino)butane). The molecular structures of the diolefinic dinuclear complexes [Rh 2(mu-S 2CR 2)(cod) 2] (R = Bn ( 1), (i) Pr ( 2); R 2 = -(CH 2) 4- ( 6)) and that of the cis complex 16 have been studied by X-ray diffraction. PMID:18507456

  4. Lithium Di- and trimethyl dimolybdenum(II) complexes with Mo-Mo quadruple bonds and bridging methyl groups.

    PubMed

    Curado, Natalia; Carrasco, Mario; Álvarez, Eleuterio; Maya, Celia; Peloso, Riccardo; Rodríguez, Amor; López-Serrano, Joaquín; Carmona, Ernesto

    2015-09-30

    New dimolybdenum complexes of composition [Mo2{μ-Me}2Li(S)}(μ-X)(μ-N^N)2] (3a-3c), where S = THF or Et2O and N^N represents a bidentate aminopyridinate or amidinate ligand that bridges the quadruply bonded molybdenum atoms, were prepared from the reaction of the appropriate [Mo2{μ-O2CMe}2(μ-N^N)2] precursors and LiMe. For complex 3a, X = MeCO2, while in 3b and 3c, X = Me. Solution NMR studies in C6D6 solvent support formulation of the complexes as contact ion pairs with weak agostic Mo-CH3···Li interactions, which were also evidenced by X-ray crystallography in the solid-state structures of the molecules of 3a and 3b. Samples of 3c enriched in (13)C (99%) at the metal-bonded methyl sites were also prepared and investigated by NMR spectroscopy employing C6D6 and THF-d8 solvents. Crystallization of 3c from toluene:tetrahydrofuran mixtures provided single crystals of the solvent separated ion pair complex [Li(THF)4] [Mo2(Me)2(μ-Me){μ-HC(NDipp)2}2] (4c), where Dipp stands for 2,6-iPr2C6H3. A computational analysis of the Mo2(μ-Me)2Li core of complexes 3a and 3b has been developed, which is consistent with a small but non-negligible electron-density sharing between the C and Li atoms of the mainly ionic CH3···Li interactions.

  5. Highly selective fluorescence sensors for the fluoride anion based on carboxylate-bridged diiron complexes.

    PubMed

    Zhou, Yuhan; Dong, Xiaoliang; Zhang, Yixin; Tong, Peng; Qu, Jingping

    2016-04-28

    A new ligand bearing anthracene and its Fe(III) and Ru(III) derivatives have been synthesized and characterized exactly. The studies show that these dinuclear metal complexes serve as candidates of fluorescence chemosensors for anions. The interactions between these complexes and anions have been investigated by means of UV-Vis absorption spectra, fluorescence spectra, titration studies and (1)H-NMR. The results illustrated that two diiron complexes, [Cp*Fe(μ-SR)2(μ-η(2)-L)FeCp*][PF6] (, R = Me; , R = Et; L = 4-(3-(anthracen-9-ylmethyl)ureido)benzoate), showed rapid and selective recognition for the fluoride ion over other anions with strong enhancement of emission intensities. The sensing mechanisms indicate that the hydrogen bonding interaction has been observed between chemosensors and F(-). PMID:26619793

  6. Enzyme-like catalysis via ternary complex mechanism: alkoxy-bridged dinuclear cobalt complex mediates chemoselective O-esterification over N-amidation.

    PubMed

    Hayashi, Yukiko; Santoro, Stefano; Azuma, Yuki; Himo, Fahmi; Ohshima, Takashi; Mashima, Kazushi

    2013-04-24

    Hydroxy group-selective acylation in the presence of more nucleophilic amines was achieved using acetates of first-row late transition metals, such as Mn, Fe, Co, Cu, and Zn. Among them, cobalt(II) acetate was the best catalyst in terms of reactivity and selectivity. The combination of an octanuclear cobalt carboxylate cluster [Co4(OCOR)6O]2 (2a: R = CF3, 2b: R = CH3, 2c: R = (t)Bu) with nitrogen-containing ligands, such as 2,2'-bipyridine, provided an efficient catalytic system for transesterification, in which an alkoxide-bridged dinuclear complex, Co2(OCO(t)Bu)2(bpy)2(μ2-OCH2-C6H4-4-CH3)2 (10), was successfully isolated as a key intermediate. Kinetic studies and density functional theory calculations revealed Michaelis-Menten behavior of the complex 10 through an ordered ternary complex mechanism similar to dinuclear metallo-enzymes, suggesting the formation of alkoxides followed by coordination of the ester.

  7. Aspartate-Based CXCR4 Chemokine Receptor Binding of Cross-Bridged Tetraazamacrocyclic Copper(II) and Zinc(II) Complexes.

    PubMed

    Maples, Randall D; Cain, Amy N; Burke, Benjamin P; Silversides, Jon D; Mewis, Ryan E; D'huys, Thomas; Schols, Dominique; Linder, Douglas P; Archibald, Stephen J; Hubin, Timothy J

    2016-08-26

    The CXCR4 chemokine receptor is implicated in a number of diseases including HIV infection and cancer development and metastasis. Previous studies have demonstrated that configurationally restricted bis-tetraazamacrocyclic metal complexes are high-affinity CXCR4 antagonists. Here, we present the synthesis of Cu(2+) and Zn(2+) acetate complexes of six cross-bridged tetraazamacrocycles to mimic their coordination interaction with the aspartate side chains known to bind them to CXCR4. X-ray crystal structures for three new Cu(2+) acetate complexes and two new Zn(2+) acetate complexes demonstrate metal-ion-dependent differences in the mode of binding the acetate ligand concomitantly with the requisite cis-V-configured cross-bridged tetraazamacrocyle. Concurrent density functional theory molecular modelling studies produced an energetic rationale for the unexpected [Zn(OAc)(H2 O)](+) coordination motif present in all of the Zn(2+) cross-bridged tetraazamacrocycle crystal structures, which differs from the chelating acetate [Zn(OAc)](+) structures of known unbridged and side-bridged tetraazamacrocyclic Zn(2+) -containing CXCR4 antagonists. PMID:27458983

  8. π-Stacking attraction vs. electrostatic repulsion: competing supramolecular interactions in a tpphz-bridged Ru(ii)/Au(iii) complex.

    PubMed

    Sorsche, Dieter; Schaub, Markus; Heinemann, Frank W; Habermehl, Johannes; Kuhri, Susanne; Guldi, Dirk; Guthmuller, Julien; Rau, Sven

    2016-08-01

    The synthesis and characterization of a mixed metal ruthenium(ii)/gold(iii) complex bridged by tetrapyridophenazine (tpphz) are described. It is isostructural and isoelectronic to the well-known photocatalysts with palladium(ii) or platinum(ii). Concentration dependent (1)H-NMR spectroscopy and XRD studies show that the electrostatic repulsion between the gold(iii) moieties exceeds the attractive π-stacking interaction. Theoretical calculations based on the new structural data confirm an increased positive charge on the bridging ligand as well as significantly altered orbital symmetry as compared to the previously investigated palladium(ii) complex. This is the first example of a tpphz ruthenium(ii) complex where π-stacking is completely inhibited. The detailed investigation of the solid-state structure showed for the first time in bimetallic tpphz bridged complexes no significant torsion within the bridging ligand itself. Although catalytic performance for proton reduction by gold(iii) is naturally not observed, its photochemical decomposition in colloidal gold particles could be shown by TEM and DLS. PMID:27472004

  9. Synthesis, crystal structure and spectroscopic and electrochemical properties of bridged trisbenzoato copper-zinc heterobinuclear complex of 2,2‧-bipyridine

    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.

  10. Studies on the electronic structure of thiolate-bridged diiron complexes and their single-electron reduction reactions

    NASA Astrophysics Data System (ADS)

    Chen, Si; Li, Yang; Yang, Dawei; Luo, Lun; Qu, Jingping; Luo, Yi

    2016-09-01

    The bdt-bridged diiron-amide complex [Cp∗Fe(μ-η2:η2-bdt)(μ-NH2)FeCp∗][BF4]2 (1[BF4]2, Cp∗ = η5-C5Me5; bdt = benzene-1,2-dithiolate) and its reduction products [Cp∗Fe(μ-η2:η2-bdt)(μ-NH2)FeCp∗][BF4] (2[BF4]) and [Cp∗Fe(μ-η2:η1-bdt)(μ-NH2)FeCp∗] (3) have been synthesized. DFT calculations suggest that the sequential reduction of 1[BF4]2 to 2[BF4] and further to 3 is a bimetal and single-metal based process, respectively. The ground state of 1[BF4]2 is predicted to be quartet. 2[BF4] has an antiferromagnetic coupling BS(1,1) ground state, and the ground state of 3 is proposed to be BS(1,0). The bdt ligand in these three complexes is better viewed as a dianion ligand rather than a monoanionic radical.

  11. Redox noninnocence of the bridge in copper(II) salophen and bis(oxamato) complexes.

    PubMed

    de Bellefeuille, David; Orio, Maylis; Barra, Anne-Laure; Aukauloo, Ally; Journaux, Yves; Philouze, Christian; Ottenwaelder, Xavier; Thomas, Fabrice

    2015-09-21

    Two square-planar copper(II) complexes of 1,2-bis(2-hydroxy-3,5-di-tert-butylbenzimino)-4,5-bis(dimethylamino)benzene (1) and N-[4,5-bis(dimethylamino)-2-(oxalylamino)benzene]oxamate (2(2-)) were prepared. The crystal structures of the proligands H2L(1) and Et2H2L(2), as well as the corresponding complexes, are reported. The proligands each display a one-electron-oxidation wave, which is assigned to oxidation of the bis(dimethylamino)benzene moiety into a π radical. Complexes 1 and 2(2-) exhibit reversible one-electron-oxidation waves in their cyclic voltammograms (E1/2(1) = 0.14 and E1/2(2) = 0.31 V for 1 and E1/2(1) = -0.47 V vs Fc(+)/Fc for 2(2-)). The first process corresponds to oxidation of the bis(dimethylamino)benzene central ring into a π radical, while the second process for 1 is ascribed to oxidation of the π radical into an α-diiminoquinone. The one-electron-oxidized species 1(+) and 2(-) exhibit intense visible-near-IR absorptions, which are diagnostic of π radicals. They display a triplet signal in their electron paramagnetic resonance spectra, which stem from magnetic coupling between the ligand-radical spin and the copper(II) spin. The zero-field-splitting parameters are larger for 2(-) than 1(+) because of greater delocalization of the spin density onto the coordinated amidato N atoms. Density functional theory calculations support a π-radical nature of the one-electron-oxidized complexes, as well as S = 1 ground spin states. The electrogenerated 1(2+) comprises a closed-shell diiminoquinone ligand coordinated to a copper(II) metal center. Both 1 and 2 catalyze the aerobic oxidation of benzyl alcohol, albeit with different yields. PMID:26340100

  12. Self-assembly molecular squares with metal complexes as bridging ligands

    SciTech Connect

    Sun, S.S.; Silva, A.S.; Brinn, I.M.; Lees, A.J.

    2000-04-03

    Polynuclear transition metal complexes containing multichromophoric units, such as metal polypyridyl complexes, are of considerable current interest. Much attention has been paid to the synthesis of multicomponent systems that exhibit photoinduced intercomponent electron and/or energy-transfer processes and to their potential applications for photonic and electronic devices. Systems incorporating Re(I)- Ru(II)-, and Os(II)-based polypyridyl chromophores are the most commonly studied because of their favorable redox and spectroscopic characteristics. In this communication, the authors combine the concepts of self-assembly and complexes as ligands and report the preparation of a series of molecular squares with the general molecular formula [fac-Br(CO){sub 3}Re({mu}-(pyterpy){sub 2}M)]{sub 4}(PF{sub 6}){sub 8}, where pyterpy is 4{prime}-(4{prime}{double_prime}-pyridyl)-2,2{prime}:6{prime}2{double_prime}-terpyridine and M = Fe, Ru, or Os. The spectroscopic properties and a preliminary anion binding study of these novel octanuclear molecular squares are also presented.

  13. Alkali Metal Variation and Twisting of the FeNNFe Core in Bridging Diiron Dinitrogen Complexes.

    PubMed

    McWilliams, Sean F; Rodgers, Kenton R; Lukat-Rodgers, Gudrun; Mercado, Brandon Q; Grubel, Katarzyna; Holland, Patrick L

    2016-03-21

    Alkali metal cations can interact with Fe-N2 complexes, potentially enhancing back-bonding or influencing the geometry of the iron atom. These influences are relevant to large-scale N2 reduction by iron, such as in the FeMoco of nitrogenase and the alkali-promoted Haber-Bosch process. However, to our knowledge there have been no systematic studies of a large range of alkali metals regarding their influence on transition metal-dinitrogen complexes. In this work, we varied the alkali metal in [alkali cation]2[LFeNNFeL] complexes (L = bulky β-diketiminate ligand) through the size range from Na(+) to K(+), Rb(+), and Cs(+). The FeNNFe cores have similar Fe-N and N-N distances and N-N stretching frequencies despite the drastic change in alkali metal cation size. The two diketiminates twist relative to one another, with larger dihedral angles accommodating the larger cations. In order to explain why the twisting has so little influence on the core, we performed density functional theory calculations on a simplified LFeNNFeL model, which show that the two metals surprisingly do not compete for back-bonding to the same π* orbital of N2, even when the ligand planes are parallel. This diiron system can tolerate distortion of the ligand planes through compensating orbital energy changes, and thus, a range of ligand orientations can give very similar energies. PMID:26925968

  14. Thiolate bridging and metal exchange in adducts of a zinc finger model and Pt(II) complexes: biomimetic studies of protein/Pt/DNA interactions.

    PubMed

    Almaraz, Elky; de Paula, Queite A; Liu, Qin; Reibenspies, Joseph H; Darensbourg, Marcetta Y; Farrell, Nicholas P

    2008-05-14

    To provide precedents for the possible interactions of platinum DNA adducts with zinc finger proteins, the complexes [Pt(dien)Cl]Cl (dien = diethylenetriamine) and [Pt(terpy)Cl]Cl (terpy = 2,2':6',2''-terpyridine) were exposed to the N,N'-bis(2-mercaptoethyl)-1,4-diazacycloheptanezinc(II) dimer, [Zn(bme-dach)]2, and the products defined by electrospray ionization mass spectrometry (ESI-MS), X-ray crystallography and (195)Pt NMR spectroscopy. The presence of a leaving chloride in both platinum(II) complexes facilitates electrophilic substitution involving sulfur-containing zinc finger synthetic models or, as in previous studies, zinc finger peptidic sequences. Monitored via ESI-MS, both reactants yielded evidence for Zn-(mu-SR)-Pt bridges followed by zinc ejection from the N2S2 coordination sphere and subsequent formation of a trimetallic Zn-(mu-SR)2-Pt-(mu-SR)2-Zn-bridged species. The isolation of Zn-(mu-SR)-Pt-bridged species [(Zn(bme-dach)Cl)(Pt(dien))]Cl is, to our knowledge, the first Zn-Pt bimetallic thiolate-bridged model demonstrating the interaction between Zn-bound thiolates and Pt(2+). In the case of the [Pt(terpy)Cl]Cl reaction with the [Zn(bme-dach)]2, ESI-MS analysis further suggests metal exchange by formation of [Zn(terpy)Cl](+), whereas the [Pt(dien)Cl]Cl reaction does not yield the corresponding [Zn(dien)Cl](+) ion. Direct synthesis of the Zn-Pt thiolate-bridged species and the Pt(N2S2) chelate, where Pt has displaced the Zn from the chelate core, permitted the isolation of X-ray-quality crystals to confirm the bridging and metal-exchanged structures. The ESI-MS, (195)Pt NMR spectroscopy, and molecular structures of the di- and trinuclear complexes will be discussed, as they provide insight into the metal-exchange mechanism.

  15. Glycosylinositol phosphorylceramides from Rosa cell cultures are boron-bridged in the plasma membrane and form complexes with rhamnogalacturonan II

    PubMed Central

    Voxeur, Aline; Fry, Stephen C

    2014-01-01

    Boron (B) is essential for plant cell-wall structure and membrane functions. Compared with its role in cross-linking the pectic domain rhamnogalacturonan II (RG-II), little information is known about the biological role of B in membranes. Here, we investigated the involvement of glycosylinositol phosphorylceramides (GIPCs), major components of lipid rafts, in the membrane requirement for B. Using thin-layer chromatography and mass spectrometry, we first characterized GIPCs from Rosa cell culture. The major GIPC has one hexose residue, one hexuronic acid residue, inositol phosphate, and a ceramide moiety with a C18 trihydroxylated mono-unsaturated long-chain base and a C24 monohydroxylated saturated fatty acid. Disrupting B bridging (by B starvation in vivo or by treatment with cold dilute HCl or with excess borate in vitro) enhanced the GIPCs’ extractability. As RG-II is the main B-binding site in plants, we investigated whether it could form a B-centred complex with GIPCs. Using high-voltage paper electrophoresis, we showed that addition of GIPCs decreased the electrophoretic mobility of radiolabelled RG-II, suggesting formation of a GIPC–B–RG-II complex. Last, using polyacrylamide gel electrophoresis, we showed that added GIPCs facilitate RG-II dimerization in vitro. We conclude that B plays a structural role in the plasma membrane. The disruption of membrane components by high borate may account for the phytotoxicity of excess B. Moreover, the in-vitro formation of a GIPC–B–RG-II complex gives the first molecular explanation of the wall–membrane attachment sites observed in vivo. Finally, our results suggest a role for GIPCs in the RG-II dimerization process. PMID:24804932

  16. Rhenium(IV)-copper(II) heterobimetallic complexes with a bridge malonato ligand. Synthesis, crystal structure, and magnetic properties.

    PubMed

    Cuevas, Alicia; Chiozzone, Raúl; Kremer, Carlos; Suescun, Leopoldo; Mombrú, Alvaro; Armentano, Donatella; De Munno, Giovanni; Lloret, Francesc; Cano, Juan; Faus, Juan

    2004-11-29

    The Re(IV) complex [ReCl4(mal)]2-, in the form of two slightly different salts, (AsPh4)1.5(HNEt3)0.5[ReCl4(mal)] (1a) and (AsPh4)(HNEt3)[ReCl4(mal)] (1b), and the Re(IV)-Cu(II) bimetallic complexes [ReCl4(mu-mal)Cu(phen)2].CH3CN (2), [ReCl4(mu-mal)Cu(bpy)2] (3), and [ReCl4(mu-mal)Cu(terpy)] (4) (mal=malonate dianion, AsPh4=tetraphenylarsonium cation, HNEt3=triethylammonium cation, phen=1,10-phenanthroline, bpy=2,2'-bipyridine and terpy=2,2':6',2' '-terpyridine) have been synthesized and the structures of 1a, 1b, 2, and 3 determined by single-crystal X-ray diffraction. The structures of 1a and 1b are made up of discrete [ReCl4(mal)]2- anions and AsPh4+ and HNEt3+ cations, held together by electrostatic forces and hydrogen bonds. The Re(IV) atom is surrounded by four chloride anions and a bidentate malonate group, in a distorted octahedral environment. The structure of 2 consist of neutral dinuclear units [ReCl4(mu-mal)Cu(phen)2], with the metal ions united through a bridge carboxilato. The environment of Re(IV) is nearly identical to that in the mononuclear complex, and Cu(II) is five coordinate, being surrounded by four nitrogen atoms of two bidentate phen ligands and one oxygen atom of the malonato ligand. In 3, there are also dinuclear units, [ReCl4(mu-mal)Cu(bpy)2], but the Cu(II) ions complete a distorted octahedral coordination by binding with the free malonato oxygen atom of a neighbor unit, resulting in an infinite chain. The magnetic properties of 1-4 were also investigated in the temperature range 2.0-300 K. The magnetic behavior of 1a and 1b is as expected for a Re(IV) complex with a large value of the zero-field splitting (2D ca. 110 cm(-1)). For the bimetallic complexes, the magnetic coupling between Re(IV) and Cu(II) is antiferromagnetic in 2 (J=-0.39 cm(-1)), ferromagnetic in 4 (J=+1.51 cm(-1)), and nearly negligible in 3 (J=-0.09 cm(-1)).

  17. Biodiesel fuel production from waste cooking oil by the inclusion complex of heteropoly acid with bridged bis-cyclodextrin.

    PubMed

    Zou, Changjun; Zhao, Pinwen; Shi, Lihong; Huang, Shaobing; Luo, Pingya

    2013-10-01

    The inclusion complex of Cs2.5H0.5PW12O40 with bridged bis-cyclodextrin (CsPW/B) is prepared as a highly efficient catalyst for the direct production of biodiesel via the transesterification of waste cooking oil. CsPW/B is characterized by X-ray diffraction, and the biodiesel is analyzed by Gas Chromatography-Mass Spectrometer. The conversion rate of waste cooking oil is up to 94.2% under the optimum experimental conditions that are methanol/oil molar ratio of 9:1, catalyst dosage of 3 wt%, temperature of 65 °C and reaction time of 180 min. The physical properties of biodiesel sample satisfy the requirement of ASTM D6751 standards. The novel CsPW/B catalyst used for the transesterification can lead to 96.9% fatty acid methyl esters and 86.5% of the biodiesel product can serve as the ideal substitute for diesel fuel, indicating its excellent potential application in biodiesel production.

  18. Luminescence rigidochromism and redox chemistry of pyrazolate-bridged binuclear platinum(II) diimine complex intercalated into zirconium phosphate layers.

    PubMed

    Rivera, Eladio J; Barbosa, Cindy; Torres, Rafael; Rivera, Harry; Fachini, Estevao R; Green, Tyler W; Connick, William B; Colón, Jorge L

    2012-03-01

    The direct intercalation of a pyrazolate-bridged platinum(II) bipyridyl dimer ([{Pt(dmbpy)(μ-pz)}(2)](2+); dmbpy = 4,4'-dimethyl-2,2'-bipyridine, pz(-) = pyrazolate) within a zirconium phosphate (ZrP) framework has been accomplished. The physical and spectroscopic properties of [{Pt(dmbpy)(μ-pz)}(2)](2+) intercalated in ZrP were investigated by X-ray powder diffraction and X-ray photoelectron, infrared, absorption, and luminescence spectroscopies. Zirconium phosphate layers have a special microenvironment that is capable of supporting a variety of platinum oxidation states. Diffuse reflectance spectra from powders of the blue-gray intercalated materials show the formation of a low-energy band at 600 nm that is not present in the platinum dimer salt. The nonintercalated complex is nonemissive in room-temperature fluid solution, but gives rise to intense blue-green emission in a 4:1 ethanol/methanol 77 K frozen glassy solution. Powders and colloidal suspensions of [{Pt(dmbpy)(μ-pz)}(2)](2+)-exchanged ZrP materials exhibit intense emissions at room-temperature. PMID:22339702

  19. Bridging the gap between uncertainty analysis for complex watershed models and decision-making for watershed-scale water management

    NASA Astrophysics Data System (ADS)

    Zheng, Y.; Han, F.; Wu, B.

    2013-12-01

    Process-based, spatially distributed and dynamic models provide desirable resolutions to watershed-scale water management. However, their reliability in solving real management problems has been seriously questioned, since the model simulation usually involves significant uncertainty with complicated origins. Uncertainty analysis (UA) for complex hydrological models has been a hot topic in the past decade, and a variety of UA approaches have been developed, but mostly in a theoretical setting. Whether and how a UA could benefit real management decisions remains to be critical questions. We have conducted a series of studies to investigate the applicability of classic approaches, such as GLUE and Markov Chain Monte Carlo (MCMC) methods, in real management settings, unravel the difficulties encountered by such methods, and tailor the methods to better serve the management. Frameworks and new algorithms, such as Probabilistic Collocation Method (PCM)-based approaches, were also proposed for specific management issues. This presentation summarize our past and ongoing studies on the role of UA in real water management. Challenges and potential strategies to bridge the gap between UA for complex models and decision-making for management will be discussed. Future directions for the research in this field will also be suggested. Two common water management settings were examined. One is the Total Maximum Daily Loads (TMDLs) management for surface water quality protection. The other is integrated water resources management for watershed sustainability. For the first setting, nutrients and pesticides TMDLs in the Newport Bay Watershed (Orange Country, California, USA) were discussed. It is a highly urbanized region with a semi-arid Mediterranean climate, typical of the western U.S. For the second setting, the water resources management in the Zhangye Basin (the midstream part of Heihe Baisn, China), where the famous 'Silk Road' came through, was investigated. The Zhangye

  20. Copper(II) and gallium(III) complexes of trans-bis(2-hydroxybenzyl) cyclen derivatives: absence of a cross-bridge proves surprisingly more favorable.

    PubMed

    Esteves, Catarina V; Madureira, Joana; Lima, Luís M P; Mateus, Pedro; Bento, Isabel; Delgado, Rita

    2014-05-01

    Two cyclen (1,4,7,10-tetraazacyclododecane) derivatives bearing trans-bis(2-hydroxybenzyl) arms, the 1,7-(2-hydroxybenzyl)-1,4,7,10-tetraazacyclododecane (H2do2ph) and its cross-bridged counterpart (H2cb-do2ph), have been synthesized, aiming toward the possible use of their copper(II) and gallium(III) complexes in nuclear medicine. The protonation of both compounds was studied in aqueous solution as well as their complexes with Cu(2+) and Ga(3+) cations. The complexes of both ligands with Ca(2+) and Zn(2+) metal ions were also studied due to the abundance of these cations in biological media. In mild conditions the complexes of Ca(2+) and Ga(3+) with H2cb-do2ph did not form. The behavior of the two ligands and their complexes was compared by the values of the equilibrium constants, the data of varied spectroscopic techniques, the values of redox potentials of their copper(II) complexes, and the resistance of the complexes to acid dissociation. It was expected that, as found for related pairs of cyclen and cyclam (1,4,8,11-tetraazacyclotetradecane) derivatives, the cross-bridged macrocyclic derivative could be an excellent ligand for the complexation of copper(II). Additionally, the N-2-hydroxybenzyl groups were chosen due to their known ability to coordinate the gallium(III) cation. Due to the small size of the latter cation and its particular propensity to form hexacoordinate complexes, it was also expected that there would be a good ability of both ligands for the uptake of Ga(3+). Surprisingly, the results revealed that the cyclen derivative H2do2ph is the best ligand for the coordination of Cu(2+) and Ga(3+) cations, not only from their thermodynamic stability as expected but also from their kinetic inertness, when compared with its cross-bridged counterpart.

  1. Strong ferromagnetic exchange interactions in hinge-like Dy(O2Cu)2 complexes involving double oxygen bridges.

    PubMed

    Ida, Yumi; Ghosh, Soumavo; Ghosh, Ashutosh; Nojiri, Hiroyuki; Ishida, Takayuki

    2015-10-01

    Two trinuclear isomeric compounds, [{(Cu(II)(salpn))(Me(CO)Me)}2Dy(III)(NO3)3] (1) and [{Cu(II)(salpn)}2Dy(III)(H2O)(NO3)3]·MeOH (2), along with one polymeric compound, {[{Cu(II)(salpn)}2Dy(III)(NO3)3bpy]·MeOH·H2O}n (3), were synthesized using a metalloligand, [Cu(II)(salpn)], where H2salpn and bpy stand for N,N'-bis(salicylidene)-1,3-propanediamine and 4,4'-bipyridine, respectively. Compounds 1 and 2 were selectively prepared with two solvents: the less polar acetone led to the exclusive crystallization of 1 with a transoid trinuclear architecture, while more polar solvent methanol provided sole construction of 2 with a cisoid trinuclear architecture. Compound 3 was prepared from 1 or 2 after bpy was introduced as a bridge. The Dy and Cu ions are doubly bridged with oxygen atoms, and the core DyO2Cu skeletons are characterized by different "butterfly angles" of 140.9(1)°, 147.1(19)°, and 142.4(2)° for 1, 2, and 3, respectively. We have examined the molecular structures and magnetic properties of 1-3 using high-frequency electron paramagnetic resonance (HF-EPR), magnetization, and magnetic susceptibility techniques. These compounds showed slow magnetization reversal in the measurements of alternating current magnetic susceptibility. We analyzed EPR frequency-field diagrams using an effective spin-Hamiltonian including only one doublet of Dy sublevels and found that the exchange couplings are ferromagnetic in all compounds. The exchange coupling parameters JDy-Cu of 1, 2, and 3 were determined as 2.25 ± 0.05, 1.82 ± 0.04, and 1.79 ± 0.04 K, respectively. These values are larger than those found in previous research using EPR analysis on [Cu(II)(L(A))(C3H6O)Dy(III)(NO3)3] (H2L(A) = N,N'-bis(3-methoxysalicylidene)-1,3-diamino-2,2-dimethylpropane) and [Dy(III)L(B)2(NO3)2{Cu(II)(CH3OH)}2](NO3)(CH3OH) (H2L(B) = 2,6-bis(acetylaceto)pyridine). The present result shows an advantage of doubly oxygen-bridged motifs to built strong ferromagnetic interactions between

  2. Strong ferromagnetic exchange interactions in hinge-like Dy(O2Cu)2 complexes involving double oxygen bridges.

    PubMed

    Ida, Yumi; Ghosh, Soumavo; Ghosh, Ashutosh; Nojiri, Hiroyuki; Ishida, Takayuki

    2015-10-01

    Two trinuclear isomeric compounds, [{(Cu(II)(salpn))(Me(CO)Me)}2Dy(III)(NO3)3] (1) and [{Cu(II)(salpn)}2Dy(III)(H2O)(NO3)3]·MeOH (2), along with one polymeric compound, {[{Cu(II)(salpn)}2Dy(III)(NO3)3bpy]·MeOH·H2O}n (3), were synthesized using a metalloligand, [Cu(II)(salpn)], where H2salpn and bpy stand for N,N'-bis(salicylidene)-1,3-propanediamine and 4,4'-bipyridine, respectively. Compounds 1 and 2 were selectively prepared with two solvents: the less polar acetone led to the exclusive crystallization of 1 with a transoid trinuclear architecture, while more polar solvent methanol provided sole construction of 2 with a cisoid trinuclear architecture. Compound 3 was prepared from 1 or 2 after bpy was introduced as a bridge. The Dy and Cu ions are doubly bridged with oxygen atoms, and the core DyO2Cu skeletons are characterized by different "butterfly angles" of 140.9(1)°, 147.1(19)°, and 142.4(2)° for 1, 2, and 3, respectively. We have examined the molecular structures and magnetic properties of 1-3 using high-frequency electron paramagnetic resonance (HF-EPR), magnetization, and magnetic susceptibility techniques. These compounds showed slow magnetization reversal in the measurements of alternating current magnetic susceptibility. We analyzed EPR frequency-field diagrams using an effective spin-Hamiltonian including only one doublet of Dy sublevels and found that the exchange couplings are ferromagnetic in all compounds. The exchange coupling parameters JDy-Cu of 1, 2, and 3 were determined as 2.25 ± 0.05, 1.82 ± 0.04, and 1.79 ± 0.04 K, respectively. These values are larger than those found in previous research using EPR analysis on [Cu(II)(L(A))(C3H6O)Dy(III)(NO3)3] (H2L(A) = N,N'-bis(3-methoxysalicylidene)-1,3-diamino-2,2-dimethylpropane) and [Dy(III)L(B)2(NO3)2{Cu(II)(CH3OH)}2](NO3)(CH3OH) (H2L(B) = 2,6-bis(acetylaceto)pyridine). The present result shows an advantage of doubly oxygen-bridged motifs to built strong ferromagnetic interactions between

  3. A Unique Coplanar Multi-center Bonding Network in Doubly Acetylide-bridged Binuclear Zirconocene Complexes: A Density Functional Theory Study

    SciTech Connect

    Niu, Shuqiang; Derecskei-Kovacs, Agnes; Hall, Michael B.

    2007-10-01

    The research described in this product was performed in part in the Environmental Molecular Sciences Laboratory, a national scientific user facility sponsored by the Department of Energy's Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory. A unique p-conjugative interaction pattern was experimentally revealed in the doubly acetylide-bridged binuclear group 4 metallocene complexes, which was involved in C–C coupling/cleavage reactions of acetylides and r-alkynyl migrations. To elucidate how this multicenter bonding network affects the structural and reaction properties of these complexes, density functional theory (DFT) calculations and molecular orbital (MO) analysis were carried out on the electronic structure and r-alkynyl migration mechanisms of the doubly acetylide-bridged binuclear Zr complexes, (L2Zr)2(l-C„CH)2 (L = Cp,Cl). The B3LYP calculations suggested that the doubly [r,p] acetylide-bridged complex C2h-(L2Zr)2(l-C„CH)2 was produced by the reaction of L2Zr(C„CH)2 with L2Zr through a C2v- (L2Zr)2(l-C„CH)2 intermediate followed by an isomerization process. In particular, the isomerization of C2h- or C2v-(L2Zr)2(l- C„CH)2 is almost thermoneutral through a low barrier of 15.3–17.0 kcal/mol. The MO Walsh diagram revealed that the two isomers have a very similar six-center-six-electron bonding network. The coplanar p-conjunctive interaction by the electron donating and backdonating interactions between the metal centers and acetylide ligands significantly stabilizes the doubly acetylide-bridged binuclear group 4 metallocene complexes and the isomerization transition state.

  4. Distributed situation awareness in complex collaborative systems: A field study of bridge operations on platform supply vessels

    PubMed Central

    Sandhåland, Hilde; Oltedal, Helle A; Hystad, Sigurd W; Eid, Jarle

    2015-01-01

    This study provides empirical data about shipboard practices in bridge operations on board a selection of platform supply vessels (PSVs). Using the theoretical concept of distributed situation awareness, the study examines how situation awareness (SA)-related information is distributed and coordinated at the bridge. This study thus favours a systems approach to studying SA, viewing it not as a phenomenon that solely happens in each individual's mind but rather as something that happens between individuals and the tools that they use in a collaborative system. Thus, this study adds to our understanding of SA as a distributed phenomenon. Data were collected in four field studies that lasted between 8 and 14 days on PSVs that operate on the Norwegian continental shelf and UK continental shelf. The study revealed pronounced variations in shipboard practices regarding how the bridge team attended to operational planning, communication procedures, and distracting/interrupting factors during operations. These findings shed new light on how SA might decrease in bridge teams during platform supply operations. The findings from this study emphasize the need to assess and establish shipboard practices that support the bridge teams' SA needs in day-to-day operations. Practitioner points Provides insights into how shipboard practices that are relevant to planning, communication and the occurrence of distracting/interrupting factors are realized in bridge operations. Notes possible areas for improvement to enhance distributed SA in bridge operations. PMID:26028823

  5. Bridge permeameter

    DOEpatents

    Graf, Darin C.; Warpinski, Norman R.

    1996-01-01

    A system for single-phase, steady-state permeability measurements of porous rock utilizes a fluid bridge arrangement analogous to a Wheatstone bridge. The arms of the bridge contain the sample and calibrated flow resistors.

  6. Isomeric Trimethylene and Ethylene Pendant-armed Cross-bridged Tetraazamacrocycles and in Vitro/in Vivo Comparisions of their Copper(II) Complexes

    PubMed Central

    2011-01-01

    Ethylene cross-bridged tetraamine macrocycles are useful chelators in coordination, catalytic, medicinal, and radiopharmaceutical chemistry. Springborg and co-workers developed trimethylene cross-bridged analogues, although their pendant-armed derivatives received little attention. We report here the synthesis of a bis-carboxymethyl pendant-armed cyclen with a trimethylene cross-bridge (C3B-DO2A) and its isomeric ethylene-cross-bridged homocyclen ligand (CB-TR2A) as well as their copper(II) complexes. The in vitro and in vivo properties of these complexes are compared with respect to their potential application as 64Cu-radiopharmaceuticals in positron emission tomography (PET imaging). The inertness of Cu-C3B-DO2A to decomplexation is remarkable, exceeding that of Cu-CB-TE2A. Electrochemical reduction of Cu-CB-TR2A is quasi-reversible, whereas that of Cu-C3B-DO2A is irreversible. The reaction conditions for preparing 64Cu-C3B-DO2A (microwaving at high temperature) are relatively harsh compared to 64Cu-CB-TR2A (basic ethanol). The in vivo behavior of the 64Cu complexes was evaluated in normal rats. Rapid and continual clearance of 64Cu-CB-TR2A through the blood, liver, and kidneys suggests relatively good in vivo stability, albeit inferior to 64Cu-CB-TE2A. Although 64Cu-C3B-DO2A clears continually, the initial uptake is high and only about half is excreted within 22 h, suggesting poor stability and transchelation of 64Cu to proteins in the blood and/or liver. These data suggest that in vitro inertness of a chelator complex may not always be a good indicator of in vivo stability. PMID:21381676

  7. Study of the transport properties of organic semiconductors based on europium diphthalocyanine and bi-tris-phthalocyanine complexes with ortho-bis(oxymethyl)phenyl bridge and based on erbium and europium dinaphthalocyanine complexes

    SciTech Connect

    Belogorokhov, I. A.; Tikhonov, E. V.; Dronov, M. A.; Ryabchikov, Yu. V.; Pashkova, N. V.; Kladova, E. I.; Belogorokhova, L. I.; Tomilova, L. G.; Khokhlov, D. R.

    2011-11-15

    The transport properties of organic semiconductors based on europium diphthalocyanine and bitris-phthalocyanine complexes with ortho-bis(oxymethyl)phenyl bridge and based on europium and erbium dinaphthalocyanine are studied. The temperature dependences of the dc conductivity for all types of the structures under study are obtained; it is shown that all dependences include two activation portions. For high-temperature portions, the activation energies are determined as 0.85 eV for europium diphthalocyanine with the ortho-bis(oxymethyl)phenyl bridge, 1.135 eV for europium bi-tris-phthalocyanine with the orthobis(oxymethyl)phenyl bridge, 0.98 eV for europium dinaphthalocyanine, and 1.18 eV for erbium dinaphthalocyanine. For the low-temperature activation portion, it is shown that lanthanide ions and their bond with a ligand make the dominant contribution to the conductivity of the structures under study.

  8. Three Bridge Fryer's Ford Bridge, Nimrod Bridge, and Ward's ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    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

  9. Synthesis, structure, solution and DFT studies of a pyrazine-bridged binuclear Cu(II) complex: On the importance of noncovalent interactions in the formation of crystalline network

    NASA Astrophysics Data System (ADS)

    Mirzaei, Masoud; Eshtiagh-Hosseini, Hossein; Karrabi, Zahra; Notash, Behrouz; Bauzá, Antonio; Frontera, Antonio; Habibi, Morteza; Ardalani, Mehdi; Shamsipur, Mojtaba

    2015-01-01

    A pyrazine-bridged binuclear Cu(II) complexes with formulae of [Cu2(chel)2(pyz)(H2O)4], (1, pyz = pyrazine, H2chel = chelidamic acid), has been synthesized and characterized by elemental analyses, IR spectroscopy and solution studies. The crystal structure of the binuclear Cu(II) complex has been determined by X-ray single-crystal diffraction technique. Both copper(II) metal centers are bridged by pyrazine. The coordination environment around each copper(II) atom can be described as a distorted octahedral geometry. The axial positions of each Cu(II) complex are occupied by two water molecules and equatorial positions are occupied by a tridentate chelidamic acid dianion and a pyrazine molecule that functions as a linear bidentate ligand bridging two Cu(II) complexes to form a dimer. Hydrogen bonding and Csbnd O⋯π interactions link the binuclear Cu(II) complex generating the 3D infinite network. These assemblies are described and analyzed by means of density functional theory (DFT) calculations since they play an important role in the construction of three-dimensional supramolecular frameworks. The protonation constants of pyrazine and chelidamic acid as the building blocks of the proton transfer systems (H2chel-pyz) and their corresponding stability constants were determined by potentiometric studies. The stoichiometry and stability constants of H2chel-pyz complex with Cu2+ was investigated by potentiometric technique in aqueous solution. The results from solution studies were compared with the solid state data, in details.

  10. A theoretical study on the molecular structure and vibrational (FT-IR and Raman) spectra of cyano-bridged heteronuclear polymeric complex of triethylenetetramine

    NASA Astrophysics Data System (ADS)

    Kürkçüoğlu, Güneş Süheyla; Çetinkaya, Fulya; Arslan, Taner

    The cyano bridged complex of triethylenetetramine was characterized by FT-IR, Raman spectroscopy and X-ray single crystal diffraction analysis. The molecular geometry and vibrational frequencies of the complex in the ground state have been calculated by using B3LYP density functional method with LANL2DZ basis set. A good correlation was found via comparison of the experimental and theoretical vibrational frequencies of complex. The complex of the type [Zn(teta)Ni(μ-CN)2(CN)2]n has been studied in the 4000-250 cm-1 region and assignment of all the observed bands were made. The analysis of the FT-IR and Raman spectra indicates that there are some structure spectra correlations.

  11. Phenoxide bridged tetranuclear Co(II), Ni(II), Cu(II) and Zn(II) complexes: Electrochemical, magnetic and antimicrobial studies

    NASA Astrophysics Data System (ADS)

    Kamath, Anupama; Kulkarni, Naveen V.; Netalkar, Priya P.; Revankar, Vidyanand K.

    2011-09-01

    Phenoxide bridged later first row transition metal(II) complexes have been prepared by the interaction of later 3d transition metal(II) chlorides with tetranucleating compartmental Schiff base ligand system derived from 2,6-diformyl-4-methylphenol, p-phenylenediamine and 2-hydrazinobenzothiazole. Ligand and complexes were characterized by analytical, spectral (IR, UV-visible, ESR, FAB-mass and fluorescence), magnetic and thermal studies. All complexes are found to have octahedral geometry. The mutual influence of metal centres in terms of cooperative effect on the electronic, magnetic, electrochemical and structural properties was investigated. The Schiff base and its complexes have been screened for their antibacterial (against Escherichia coli, Staphylococcus aureus, Pseudomonas aeruginosa) and antifungal activities (against Aspergillus niger, and Candida albicans).

  12. A synthetic strategy for a new series of oxo-centered tricobalt complexes with mixed bridging ligands of acetate and pyrazolate anions.

    PubMed

    Yoshida, Jun; Kondo, Shohei; Yuge, Hidetaka

    2013-02-21

    A new series of oxo-centered tricobalt(III, III, III) complexes, containing mixed bridges of acetate and pyrazolate anions, has been synthesized based on a strategy consisting of two stages. In the first stage, the reaction of cobalt(II) acetate tetrahydrate with pyrazole in the presence of oxidants, followed by purification with silica-gel column chromatography, afforded six tricobalt complexes: [Co(3)O(μ-OAc)(5)(μ-pz)(Hpz)(3)](PF(6)) (mono), two isomers of [Co(3)O(μ-OAc)(4)(μ-pz)(2)(Hpz)(3)](PF(6)) (bis-1 and bis-2), two isomers of [Co(3)O(μ-OAc)(3)(μ-pz)(3)(Hpz)(3)](PF(6)) (tris-2 and tris-3), and one isomer of [Co(3)O(μ-OAc)(2)(μ-pz)(4)(Hpz)(3)](PF(6)) (tetra-1). In the second stage, substitution reactions have been examined for the complexes obtained in the first stage. As a result, one acetate bridge in bis-1, bis-2, and tris-3 could be substituted with one pyrazolate site-selectively. Bis-1, bis-2, and tris-3 were converted to another isomer of [Co(3)O(μ-OAc)(3)(μ-pz)(3)(Hpz)(3)](PF(6)) (tris-1), tris-2, and tetra-1, respectively. Single-crystal X-ray diffraction studies found that in every complex acetato and pyrazolato work as bridging ligands, while pyrazole (Hpz) acts as a terminal ligand. Moreover, the electrochemical properties of the seven new tricobalt complexes (mono, bis-1, bis-2, tris-1, tris-2, tris-3, and tetra-1) were investigated by cyclic voltammetry and it was found that (1) each complex shows reversible redox behaviour corresponding to the Co(III)Co(III)Co(III)/Co(III)Co(III)Co(IV) couple and (2) the redox potential decreases from 1.21 V vs. Fc/Fc(+) in mono to 1.09 V vs. Fc/Fc(+) in tetra-1, as the number of pyrazolate bridges increases.

  13. Doubly end-on azido bridged mixed-valence cobalt trinuclear complex: Spectral study, VTM, inhibitory effect and antimycobacterial activity on human carcinoma and tuberculosis cells

    NASA Astrophysics Data System (ADS)

    Datta, Amitabha; Das, Kuheli; Sen, Chandana; Karan, Nirmal Kumar; Huang, Jui-Hsien; Lin, Chia-Her; Garribba, Eugenio; Sinha, Chittaranjan; Askun, Tulin; Celikboyun, Pinar; Mane, Sandeep B.

    2015-09-01

    Doubly end-on azido-bridged mixed-valence trinuclear cobalt complex, [Co3(L)2(N3)6(CH3OH)2] (1) is afforded by employing a potential monoanionic tetradentate-N2O2 Schiff base precursor (2-[{[2-(dimethylamino)ethyl]imino}methyl]-6-methoxyphenol; HL). Single crystal X-ray structure reveals that in 1, the adjacent CoII and CoIII ions are linked by double end-on azido bridges and thus the full molecule is generated by the site symmetry of a crystallographic twofold rotation axis. Complex 1 is subjected on different spectral analysis such as IR, UV-vis, emission and EPR spectroscopy. On variable temperature magnetic study, we observe that during cooling, the χMT values decrease smoothly until 15 K and then reaches to the value 1.56 cm3 K mol-1 at 2 K. Complex 1 inhibits the cell growth on human lung carcinoma (A549 cells), human colorectal (COLO 205 and HT-29 cells), and human heptacellular (PLC5 cells) carcinoma cells. Complex 1 exhibits anti-mycobacterial activity and considerable efficacy on Mycobacterium tuberculosis H37Rv ATCC 27294 and H37Ra ATCC 25177 strains.

  14. Bimetallic ruthenium complexes bridged by divinylphenylene bearing oligo(ethylene glycol)methylether: synthesis, (spectro)electrochemistry and the lithium cation effect.

    PubMed

    Tian, Li Yan; Liu, Yuan Mei; Tian, Guang-Xuan; Wu, Xiang Hua; Li, Zhen; Kou, Jun-Feng; Ou, Ya-Ping; Liu, Sheng Hua; Fu, Wen-Fu

    2014-03-14

    A series of 1,4-disubstituted ruthenium-vinyl complexes, (E,E)-[{(PMe3)3(CO)ClRu}2(μ-HC=CH-Ar-CH=CH)], in which the 1,4-diethenylphenylene bridge bears two oligo(ethylene glycol)methyl ether side chains at different positions (2,5- and 2,3-positions), were prepared. The respective products were characterized by elemental analyses and NMR spectroscopy. The structures of complexes 1b and 1e were established by X-ray crystallography. The electronic properties of the complexes were investigated by cyclic voltammetry, and IR and UV-vis/NIR spectroscopies. Electrochemical studies showed that the 2,5-substituents better stabilized the mixed-valence states; the electrochemical behavior was greatly affected by lithium cations, especially complex 1g with 2,3-substituents, which was further supported by IR and UV-vis/NIR spectra changes. Spectroelectrochemical studies showed that the redox chemistry was dominated by the non-innocent character of the bridging fragment. PMID:24457499

  15. Photophysical study of spiro-bifluorene bridged Pt(II), Os(II) and Ir(III) luminescent complexes and supramolecular arrays.

    PubMed

    Gullo, Maria Pia; Seneclauze, Julie Batcha; Ventura, Barbara; Barbieri, Andrea; Ziessel, Raymond

    2013-12-28

    This paper describes expeditious stepwise synthesis of polynuclear complexes based on heteroleptic iridium(iii) and osmium(ii) fragments linked to a central Pt(ii) module via a spirobifluorene-bridge using a strategy based on the construction of preformed complexes. The luminescence features of the final multi-chromophoric array, i.e. a tetrad consisting of spirobifluorene-bridged Pt, Ir and Os complexes, have been studied by comparison with the features of reference complexes bearing two identical luminophores (Ir or Os) at the periphery. The (3)MPtLCT and (3)LC states of the Pt and spiro ligand undergo fast energy transfer into the (3)MIrLCT or the (3)MOsLCT state in the Pt-M2 (M = Ir or Os) arrays, whereas the (3)LC and the (3)MPtLCT states function as energy reservoirs for the metal excited states close in energy, resulting in a pronounced increase of the excited state lifetimes of these arrays. The tetrad efficiently works as an antenna system where the collected light energy is transferred to the Os unit acting as the final collector.

  16. Bimetallic ruthenium complexes bridged by divinylphenylene bearing oligo(ethylene glycol)methylether: synthesis, (spectro)electrochemistry and the lithium cation effect.

    PubMed

    Tian, Li Yan; Liu, Yuan Mei; Tian, Guang-Xuan; Wu, Xiang Hua; Li, Zhen; Kou, Jun-Feng; Ou, Ya-Ping; Liu, Sheng Hua; Fu, Wen-Fu

    2014-03-14

    A series of 1,4-disubstituted ruthenium-vinyl complexes, (E,E)-[{(PMe3)3(CO)ClRu}2(μ-HC=CH-Ar-CH=CH)], in which the 1,4-diethenylphenylene bridge bears two oligo(ethylene glycol)methyl ether side chains at different positions (2,5- and 2,3-positions), were prepared. The respective products were characterized by elemental analyses and NMR spectroscopy. The structures of complexes 1b and 1e were established by X-ray crystallography. The electronic properties of the complexes were investigated by cyclic voltammetry, and IR and UV-vis/NIR spectroscopies. Electrochemical studies showed that the 2,5-substituents better stabilized the mixed-valence states; the electrochemical behavior was greatly affected by lithium cations, especially complex 1g with 2,3-substituents, which was further supported by IR and UV-vis/NIR spectra changes. Spectroelectrochemical studies showed that the redox chemistry was dominated by the non-innocent character of the bridging fragment.

  17. Synthesis and structure of dimeric anthracene-9-carboxylato bridged dinuclear erbium(III) complex, [Er(2)(9-AC)(6)(DMF)(2)(H(2)O)(2)].

    PubMed

    Kusrini, Eny; Adnan, Rohana; Saleh, Muhammad I; Yan, Lim-Kong; Fun, Hoong-Kun

    2009-05-01

    We study the influence of the bulky aromatic rings, e.g. anthracence-9-carboxylic acid (9-ACA) with a large conjugated pi-system on the structure and spectroscopic properties of [Er(2)(9-AC)(6)(DMF)(2)(H(2)O)(2)] complex where 9-AC=anthracence-9-carboxylato and DMF=N,N'-dimethylformamide. The complex has been prepared from the erbium chloride and 9-ACA in the mixture of H(2)O:DMF solution (4:1, v/v) followed by pH adjustment to 6. The complex is crystallized in a monoclinic system with space group P2(1)/n. The two Er(III) ions are double bridged by the deprotonated carboxyl groups of two 9-AC anions (O1 and O1A), forming an eight-coordination number. The chelating bidentate (O,O), chelating-bridging tridentate (O,O,O') and monodentate of 9-AC anions are observed in the dinuclear [Er(2)(9-AC)(6)(DMF)(2)(H(2)O)(2)] complex. The Er-Er distance is 4.015A in the dimeric unit. Intramolecular O-Hcdots, three dots, centeredO and C-Hcdots, three dots, centeredO hydrogen bonds as well as numerous of intermolecular C-Hcdots, three dots, centeredpi interactions between the anthracene rings by edge-to-face interactions linked the dinuclear dimeric units into two-dimensional supramolecular network in a propeller-arrangement. Electronic absorption spectra of the Er(III) complex and its salt were measured. The emission spectrum of the complex is composed of a broad band due to the emission of intraligand pi*-->pi transition from the 9-AC anions and a shoulder peak originating from the 4f-4f emission transition of the Er(III) ions. The complex has a high thermal stability which can be attributed to the effectively increase the rigidity of the 9-AC anions.

  18. Ferromagnetic coupling in the three-dimensional malonato-bridged gadoliniumIII complex [Gd2(mal)3(H2O)6] (H2mal = malonic acid).

    PubMed

    Hernández-Molina, María; Ruiz-Pérez, Catalina; López, Trinidad; Lloret, Francesc; Julve, Miguel

    2003-09-01

    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))).

  19. Bridging the Gap in the Chemical Thermodynamic Database for Nuclear Waste Repository: Studies of the Effect of Temperature on Actinide Complexation

    SciTech Connect

    Rao, Linfeng; Tian, Guoxin; Xia, Yuanxian; Friese, Judah I.; Zanonato, PierLuigi; Di Bernardo, Plinio

    2009-12-21

    Recent results of thermodynamic studies on the complexation of actinides (UO{sub 2}{sup 2+}, NpO{sub 2}{sup +} and Pu{sup 4+}) with F{sup -}, SO{sub 4}{sup 2-} and H{sub 2}PO{sub 4}{sup -}/HPO{sub 4}{sup 2-} at elevated temperatures are reviewed. The data indicate that, for all systems except the 1:1 complexation of Np(V) with HPO{sub 4}{sup 2-}, the complexation of actinides is enhanced by the increase in temperature. The enhancement is primarily due to the increase in the entropy term (T{Delta}S) that exceeds the increase in the enthalpy ({Delta}H) as the temperature is increased. These data bridge the gaps in the chemical thermodynamic database for nuclear waste repository where the temperature could remain significantly higher than 25 C for a long time after the closure of the repository.

  20. A novel Schiff base bearing dopamine groups with tripodal structure. Synthesis and its salen/salophen-bridged Fe/Cr(III) capped complexes

    NASA Astrophysics Data System (ADS)

    Kocyigit, Ozcan

    2013-02-01

    This work presents the synthesis of a novel Schiff base and its complexation properties with Fe(III) and Cr(III). A Schiff base bearing dopamine (TRDPA) was synthesized using dopamine hydrochloride and 1,3,5-tris (formylphenoxymethyl)benzene in methanol media. The prepared TRDPA was then reacted with four new trinuclear Fe(III) and Cr(III) complexes involving tetradenta Schiff bases N,N-bis(salicylidene)ethylenediamine-(salenH2) or bis(salicylidene)-o-phenylenediamine-(salophenH2). The structures of these compounds were characterized through 1H NMR, 13C NMR, FT-IR, thermal analysis (TG), elemental analysis, and magnetic susceptibility measurements. The complexes were also characterized as low-spin distorted octahedral Fe(III) and Cr(III) bridged by a catechol group.

  1. Synthesis, spectral and structural characterization of a novel phenoxo-bridged dinuclear Co II complex with a tridentate phenol-functionalized diazamesocyclic ligand

    NASA Astrophysics Data System (ADS)

    Du, Miao; An, Dao-Li; Guo, Ya-Mei; Bu, Xian-He

    2002-11-01

    A novel phenoxo-bridged dinuclear Co II complex with a diazamesocyclic ligand bearing one additional phenol functional donor group, [CoLCl] 2·2C 3H 6O ( 1) (where HL=1-(2-hydroxybenzyl)-1,5-diazacyclooctane), has been synthesized and characterized by elemental analyses, conductance, thermal analyses, IR and UV-vis spectra. The crystal structure of complex 1 has been determined by X-ray diffraction technique, which reveals that it is a neutral complex and resides on a crystallographic inversion center. The two Co II centers bridged by the phenoxo groups are penta-coordinated, taking a coordination sphere in the midst of the ideal square-pyramid and trigonal bipyramid. 1,5-Diazacyclooctane of the ligand takes a boat/ chair conformation and an H atom from it effectively blocks the axial coordination site opposite the Cl - ligand to form CoN 2O 2Cl geometry. The crystal structure is stabilized by the N-H⋯O hydrogen bond between the amino group and the acetone molecule.

  2. Targeted construction of azido-bridged Ni4 complexes with decisive effect of mu-1,3-azide torsion on the spin ground state.

    PubMed

    Demeshko, Serhiy; Leibeling, Guido; Dechert, Sebastian; Meyer, Franc

    2006-07-28

    Highly preorganized pyrazolate-based dinickel(II) systems are shown to constitute suitable building blocks for the targeted assembly of azido-bridged Ni4 complexes with rectangular arrangement of the metal ions. A set of such complexes has been prepared and structurally characterized. mu-1,1-Azide binding within the bimetallic sub-units is controlled by the chosen topology of the pyrazolate ligand scaffold and gives rise to the anticipated ferromagnetic intradimer coupling. Overall magnetic properties of the Ni4 array, however, are mainly determined by the Ni-NNN-Ni torsion of the interdimer mu-1,3-azido linkages. According to the crystallographic results, these torsion angles vary over a wide range, and partial disorder of the mu-1,3-azide bridge in one of the compounds indicates high structural flexibility even in the solid state. Two of the compounds represent rare examples of molecular complexes with a Ni-NNN-Ni torsion angle of almost exactly 90 degrees . The resulting magnetic ground state (neglecting zero-field splitting) is either S = 0 or S = 4 depending on the Ni-NNN-Ni torsion, and in one case a drastic change is observed upon extrusion of lattice solvent.

  3. Copper(II) cyanido-bridged bimetallic nitroprusside-based complexes: Syntheses, X-ray structures, magnetic properties, {sup 57}Fe Moessbauer spectroscopy and thermal studies

    SciTech Connect

    Travnicek, Zdenek; Herchel, Radovan; Mikulik, Jiri; Zboril, Radek

    2010-05-15

    Three heterobimetallic cyanido-bridged copper(II) nitroprusside-based complexes of the compositions [Cu(tet)Fe(CN){sub 5}NO].H{sub 2}O (1), where tet=N,N'-bis(3-aminopropyl)ethylenediamine, [Cu(hto)Fe(CN){sub 5}NO].2H{sub 2}O (2), where hto=1,3,6,9,11,14-hexaazatricyclo[12.2.1.1{sup 6,9}]octadecane and [Cu(nme){sub 2}Fe(CN){sub 5}NO].H{sub 2}O (3), where nme=N-methylethylenediamine, were synthesized and characterized by elemental analyses, {sup 57}Fe Moessbauer and FTIR spectroscopies, thermal analysis, magnetic measurements and single-crystal X-ray analysis. The products of thermal degradation processes of 2 and 3 were studied by XRD, {sup 57}Fe Moessbauer spectroscopy, SEM and EDS, and they were identified as mixtures of CuFe{sub 2}O{sub 4} and CuO. - Three heterobimetallic cyano-bridged copper(II) nitroprusside-based complexes of the general compositions of [Cu(L)Fe(CN){sub 5}NO].xH{sub 2}O, where L=N,N'-bis(3-aminopropyl)ethylenediamine (complex 1), 1,3,6,9,11,14-hexaazatricyclo[12.2.1.1{sup 6,9}]-octadecane (complex 2) and N-methylethylenediamine (complex 3), were synthesized, and fully structurally and magnetically characterized. SEM, EDS, XRD and {sup 57}Fe Moessbauer experiments were used for characterization of thermal decomposition products of complexes 2 and 3.

  4. Bridge permeameter

    DOEpatents

    Graf, D.C.; Warpinski, N.R.

    1996-08-13

    A system is described for single-phase, steady-state permeability measurements of porous rock which utilizes a fluid bridge arrangement analogous to a Wheatstone bridge. The arms of the bridge contain the sample and calibrated flow resistors. 8 figs.

  5. Synthesis, magnetic behaviour, and X-ray structures of dinuclear copper complexes with multiple bridges. Efficient and selective catalysts for polymerization of 2,6-dimethylphenol.

    PubMed

    Murugavel, Ramaswamy; Pothiraja, Ramasamy; Gogoi, Nayanmoni; Clérac, Rodolphe; Lecren, Lollita; Butcher, Ray J; Nethaji, Munirathinam

    2007-06-21

    The use of a potentially tridentate mono-anionic bridging ligand, 1,3-bis(3,5-dimethylpyrazol-1-yl)-propan-2-ol (bdmpp-H), in assembling new dimeric copper complexes with interesting magnetic properties has been investigated. The reaction of copper hydroxide or copper acetate with phenyl phosphinic acid or diphenyl phosphinic acid in the presence of bdmpp-H produces the dinuclear complexes [Cu(bdmpp)(ppi)]2 (1) and [Cu(bdmpp)(dppi-H)]2(dppi)2 (2) (ppi-H = phenylphosphinic acid: dppi-H = diphenylphosphinic acid), respectively. The products have been characterized with the help of analytical, thermal, and spectroscopic (IR, UV-vis, and EPR) techniques. Single crystal X-ray diffraction studies of 1 and 2 reveal that the two bdmpp ligands hold together the dimeric copper unit in each complex through mu-O alkoxide and the pyrazolyl nitrogen ligating centers. Two phenyl phosphinate ligands additionally bridge the dicopper core in 1 to result in octahedral coordination geometry around each metal ion. The diphenyl phosphinic acid acts as a terminal ligand in 2, and thus completes a square pyramidal geometry around each copper ion. Both complexes show a very short Cu...Cu separation (3.001 and 3.065 angstroms for 1 and 2, respectively). The investigation of the magnetic properties reveals the efficiency of the double alkoxide bridge between the two paramagnetic copper ions to mediate strong antiferromagnetic interactions [J/k(B) = -620(5) K (-431(4) cm(-1)) and -685(5) K (-476(4) cm(-1)) for 1 and 2, respectively]. Compounds 1 and 2, along with a few other copper phosphate complexes, were tested as catalysts for the oxidative polymerization of 2,6-dimethylphenol; 1 and 2 were found to be efficient catalysts with an increased selectivity for the formation of the polyphenylene ether. However a related mononuclear octahedral copper complex [Cu(imz)4(dtbp)2] (dtbp-H = di-tert-butylphosphate) was found to be more efficient. PMID:17844662

  6. Synthesis, characterization, and reactivity studies of a water-soluble bis(alkoxo)(carboxylato)-bridged diMn(III) complex modeling the active site in catalase.

    PubMed

    Palopoli, Claudia; Duhayon, Carine; Tuchagues, Jean-Pierre; Signorella, Sandra

    2014-12-01

    A new diMn(III) complex, Na[Mn2(5-SO3-salpentO)(μ-OAc)(μ-OMe)(H2O)]·4H2O, where 5-SO3-salpentOH = 1,5-bis(5-sulphonatosalicylidenamino)pentan-3-ol, has been prepared and characterized. ESI-mass spectrometry, paramagnetic (1)H NMR, EPR and UV-visible spectroscopic studies on freshly prepared solutions of the complex in methanol and 9 : 1 methanol-water mixtures showed that the compound retains the triply bridged bis(μ-alkoxo)(μ-acetato)Mn2(3+) core in solution. In the 9 : 1 methanol-water mixture, slow substitution of acetate by water molecules took place, and after one month, the doubly bridged diMn(III) complex, [Mn2(5-SO3-salpentO)(μ-OMe)(H2O)3]·5H2O, formed and could be characterized by X-ray diffraction analysis. In methanolic or aqueous basic media, acetate shifts from a bridging to a terminal coordination mode, affording the highly stable [Mn2(5-SO3-salpentO)(μ-OMe)(OAc)](-) anion. The efficiency of the complex in disproportionating H2O2 depends on the solvent and correlates with the stability of the complex (towards metal dissociation) in each medium: basic buffer > aqueous base > water. The buffer preserves the integrity of the catalyst and the rate of O2 evolution remains essentially constant after successive additions of excess of H2O2. Turnovers as high as 3000 mol H2O2 per mol of catalyst, without significant decomposition and with an efficiency of k(cat)/K(M) = 1028 M(-1) s(-1), were measured for the complex in aqueous buffers of pH 11. Kinetic and spectroscopic results suggest a catalytic cycle that runs between Mn(III)2 and Mn(IV)2 oxidation states, which is consistent with the low redox potential observed for the Mn(III)2/Mn(III)Mn(IV) couple of the catalyst in basic medium.

  7. Spin crossover and polymorphism in a family of 1,2-bis(4-pyridyl)ethene-bridged binuclear iron(II) complexes. A key role of structural distortions.

    PubMed

    Matouzenko, Galina S; Jeanneau, Erwann; Verat, Alexander Yu; Bousseksou, Azzedine

    2011-10-01

    Two polymorphic modifications 1 and 3 of binuclear compound [{Fe(dpia)(NCS)(2)}(2)(bpe)] and pseudo-polymorphic modification [{Fe(dpia)(NCS)(2)}(2)(bpe)]·2CH(3)OH (2), where dpia = di-(2-picolyl)amine, bpe = 1,2-bis(4-pyridyl)ethene, were synthesized, and their structures, magnetic properties, and Mössbauer spectra were studied. Variable-temperature magnetic susceptibility measurements of three binuclear compounds show different types of magnetic behaviour. The complex 1 exhibits a gradual two-step spin crossover (SCO) suggesting the occurrence of the mixed [HS-LS] (HS: high spin, LS: low spin) pair at the plateau temperature (182 K), at which about 50% of the complexes undergoes a thermal spin conversion. The complex 2 displays an abrupt full one-step spin transition without hysteresis, centred at about 159 K. The complex 3 is paramagnetic over the temperature range 20-290 K. The single-crystal X-ray studies show that all three compounds are built up from the bpe-bridged binuclear molecules. The structure of 1 was solved for three spin isomers [HS-HS], [HS-LS], and [LS-LS] at three temperatures 300 K, 183 K, and 90 K. The crystal structures for 2 and 3 were determined for the [HS-HS] complexes at room temperature. The analysis of correlations between the structural characteristics and different types of magnetic behaviour for new 1-3 binuclear complexes, as well as for previously reported binuclear compounds, revealed that the SCO process (occurrence of full one-step, two-step, or partial (50%) SCO) is specified by the degree of distortion of the octahedral geometry of the [FeN(6)] core, caused by both packing and strain effects arising from terminal and/or bridging ligands. The comparison of the magnetic properties and the networks of intra- and inter-molecular interactions in the crystal lattice for the family of related SCO binuclear compounds suggests that the intermolecular interactions play a predominant role in the cooperativeness of the spin transition

  8. Synthesis, structure, and electrochemical characterization of a mixed-ligand diruthenium(III,II) complex with an unusual arrangement of the bridging ligands.

    PubMed

    Ngubane, Siyabonga; Kadish, Karl M; Bear, John L; Van Caemelbecke, Eric; Thuriere, Antoine; Ramirez, Kevin P

    2013-03-14

    A mixed-ligand metal-metal bonded diruthenium complex having the formula Ru(2)(2,4,6-(CH(3))(3)ap)(3)(O(2)CCH(3))Cl where ap is the anilinopyridinate anion was synthesized from the reaction of Ru(2)(O(2)CCH(3))(4)Cl and H(2,4,6-(CH(3))(3)ap), after which the isolated product was structurally, spectroscopically and electrochemically characterized. The crystal structure reveals an unusual arrangement of the bridging ligands around the dimetal unit where one ruthenium atom is coordinated to one anilino and two pyridyl nitrogen atoms while the other ruthenium atom is coordinated to one pyridyl and two anilino nitrogen atoms. To our knowledge, Ru(2)(2,4,6-(CH(3))(3)ap)(3)(O(2)CCH(3))Cl is the only example of a mixed-ligand diruthenium complex of the type [Ru(2)L(3)(O(2)CCH(3))](+), where L is an unsymmetrical anionic bridging ligand that has been structurally characterized with a "(2,1)" geometric conformation of the bridging ligands, all others being "(3,0)". The initial Ru(2)(5+) compound in CH(2)Cl(2) or CH(3)CN containing 0.1 M tetra-n-butylammonium perchlorate (TBAP) undergoes up to four one-electron redox processes involving the dimetal unit. The Ru(2)(5+/4+) and Ru(2)(5+/6+) processes were characterized under N(2) using thin-layer UV-visible spectroelectrochemistry and this data is compared to UV-visible spectral changes obtained during similar electrode reactions for related diruthenium compounds having the formula Ru(2)L(4)Cl or Ru(2)L(3)(O(2)CCH(3))Cl where L is an anionic bridging ligand. Ru(2)(2,4,6-(CH(3))(3)ap)(3)(O(2)CCH(3))Cl was also examined by UV-visible and FTIR spectroelectrochemistry under a CO atmosphere and two singly reduced Ru(2)(4+) species, [Ru(2)(2,4,6-(CH(3))(3)ap)(3)(O(2)CCH(3))(CO)Cl](-) and Ru(2)(2,4,6-(CH(3))(3)ap)(3)(O(2)CCH(3))(CO) were in situ generated for further characterization. The CO-bound complexes could be further reduced and exhibited additional reductions to their Ru(2)(3+) and Ru(2)(2+) oxidation states. PMID:23283183

  9. DNA Binding and Photocleavage Properties, Cellular Uptake and Localization, and in-Vitro Cytotoxicity of Dinuclear Ruthenium(II) Complexes with Varying Lengths in Bridging Alkyl Linkers.

    PubMed

    Liu, Ping; Wu, Bao-Yan; Liu, Jin; Dai, Yong-Cheng; Wang, You-Jun; Wang, Ke-Zhi

    2016-02-15

    Two new dinuclear Ru(II) polypyridyl complexes containing three and ten methylene chains in their bridging linkers are synthesized and characterized. Their calf thymus DNA-binding and plasmid DNA photocleavage behaviors are comparatively studied with a previously reported, six-methylene-containing analog by absorption and luminescence spectroscopy, steady-state emission quenching by [Fe(CN)6](4-), DNA competitive binding with ethidium bromide, DNA viscosity measurements, DNA thermal denaturation, and agarose gel electrophoresis analyses. Theoretical calculations applying the density functional theory (DFT) method for the three complexes are also performed to understand experimentally observed DNA binding properties. The results show that the two complexes partially intercalate between the base pairs of DNA. Cellular uptake and colocalization studies have demonstrated that the complexes could enter HeLa cells efficiently and localize within lysosomes. The in-vitro antitumor activity against HeLa and MCF-7 tumor cells of the complexes are studied by MTT cytotoxic analysis. A new method, high-content analysis (HCA), is also used to assess cytotoxicity, apoptosis and cell cycle arrest of the three complexes. The results show that the lengths of the alkyl linkers could effectively tune their biological properties and that HCA is suitable for rapidly identifying cytotoxicity and can be substituted for MTT assays to evaluate the cell cytotoxicity of chemotherapeutic agents.

  10. Synthesis, Cu(II) complexation, 64Cu-labeling and biological evaluation of cross-bridged cyclam chelators with phosphonate pendant arms†

    PubMed Central

    Ferdani, Riccardo; Stigers, Dannon J.; Fiamengo, Ashley L.; Wei, Lihui; Li, Barbara T. Y.; Golen, James A.; Rheingold, Arnold L.; Weisman, Gary R.; Wong, Edward H.; Anderson, Carolyn J.

    2012-01-01

    A new class of cross-bridged cyclam-based macrocycles featuring phosphonate pendant groups has been developed. 1,4,8,11-tetraazacyclotetradecane-1,8-di(methanephosphonic acid) (CB-TE2P, 1) and 1,4,8,11-tetraazacyclotetradecane-1-(methanephosphonic acid)-8-(methanecarboxylic acid) (CB-TE1A1P, 2) have been synthesized and have been shown to readily form neutral copper (II) complexes at room temperature as the corresponding dianions. Both complexes showed high kinetic inertness to demetallation and crystal structures confirmed complete encapsulation of copper (II) ion within each macrocycle’s cleft-like structure. Unprecedented for cross-bridged cyclam derivatives, both CB-TE2P (1) and CB-TE1A1P (2) can be radiolabeled with 64Cu at room temperature in less than 1 hour with specific activities >1mCi/μg. The in vivo behavior of both 64Cu-CB-TE2P and 64Cu-CB-TE1A1P were investigated through biodistribution studies using healthy, male, Lewis rats. Both new compounds showed rapid clearance with similar or lower accumulation in non-target organs/tissues when compared to other copper chelators including CB-TE2A, NOTA and Diamsar. PMID:22170043

  11. Exploring the active site of the Streptococcus pneumoniae topoisomerase IV–DNA cleavage complex with novel 7,8-bridged fluoroquinolones

    PubMed Central

    Laponogov, Ivan; Pan, Xiao-Su; Veselkov, Dennis A.; Cirz, Ryan T.; Wagman, Allan; Moser, Heinz E.

    2016-01-01

    As part of a programme of synthesizing and investigating the biological properties of new fluoroquinolone antibacterials and their targeting of topoisomerase IV from Streptococcus pneumoniae, we have solved the X-ray structure of the complexes of two new 7,8-bridged fluoroquinolones (with restricted C7 group rotation favouring tight binding) in complex with the topoisomerase IV from S. pneumoniae and an 18-base-pair DNA binding site—the E-site—found by our DNA mapping studies to bind drug strongly in the presence of topoisomerase IV (Leo et al. 2005 J. Biol. Chem. 280, 14 252–14 263, doi:10.1074/jbc.M500156200). Although the degree of antibiotic resistance towards fluoroquinolones is much lower than that of β-lactams and a range of ribosome-bound antibiotics, there is a pressing need to increase the diversity of members of this successful clinically used class of drugs. The quinolone moiety of the new 7,8-bridged agents ACHN-245 and ACHN-454 binds similarly to that of clinafloxocin, levofloxacin, moxifloxacin and trovofloxacin but the cyclic scaffold offers the possibility of chemical modification to produce interactions with other topoisomerase residues at the active site. PMID:27655731

  12. Synthesis and characterization of perchlorato bridged Cu2(II)Zn(II) heterotrinuclear complexes derived from succinoyldihydrazones.

    PubMed

    Borthakur, Rosmita; Kumar, Arvind; Shangpung, Sankey; Lal, Ram A

    2015-03-01

    In the present paper three new heterotrimetallic Cu(II)-Zn(II)-Cu(II) complexes have been synthesized and characterized by analytical and spectroscopic studies. The molar conductance values for the complexes fall in the region 1.2-1.7Ω(-1)cm(2)mol(-1) in DMSO solution indicating that all of the complexes are non-electrolyte. The dihydrazone ligand is present in enol form in all of the complexes. Both the copper centres have distorted square pyramidal stereochemistry in all of the complexes while the zinc centre in all hetero metal complexes has octahedral stereochemistry. The EPR parameters of the complexes indicate that the copper centre has [Formula: see text] orbital as the ground state. The electron transfer reactions of the complexes have been investigated by cyclic voltammetry.

  13. High-spin ground states via electron delocalization in mixed-valence imidazolate-bridged divanadium complexes.

    PubMed

    Bechlars, Bettina; D'Alessandro, Deanna M; Jenkins, David M; Iavarone, Anthony T; Glover, Starla D; Kubiak, Clifford P; Long, Jeffrey R

    2010-05-01

    The field of molecular magnetism has grown tremendously since the discovery of single-molecule magnets, but it remains centred around the superexchange mechanism. The possibility of instead using a double-exchange mechanism (based on electron delocalization rather than Heisenberg exchange through a non-magnetic bridge) presents a tantalizing prospect for synthesizing molecules with high-spin ground states that are well isolated in energy. We now demonstrate that magnetic double exchange can be sustained by simple imidazolate bridging ligands, known to be well suited for the construction of coordination clusters and solids. A series of mixed-valence molecules of the type [(PY5Me(2))V(II)(micro-L(br)) V(III)(PY5Me(2))](4+) were synthesized and their electron delocalization probed through cyclic voltammetry and spectroelectrochemistry. Magnetic susceptibility data reveal a well-isolated S = 5/2 ground state arising from double exchange for [(PY5Me(2))(2)V(2)(micro-5,6-dimethylbenzimidazolate)](4+). Combined modelling of the magnetic data and spectral analysis leads to an estimate of the double-exchange parameter of B = 220 cm(-1) when vibronic coupling is taken into account.

  14. Dinuclear and 1D iron(III) Schiff base complexes bridged by 4-salicylideneamino-1,2,4-triazolate: X-ray structures and magnetic properties.

    PubMed

    Herchel, Radovan; Pavelek, Lubomír; Trávníček, Zdeněk

    2011-11-28

    Four new iron(III) complexes were obtained by the reaction of 4-salicylideneamino-1,2,4-triazole (Hsaltrz) and selected dinuclear μ-oxo-bridged iron(III) Schiff base complexes [{FeL(4)}(2)(μ-O)], where L(4) represents a terminal tetradentate dianionic Schiff-base ligand. X-ray structural analysis revealed a novel bridging mode of κN,κO of the saltrz ligand to form dinuclear complexes [{Fe(salen)(μ-saltrz)}(2)]·CH(3)OH (1) (H(2)salen = N,N'-ethylenebis(salicylimine)) and [{Fe(salpn)(μ-saltrz)}(2)] (2) (H(2)salpn = N,N'-1,2-propylenbis(salicylimine)), whereas one-dimensional (1D) zig-zag chains were formed in the case of [{Fe(salch)(μ-saltrz)}·0.5CH(3)OH](n) (3) (H(2)salch = N,N'-cyclohexanebis(salicylimine)) and [Fe(salophen)(μ-saltrz)](n) (4) (H(2)salophen = N,N'-o-phenylenebis(salicylimine)). It was also shown that the rigidity of the terminal ligand L(4) can be considered as the key factor for the molecular dimensionality of the products. The thorough magnetic analysis based on SQUID experiments, including the isotropic exchange and the zero-field splitting of both temperature and field dependent data, was performed for dimeric (1 and 2) and also for polymeric compounds (3 and 4) and revealed weak antiferromagnetic exchange mediated by the saltrz anions with much larger D-parameter (|D|≫|J|). PMID:21968851

  15. Stepwise preparation and characterization of molecular wires made of zinc octaethylporphyrin complexes bridged by 4,4'-bipyridine on HOPG.

    PubMed

    Ferreira, Quirina; Alcácer, Luís; Morgado, Jorge

    2011-10-28

    Molecular-scale devices can be made using a step-by-step procedure, in a controllable and highly versatile way. In this report, we describe the growth of molecular wires (MW) from zinc (II) octaethylporphyrin (ZnOEP) assembled on highly oriented pyrolytic graphite (HOPG) by a step-by-step approach using 4,4'-bipyridine (BP) to bridge the porphyrin units, via coordination of the nitrogen atom to zinc. In order to gain an insight into the molecular self-organization of these wires, we carried out a detailed scanning tunnelling microscopy (STM) analysis of each monolayer, using a solid/liquid interface technique, up to a complete ZnOEP/BP/ZnOEP/BP/ZnOEP-assembled structure. The electrical properties of the MWs were assessed by scanning tunnelling spectroscopy (STS) and by current-sensing atomic force microscopy (CS-AFM), showing an increase of electrical resistance with the length of the MW.

  16. Myocardial Bridging

    PubMed Central

    Yuan, Shi-Min

    2016-01-01

    Myocardial bridging is rare. Myocardial bridges are most commonly localized in the middle segment of the left anterior descending coronary artery. The anatomic features of the bridges vary significantly. Alterations of the endothelial morphology and the vasoactive agents impact on the progression of atherosclerosis of myocardial bridging. Patients may present with chest pain, myocardial infarction, arrhythmia and even sudden death. Patients who respond poorly to the medical treatment with β-blockers warrant a surgical intervention. Myotomy is a preferred surgical procedure for the symptomatic patients. Coronary stent deployment has been in limited use due to the unsatisfactory long-term results. PMID:27074276

  17. Dinuclear Ruthenium Complex Based on a π-Extended Bridging Ligand with Redox-Active Tetrathiafulvalene and 1,10-Phenanthroline Units.

    PubMed

    Chen, Bin; Lv, Zhong-Peng; Hua, Carol; Leong, Chanel F; Tuna, Floriana; D'Alessandro, Deanna M; Collison, David; Zuo, Jing-Lin

    2016-05-01

    The synthesis of a π-extended bridging ligand with both redox-active tetrathiafulvalene (TTF) and 1,10-phenanthroline (phen) units, namely, bis(1,10-phenanthro[5,6-b])tetrathiafulvalene (BPTTF), was realized via a self-coupling reaction. Using this ligand and Ru(tbbpy)2Cl2 (tbbpy = 4,4'-di-tert-butyl-2,2'-bipyridine), the dinuclear ruthenium(II) compound [{Ru(tbbpy)2}2(BPTTF)](PF6)4 (1) has been obtained by microwave-assisted synthesis. Structural characterization of 1 revealed a crossed arrangement of the TTF moieties on adjacent dimers within the crystal structure. The optical and redox properties of 1 were investigated using electrochemical, spectroelectrochemical, electron paramagnetic resonance (EPR), and absorption spectroscopic studies combined with theoretical calculations. One exhibits a rich electrochemical behavior owing to the multiple redox-active centers. Interestingly, both the ligand BPTTF and the ruthenium compound 1 are EPR-active in the solid state owing to intramolecular charge-transfer processes. The results demonstrate that the TTF-annulated bis(phen) ligand is a promising bridging ligand to construct oligomeric or polymeric metal complexes with multiple redox-active centers. PMID:27070295

  18. Precise investigation of the axial ligand substitution mechanism on a hydrogenphosphato-bridged lantern-type platinum(III) binuclear complex in acidic aqueous solution.

    PubMed

    Iwatsuki, Satoshi; Mizushima, Chiho; Morimoto, Naoyuki; Muranaka, Shinji; Ishihara, Koji; Matsumoto, Kazuko

    2005-10-31

    Detailed equilibrium and kinetic studies on axial water ligand substitution reactions of the "lantern-type" platinum(III) binuclear complex, [Pt(2)(mu-HPO(4))(4)(H(2)O)(2)](2)(-), with halide and pseudo-halide ions (X(-) = Cl(-), Br(-), and SCN(-)) were carried out in acidic aqueous solution at 25 degrees C with I = 1.0 M. The diaqua Pt(III) dimer complex is in acid dissociation equilibrium in aqueous solution with -log K(h1) = 2.69 +/- 0.04. The consecutive formation constants of the aquahalo complex () and the dihalo complex () were determined spectrophotometrically to be log = 2.36 +/- 0.01 and log = 1.47 +/- 0.01 for the reaction with Cl(-) and log = 2.90 +/- 0.04 and log = 2.28 +/- 0.01 for the reaction with Br(-), respectively. In the kinetic measurements carried out under the pseudo-first-order conditions with a large excess concentration of halide ion compared to that of Pt(III) dimer (C(X)()- > C(Pt)), all of the reactions proceeded via a one-step first-order reaction, which is a contrast to the consecutive two-step reaction for the amidato-bridged platinum(III) binuclear complexes. The conditional first-order rate constant (k(obs)) depended on C(X)()- as well as the acidity of the solution. From kinetic analyses, the rate-limiting step was determined to be the first substitution process that forms the monohalo species, which is in rapid equilibrium with the dihalo complex. The reaction with 4-penten-1-ol was also kinetically investigated to examine the reactivity of the lantern complex with olefin compounds.

  19. Aggregation-induced emission enhancement in alkoxy-bridged binuclear rhenium(I) complexes: application as sensor for explosives and interaction with microheterogeneous media.

    PubMed

    Sathish, Veerasamy; Ramdass, Arumugam; Lu, Zong-Zhan; Velayudham, Murugesan; Thanasekaran, Pounraj; Lu, Kuang-Lieh; Rajagopal, Seenivasan

    2013-11-21

    The aggregation-induced emission enhancement (AIEE) characteristics of the two alkoxy-bridged binuclear Re(I) complexes [{Re(CO)3(1,4-NVP)}2(μ2-OR)2] (1, R = C4H9; 2, C10H21) bearing a long alkyl chain with 4-(1-naphthylvinyl)pyridine (1,4-NVP) ligand are illustrated. These complexes in CH2Cl2 (good solvent) are weakly luminescent, but their intensity increased enormously by almost 500 times by the addition of poor solvent (CH3CN) due to aggregation. By tracking this process via UV-vis absorption and emission spectral and TEM techniques, the enhanced emission is attributed to the formation of nanoaggregates. The nanoaggregate of complex 2 is used as a sensor for nitroaromatic compounds. Furthermore, the study of the photophysical properties of these binuclear Re(I) complexes in cationic, cetyltrimethylammonium bromide (CTAB), anionic, sodium dodecyl sulfate (SDS), and nonionic, p-tert-octylphenoxypolyoxyethanol (TritonX-100, TX-100), micelles as well as in CTAB-hexane-water and AOT-isooctane-water reverse micelles using steady-state and time-resolved spectroscopy and TEM analysis reveals that the nanoaggregates became small and compact size.

  20. 1,5-Diamido-9,10-anthraquinone, a Centrosymmetric Redox-Active Bridge with Two Coupled β-Ketiminato Chelate Functions: Symmetric and Asymmetric Diruthenium Complexes.

    PubMed

    Ansari, Mohd Asif; Mandal, Abhishek; Paretzki, Alexa; Beyer, Katharina; Fiedler, Jan; Kaim, Wolfgang; Lahiri, Goutam Kumar

    2016-06-01

    The dinuclear complexes {(μ-H2L)[Ru(bpy)2]2}(ClO4)2 ([3](ClO4)2), {(μ-H2L)[Ru(pap)2]2}(ClO4)2 ([4](ClO4)2), and the asymmetric [(bpy)2Ru(μ-H2L)Ru(pap)2](ClO4)2 ([5](ClO4)2) were synthesized via the mononuclear species [Ru(H3L)(bpy)2]ClO4 ([1]ClO4) and [Ru(H3L)(pap)2]ClO4 ([2]ClO4), where H4L is the centrosymmetric 1,5-diamino-9,10-anthraquinone, bpy is 2,2'-bipyridine, and pap is 2-phenylazopyridine. Electrochemistry of the structurally characterized [1]ClO4, [2]ClO4, [3](ClO4)2, [4](ClO4)2, and [5](ClO4)2 reveals multistep oxidation and reduction processes, which were analyzed by electron paramagnetic resonance (EPR) of paramagnetic intermediates and by UV-vis-NIR spectro-electrochemistry. With support by time-dependent density functional theory (DFT) calculations the redox processes could be assigned. Significant results include the dimetal/bridging ligand mixed spin distribution in 3(3+) versus largely bridge-centered spin in 4(3+)-a result of the presence of Ru(II)-stabilizig pap coligands. In addition to the metal/ligand alternative for electron transfer and spin location, the dinuclear systems allow for the observation of ligand/ligand and metal/metal site differentiation within the multistep redox series. DFT-supported EPR and NIR absorption spectroscopy of the latter case revealed class II mixed-valence behavior of the oxidized asymmetric system 5(3+) with about equal contributions from a radical bridge formulation. In comparison to the analogues with the deprotonated 1,4-diaminoanthraquinone isomer the centrosymmetric H2L(2-) bridge shows anodically shifted redox potentials and weaker electronic coupling between the chelate sites. PMID:27171539

  1. 1,5-Diamido-9,10-anthraquinone, a Centrosymmetric Redox-Active Bridge with Two Coupled β-Ketiminato Chelate Functions: Symmetric and Asymmetric Diruthenium Complexes.

    PubMed

    Ansari, Mohd Asif; Mandal, Abhishek; Paretzki, Alexa; Beyer, Katharina; Fiedler, Jan; Kaim, Wolfgang; Lahiri, Goutam Kumar

    2016-06-01

    The dinuclear complexes {(μ-H2L)[Ru(bpy)2]2}(ClO4)2 ([3](ClO4)2), {(μ-H2L)[Ru(pap)2]2}(ClO4)2 ([4](ClO4)2), and the asymmetric [(bpy)2Ru(μ-H2L)Ru(pap)2](ClO4)2 ([5](ClO4)2) were synthesized via the mononuclear species [Ru(H3L)(bpy)2]ClO4 ([1]ClO4) and [Ru(H3L)(pap)2]ClO4 ([2]ClO4), where H4L is the centrosymmetric 1,5-diamino-9,10-anthraquinone, bpy is 2,2'-bipyridine, and pap is 2-phenylazopyridine. Electrochemistry of the structurally characterized [1]ClO4, [2]ClO4, [3](ClO4)2, [4](ClO4)2, and [5](ClO4)2 reveals multistep oxidation and reduction processes, which were analyzed by electron paramagnetic resonance (EPR) of paramagnetic intermediates and by UV-vis-NIR spectro-electrochemistry. With support by time-dependent density functional theory (DFT) calculations the redox processes could be assigned. Significant results include the dimetal/bridging ligand mixed spin distribution in 3(3+) versus largely bridge-centered spin in 4(3+)-a result of the presence of Ru(II)-stabilizig pap coligands. In addition to the metal/ligand alternative for electron transfer and spin location, the dinuclear systems allow for the observation of ligand/ligand and metal/metal site differentiation within the multistep redox series. DFT-supported EPR and NIR absorption spectroscopy of the latter case revealed class II mixed-valence behavior of the oxidized asymmetric system 5(3+) with about equal contributions from a radical bridge formulation. In comparison to the analogues with the deprotonated 1,4-diaminoanthraquinone isomer the centrosymmetric H2L(2-) bridge shows anodically shifted redox potentials and weaker electronic coupling between the chelate sites.

  2. Dinuclear iridium and rhodium complexes with bridging arylimidazolide-N(3),C(2) ligands: synthetic, structural, reactivity, electrochemical and spectroscopic studies.

    PubMed

    He, Fan; Ruhlmann, Laurent; Gisselbrecht, Jean-Paul; Choua, Sylvie; Orio, Maylis; Wesolek, Marcel; Danopoulos, Andreas A; Braunstein, Pierre

    2015-10-21

    Deprotonation of 1-arylimidazoles (aryl = mesityl (Mes), 2,6-diisopropylphenyl (Dipp)), with n-butyl lithium afforded the corresponding derivatives (1-aryl-1H-imidazol-2-yl)lithium (1a, Ar = Mes; 1b, Ar = Dipp) in good yield. Reaction of 1a with 0.5 equiv. of [Ir(cod)(μ-Cl)]2 yielded two geometrical isomers of a doubly C2,N3-bridged dinuclear complex [Ir(cod){μ-C3H2N2(Mes)-κC2,κN3}]2 (3), 3H-H, a head-to-head (H-H) isomer of CS symmetry, and 3H-T, the thermodynamically preferred head-to-tail (H-T) isomer of C2 symmetry. The metallated carbon of the 4 electron donor anionic bridging ligands has some carbene character, reminiscent of the situation in N-metallated protic NHC complexes. Displacement of cod ligands from 3H-H and 3H-T afforded the tetracarbonyl complexes [Ir(CO)2{μ-C3H2N2(Mes)-κC2,κN3}]24H-H and 4H-T, respectively. The reaction with PMe3, which gave only one complex, [Ir(CO)(PMe3){μ-C3H2N2(Mes)-κC2,κN3}]2 (5), demonstrates that the isomerization of the central core Ir[μ-C3H2N2(Mes)-κC2,κN3]2Ir from H-H to H-T on going from 4H-H to 5 is readily triggered by phosphine substitution under mild conditions. Oxidative-addition of MeI to 5 afforded the formally metal-metal bonded d(7)-d(7) complex [Ir2(CO)2(PMe3)2(Me)I{μ-C3H2N2(Mes)-κC2,κN3}2] (6). The blue [Ir(C2H4)2{μ-C3H2N2(Mes)-κC2,κN3}]2 (7) and purple [Rh(C2H4)2{μ-C3H2N2(Dipp)-κC2,κN3}]2 (9) tetraethylene complexes were also obtained with only a H-T arrangement of the bridging ligands. Although only modestly efficient in alkane dehydrogenation, complex 7 was found to be a more active pre-catalyst than 3H-T, 4H-T and 5, probably because of the favorable lability of the ethylene ligands. From cyclic voltammetry, exhaustive coulometry and spectroelectrochemistry studies, it was concluded that 3H-T undergoes a metal-based one electron oxidation to generate the mixed-valent Ir(i)/Ir(ii) system. The energy of the intervalence band for the orange dirhodium complex [Rh(cod){μ-C3H2N2(Mes

  3. Synthesis, structural characterization and antimicrobial activities of diorganotin(IV) complexes with azo-imino carboxylic acid ligand: Crystal structure and topological study of a doubly phenoxide-bridged dimeric dimethyltin(IV) complex appended with free carboxylic acid groups

    NASA Astrophysics Data System (ADS)

    Roy, Manojit; Roy, Subhadip; Devi, N. Manglembi; Singh, Ch. Brajakishor; Singh, Keisham Surjit

    2016-09-01

    Diorganotin(IV) complexes appended with free carboxylic acids were synthesized by reacting diorganotin(IV) dichlorides [R2SnCl2; R = Me (1), Bu (2) and Ph (3)] with an azo-imino carboxylic acid ligand i.e. 2-{4-hydroxy-3-[(2-hydroxyphenylimino)methyl]phenylazo}benzoic acid in presence of triethylamine. The complexes were characterized by elemental analysis, IR and multinuclear NMR (1H, 13C and 119Sn) spectroscopy. The structure of 1 in solid state has been determined by X-ray crystallography. Crystal structure of 1 reveals that the compound crystallizes in monoclinic space group P21/c and is a dimeric dimethyltin(IV) complex appended with free carboxylic acid groups. In the structure of 1, the Sn(IV) atoms are hexacoordinated and have a distorted octahedral coordination geometry in which two phenoxy oxygen atoms and the azomethine nitrogen atom of the ligand coordinate to each tin atom. One of the phenoxy oxygen atom bridges the two tin centers resulting in a planar Sn2O2 core. Topological analysis is used for the description of molecular packing in 1. Tin NMR spectroscopy study indicates that the complexes have five coordinate geometry around tin atom in solution state. Since the complexes have free carboxylic acids, these compounds could be further used as potential metallo-ligands for the synthesis of other complexes. The synthesized diorganotin(IV) complexes were also screened for their antimicrobial activities and compound 2 showed effective antimicrobial activities.

  4. Dinuclear Zinc (II) Complexes of Macrocyclic Polyamine Ligands Containing an Imidazolium Bridge: Synthesis, Characterization, and Their Interaction with Plasmid DNA

    PubMed Central

    Huang, Jun; Huang, Qing-Dong; Zhang, Ji; Zhou, Li-Hong; Li, Qiang-Lin; Li, Kun; Jiang, Ning; Lin, Hong-Hui; Wu, Jiang; Yu, Xiao-Qi

    2007-01-01

    Two novel macrocyclic polyamine ligands and their dinuclear zinc (II) complexes were synthesized and characterized. Their interaction with plasmid DNA was studied by gel electrophoresis and fluorescence quenching experiment. The result showed that these complexes could bind DNA efficiently under physiological conditions.

  5. Nonlinear lattice relaxation of photogenerated charge-transfer excitation in halogen-bridged mixed-valence metal complexes. II. Polaron channel

    NASA Astrophysics Data System (ADS)

    Mishima, A.; Nasu, K.

    1989-03-01

    The one-dimensional extended Peierls-Hubbard model with half-filled-band electrons is studied in order to clarify the lattice relaxation path of the photogenerated charge-transfer excitation in halogen-bridged mixed-valence metal complexes. The ground and excited states are calculated within mean-field theory for electrons and the adiabatic approximation for phonons. It is concluded that the main origin of the photoinduced absorption is a distant pair of the hole-polaron and the electron-polaron. This distant pair is created not from the ground state of the self-trapped exciton (STE), but from the excited states of the STE through their autodissociation. This is consistent with the experiment on the excitation energy dependence of the photoinduced absorption yield.

  6. Probabilistic model-based methodology for the conformational study of cyclic systems: application to copper complexes double-bridged by phosphate and related ligands.

    PubMed

    Kessler, M; Pérez, J; Bueso, M C; García, L; Pérez, E; Serrano, J L; Carrascosa, R

    2007-12-01

    A methodology for the conformational study of cyclic systems through the statistical analysis of torsion angles is presented. It relies on a combination of different methods based on a probabilistic model which takes into account the topological symmetry of the structures. This methodology is applied to copper complexes double-bridged by phosphate and related ligands. Structures from the Cambridge Structural Database (CSD) are analyzed and the chair, boat-chair and boat conformations are identified as the most frequent conformations. The output of the methodology also provides information about distortions from the ideal conformations, the most frequent being: chair <--> twist-chair, chair <--> twist-boat-chair and boat <--> twist-boat. Molecular mechanics calculations identify these distortions as energetically accessible pathways.

  7. Chromatin folding and DNA replication inhibition mediated by a highly antitumor-active tetrazolato-bridged dinuclear platinum(II) complex

    PubMed Central

    Imai, Ryosuke; Komeda, Seiji; Shimura, Mari; Tamura, Sachiko; Matsuyama, Satoshi; Nishimura, Kohei; Rogge, Ryan; Matsunaga, Akihiro; Hiratani, Ichiro; Takata, Hideaki; Uemura, Masako; Iida, Yutaka; Yoshikawa, Yuko; Hansen, Jeffrey C.; Yamauchi, Kazuto; Kanemaki, Masato T.; Maeshima, Kazuhiro

    2016-01-01

    Chromatin DNA must be read out for various cellular functions, and copied for the next cell division. These processes are targets of many anticancer agents. Platinum-based drugs, such as cisplatin, have been used extensively in cancer chemotherapy. The drug–DNA interaction causes DNA crosslinks and subsequent cytotoxicity. Recently, it was reported that an azolato-bridged dinuclear platinum(II) complex, 5-H-Y, exhibits a different anticancer spectrum from cisplatin. Here, using an interdisciplinary approach, we reveal that the cytotoxic mechanism of 5-H-Y is distinct from that of cisplatin. 5-H-Y inhibits DNA replication and also RNA transcription, arresting cells in the S/G2 phase, and are effective against cisplatin-resistant cancer cells. Moreover, it causes much less DNA crosslinking than cisplatin, and induces chromatin folding. 5-H-Y will expand the clinical applications for the treatment of chemotherapy-insensitive cancers. PMID:27094881

  8. Hydroxide-bridged cubane complexes of nickel(II) and cadmium(II): magnetic, EPR, and unusual dynamic properties.

    PubMed

    Reger, Daniel L; Pascui, Andrea E; Pellechia, Perry J; Smith, Mark D; Jezierska, Julia; Ozarowski, Andrew

    2014-05-01

    The reactions of M(ClO4)2·xH2O (M = Ni(II) or Cd(II)) and m-bis[bis(1-pyrazolyl)methyl]benzene (Lm) in the presence of triethylamine lead to the formation of hydroxide-bridged cubane compounds of the formula [M4(μ3-OH)4(μ-Lm)2(solvent)4](ClO4)4, where solvent = dimethylformamide, water, acetone. In the solid state the metal centers are in an octahedral coordination environment, two sites are occupied by pyrazolyl nitrogens from Lm, three sites are occupied by bridging hydroxides, and one site contains a weakly coordinated solvent molecule. A series of multinuclear, two-dimensional and variable-temperature NMR experiments showed that the cadmium(II) compound in acetonitrile-d3 has C2 symmetry and undergoes an unusual dynamic process at higher temperatures (ΔGLm‡ = 15.8 ± 0.8 kcal/mol at 25 °C) that equilibrates the pyrazolyl rings, the hydroxide hydrogens, and cadmium(II) centers. The proposed mechanism for this process combines two motions in the semirigid Lm ligand termed the “Columbia Twist and Flip:” twisting of the pyrazolyl rings along the Cpz–Cmethine bond and 180° ring flip of the phenylene spacer along the CPh–Cmethine bond. This dynamic process was also followed using the spin saturation method, as was the exchange of the hydroxide hydrogens with the trace water present in acetonitrile-d3. The nickel(II) analogue, as shown by magnetic susceptibility and electron paramagnetic resonance measurements, has an S = 4 ground state, and the nickel(II) centers are ferromagnetically coupled with strongly nonaxial zero-field splitting parameters. Depending on the Ni–O–Ni angles two types of interactions are observed: J1 = 9.1 cm(–1) (97.9 to 99.5°) and J2 = 2.1 cm(–1) (from 100.3 to 101.5°). “Broken symmetry” density functional theory calculations performed on a model of the nickel(II) compound support these observations.

  9. Comparative Study of f-Element Electronic Structure across a Series of Multimetallic Actinide, Lanthanide-Actinide and Lanthanum-Actinide Complexes Possessing Redox-Active Bridging Ligands

    SciTech Connect

    Schelter, Eric J.; Wu, Ruilian; Veauthier, Jacqueline M.; Bauer, Eric D.; Booth, Corwin H.; Thomson, Robert K.; Graves, Christopher R.; John, Kevin D.; Scott, Brian L.; Thompson, Joe D.; Morris, David E.; Kiplinger, Jaqueline L.

    2010-02-24

    A comparative examination of the electronic interactions across a series of trimetallic actinide and mixed lanthanide-actinide and lanthanum-actinide complexes is presented. Using reduced, radical terpyridyl ligands as conduits in a bridging framework to promote intramolecular metal-metal communication, studies containing structural, electrochemical, and X-ray absorption spectroscopy are presented for (C{sub 5}Me{sub 5}){sub 2}An[-N=C(Bn)(tpy-M{l_brace}C{sub 5}Me4R{r_brace}{sub 2})]{sub 2} (where An = Th{sup IV}, U{sup IV}; Bn = CH{sub 2}C{sub 6}H{sub 5}; M = La{sup III}, Sm{sup III}, Yb{sup III}, U{sup III}; R = H, Me, Et) to reveal effects dependent on the identities of the metal ions and R-groups. The electrochemical results show differences in redox energetics at the peripheral 'M' site between complexes and significant wave splitting of the metal- and ligand-based processes indicating substantial electronic interactions between multiple redox sites across the actinide-containing bridge. Most striking is the appearance of strong electronic coupling for the trimetallic Yb{sup III}-U{sup IV}-Yb{sup III}, Sm{sup III}-U{sup IV}-Sm{sup III}, and La{sup III}-U{sup IV}-La{sup III} complexes, [8]{sup -}, [9b]{sup -} and [10b]{sup -}, respectively, whose calculated comproportionation constant K{sub c} is slightly larger than that reported for the benchmark Creutz-Taube ion. X-ray absorption studies for monometallic metallocene complexes of U{sup III}, U{sup IV}, and U{sup V} reveal small but detectable energy differences in the 'white-line' feature of the uranium L{sub III}-edges consistent with these variations in nominal oxidation state. The sum of this data provides evidence of 5f/6d-orbital participation in bonding and electronic delocalization in these multimetallic f-element complexes. An improved, high-yielding synthesis of 4{prime}-cyano-2,2{prime}:6{prime},2{double_prime}-terpyridine is also reported.

  10. Safer Bridges

    NASA Technical Reports Server (NTRS)

    1977-01-01

    Safer bridges are among a number of spinoff benefits from NASA procedures for testing 'cfracture toughness" of a structural part, meaning its ability to -siscracktsh at might cause failure. The New River Bridge in West Virginia, shown under construction, is the world's largest single span bridge. U.S. Steel fracture toughness requirements for such bridges include NASA-developed test procedures. Bridge materials and other metal structures may develop flaws during their service lifetimes. Such flaws can affect the structural integrity of the part. Thus, it is important to know the "fracture toughness" of a structural part, or its ability to resist cracks. NASA has long experience in developing fracture toughness tests for aerospace hardware. Since 1960, NASA-Lewis has worked closely with the American Society for Testing & Materials. Lewis and NASA-funded industrial contractors have made many important contributions to test procedures, now recommended by ASTM, for measuring fracture toughness.

  11. Multimolecular salivary mucin complex is altered in saliva of cigarette smokers: detection of disulfide bridges by Raman spectroscopy.

    PubMed

    Taniguchi, Motoe; Iizuka, Junko; Murata, Yukari; Ito, Yumi; Iwamiya, Mariko; Mori, Hiroshi; Hirata, Yukio; Mukai, Yoshiharu; Mikuni-Takagaki, Yuko

    2013-01-01

    Saliva contains mucins, which protect epithelial cells. We showed a smaller amount of salivary mucin, both MG1 and MG2, in the premenopausal female smokers than in their nonsmoking counterparts. Smokers' MG1, which contains almost 2% cysteine/half cystine in its amino acid residues, turned out to be chemically altered in the nonsmoker's saliva. The smaller acidic glycoprotein bands were detectable only in smoker's saliva in the range of 20-25 kDa and at 45 kDa, suggesting that degradation, at least in part, caused the reduction of MG1 mucin. This is in agreement with the previous finding that free radicals in cigarette smoke modify mucins in both sugar and protein moieties. Moreover, proteins such as amylase and albumin are bound to other proteins through disulfide bonds and are identifiable only after reduction with DTT. Confocal laser Raman microspectroscopy identified a disulfide stretch band of significantly stronger intensity per protein in the stimulated saliva of smokers alone. We conclude that the saliva of smokers, especially stimulated saliva, contains significantly more oxidized form of proteins with increased disulfide bridges, that reduces protection for oral epithelium. Raman microspectroscopy can be used for an easy detection of the damaged salivary proteins. PMID:23509686

  12. Cyanide bridged hetero-metallic polymeric complexes: Syntheses, vibrational spectra, thermal analyses and crystal structures of complexes [M(1,2-dmi)2Ni(μ-CN)4]n (M = Zn(II) and Cd(II))

    NASA Astrophysics Data System (ADS)

    Kürkçüoğlu, Güneş Süheyla; Sayın, Elvan; Şahin, Onur

    2015-12-01

    Two cyanide bridged hetero-metallic complexes of general formula, [M(1,2-dmi)2Ni(μ-CN)4]n (1,2-dmi = 1,2-dimethylimidazole and M = Zn(II) or Cd(II)) have been synthesized and characterized by vibrational (FT-IR and Raman) spectroscopy, single crystal X-ray diffraction, thermal analyses and elemental analyses. The crystallographic analyses reveal that the complexes, [Zn(1,2-dmi)2Ni(μ-CN)4] (1) and [Cd(1,2-dmi)2Ni(μ-CN)4] (2), have polymeric 2D networks. In the complexes, four cyanide groups of [Ni(CN)4]2- coordinated to the adjacent M(II) ions and distorted octahedral geometries of complexes are completed by two nitrogen atoms of trans 1,2-dmi ligands. The structures of 1 and 2 are similar and linked via intermolecular hydrogen bonding, C-H⋯Ni interactions to give rise to 3D networks. Vibration assignments are given for all the observed bands and the spectral features also supported to the crystal structures of heteronuclear complexes. The FT-IR and Raman spectra of the complexes are very much consistent with the structural data presented.

  13. Inclusion complexation behavior of dyestuff guest molecules by a bridged bis(cyclomaltoheptaose)[bis(beta-cyclodextrin)] with a pyromellitic acid diamide tether.

    PubMed

    Liu, Yu; Li, Li; Zhang, Heng-Yi; Liang, Peng; Wang, Hao

    2003-08-12

    A novel bridged bis(beta-cyclodextrin) with a pyromellitic acid 2,5-diamide tether (2) has been synthesized by reaction of 6(I)-(2-aminoethyleneamino)-6-deoxycyclomaltoheptaose [mono 6-(2-aminoethyleneamino)-6-deoxy-beta-cyclodextrin] with 1,2,4,5-benzenetetracarboxylic dianhydride. Its inclusion complexation behavior with some representative dyestuffs, i.e., Acridine Red (AR), Rhodamine B (RhB), Neutral Red (NR), Brilliant Green (BG), was studied by using UV-absorption, fluorescence, and 2D NMR spectroscopy. Fluorescence titrations have been performed at 25 degrees C in pH 7.2 buffer solution to calculate the binding constants of resulting complexes. These results obtained indicated that bis(beta-cyclodextrin) 2 exhibits the strongly enhanced binding ability with all dye molecules examined compared with natural cyclodextrins. The binding modes of 2 with dye molecules have been deduced by 2D NMR experiments to establish the correlations between molecular conformations and binding constants of inclusion complexation. It is found that the improved binding ability and molecular selectivity of 2 could be attributed to double-cavity cooperative inclusion interaction and the size/shape matching between the host and guest.

  14. Neutral-Type One-Dimensional Mixed-Valence Halogen-Bridged Platinum Chain Complexes with Large Charge-Transfer Band Gaps.

    PubMed

    Otake, Ken-ichi; Otsubo, Kazuya; Sugimoto, Kunihisa; Fujiwara, Akihiko; Kitagawa, Hiroshi

    2016-03-01

    One-dimensional (1D) electronic systems have attracted significant attention for a long time because of their various physical properties. Among 1D electronic systems, 1D halogen-bridged mixed-valence transition-metal complexes (the so-called MX chains) have been thoroughly studied owing to designable structures and electronic states. Here, we report the syntheses, structures, and electronic properties of three kinds of novel neutral MX-chain complexes. The crystal structures consist of 1D chains of Pt-X repeating units with (1R,2R)-(-)-diaminocychlohexane and CN(-) in-plane ligands. Because of the absence of a counteranion, the neutral MX chains have short interchain distances, so that strong interchain electronic interaction is expected. Resonance Raman spectra and diffuse-reflectance UV-vis spectra indicate that their electronic states are mixed-valence states (charge-density-wave state: Pt(2+)···X-Pt(4+)-X···Pt(2+)···X-Pt(4+)-X···). In addition, the relationship between the intervalence charge-transfer (IVCT) band gap and the degree of distortion of the 1D chain shows that the neutral MX chains have a larger IVCT band gap than that of cationic MX-chain complexes. These results provide new insight into the physical and electronic properties of 1D chain compounds. PMID:26901774

  15. Molecular and electronic structure of osmium complexes confined to Au(111) surfaces using a self-assembled molecular bridge

    SciTech Connect

    Llave, Ezequiel de la; Herrera, Santiago E.; Adam, Catherine; Méndez De Leo, Lucila P.; Calvo, Ernesto J.; Williams, Federico J.

    2015-11-14

    The molecular and electronic structure of Os(II) complexes covalently bonded to self-assembled monolayers (SAMs) on Au(111) surfaces was studied by means of polarization modulation infrared reflection absorption spectroscopy, photoelectron spectroscopies, scanning tunneling microscopy, scanning tunneling spectroscopy, and density functional theory calculations. Attachment of the Os complex to the SAM proceeds via an amide covalent bond with the SAM alkyl chain 40° tilted with respect to the surface normal and a total thickness of 26 Å. The highest occupied molecular orbital of the Os complex is mainly based on the Os(II) center located 2.2 eV below the Fermi edge and the LUMO molecular orbital is mainly based on the bipyridine ligands located 1.5 eV above the Fermi edge.

  16. Molecular and electronic structure of osmium complexes confined to Au(111) surfaces using a self-assembled molecular bridge.

    PubMed

    de la Llave, Ezequiel; Herrera, Santiago E; Adam, Catherine; Méndez De Leo, Lucila P; Calvo, Ernesto J; Williams, Federico J

    2015-11-14

    The molecular and electronic structure of Os(II) complexes covalently bonded to self-assembled monolayers (SAMs) on Au(111) surfaces was studied by means of polarization modulation infrared reflection absorption spectroscopy, photoelectron spectroscopies, scanning tunneling microscopy, scanning tunneling spectroscopy, and density functional theory calculations. Attachment of the Os complex to the SAM proceeds via an amide covalent bond with the SAM alkyl chain 40° tilted with respect to the surface normal and a total thickness of 26 Å. The highest occupied molecular orbital of the Os complex is mainly based on the Os(II) center located 2.2 eV below the Fermi edge and the LUMO molecular orbital is mainly based on the bipyridine ligands located 1.5 eV above the Fermi edge. PMID:26567676

  17. Molecular and electronic structure of osmium complexes confined to Au(111) surfaces using a self-assembled molecular bridge

    NASA Astrophysics Data System (ADS)

    de la Llave, Ezequiel; Herrera, Santiago E.; Adam, Catherine; Méndez De Leo, Lucila P.; Calvo, Ernesto J.; Williams, Federico J.

    2015-11-01

    The molecular and electronic structure of Os(II) complexes covalently bonded to self-assembled monolayers (SAMs) on Au(111) surfaces was studied by means of polarization modulation infrared reflection absorption spectroscopy, photoelectron spectroscopies, scanning tunneling microscopy, scanning tunneling spectroscopy, and density functional theory calculations. Attachment of the Os complex to the SAM proceeds via an amide covalent bond with the SAM alkyl chain 40° tilted with respect to the surface normal and a total thickness of 26 Å. The highest occupied molecular orbital of the Os complex is mainly based on the Os(II) center located 2.2 eV below the Fermi edge and the LUMO molecular orbital is mainly based on the bipyridine ligands located 1.5 eV above the Fermi edge.

  18. Electrochemical and photophysical properties of new triazole-bridged heterobimetallic ruthenium-rhodium and ruthenium-iridium complexes

    SciTech Connect

    Diemen, J.H. van; Hage, R.; Haasnoot, J.G.; Lempers, H.E.B.; Reedijk, J. ); Vos, J.G. ); Cola, L. de; Barigelletti, F.; Balzani, V. )

    1992-08-19

    The synthesis, characterization, and the electrochemical and photophysical properties of ((bpy){sub 2}Ru{sup II}(bpt)Rh{sup III}(ppy){sub 2}){sup 2+}, ((bpy){sub 2}Ru{sup II}(bpt)Ir{sup III}(ppy){sub 2}){sup 2+}, ((Rh{sup III}(ppy){sub 2}){sub 2}(bpt)){sup +}, and ((Ir{sup III}(ppy){sub 2}){sub 2}(bpt)){sup +} are reported (Hppy = 2-phenylpyridine; bpy = 2,2{prime}-bipyridine, Hbpt = 3,5-bis(pyridin-2-yl)-1,2,4-triazole). The Ru(bpy){sub 2} moiety is bound via N1 of the triazole ring, while the M(ppy){sub 2} center (M = Rh or Ir) is coordinated via the N4 of the triazole ring. The electrochemical measurements show that in the mixed-metal complexes the first oxidized metal is Ru and the first reduced ligand is bpy. The homobimetallic Ir and Rh complexes exhibit a bpt{sup {minus}}-based reduction. The absorption spectra of the mixed-metal complexes exhibit both Ru {yields} bpy and M {yields} ppy{sup {minus}} transitions. The energies of these transitions are different from those of their homobimetallic analogs. The emission observed for ((Rh(ppy){sub 2}){sub 2}-(bpt)){sup +} at 77 K corresponds to a ligand-centered excited state, while for the analogous iridium complex a charge-transfer emission, which involves the bpt{sup {minus}} ligand, is observed. In the mixed-metal complexes efficient energy transfer occurs from higher energy excited states centered on the M(ppy){sub 2} component to the lowest energy excited state, which is a metal-to-ligand charge transfer level localized on the Ru(bpy){sub 2} component.

  19. Rational design of azide-bridged bimetallic complexes. Crystal structure and magnetic properties of Fe(III)MFe(III) (M = Ni(II) and Cu(II)) trinuclear species.

    PubMed

    Colacio, Enrique; Costes, Jean-Pierre; Domínguez-Vera, José M; Maimoun, Ikram Ben; Suárez-Varela, José

    2005-01-28

    The first examples of azide-bridged bimetallic trinuclear complexes ([M(cyclam)][FeL(N3)(mu1,5-N3)]2) (H2L = 4,5-dichloro-1,2-bis(pyridine-2-carboxamido) benzene) have been structurally and magnetically characterized.

  20. Controlled synthesis of racemic indenyl rare-earth metal complexes via the cooperation between the intramolecular coordination of donor atoms and a bridge.

    PubMed

    Zhou, Shuangliu; Wu, Zhangshuan; Zhou, Lingmin; Wang, Shaowu; Zhang, Lijun; Zhu, Xiancui; Wei, Yun; Zhai, Jinhua; Wu, Jie

    2013-06-01

    The reactions of Me2Si(C9H6CH2CH2-DG)2 (DG = NMe2 (1), CH2NMe2 (2), OMe (3), and N(CH2CH2)2O (4)) with [(Me3Si)2N]3RE(μ-Cl)Li(THF)3 in toluene afforded a series of racemic divalent rare-earth metal complexes: {η(5):η(1):η(5):η(1)-Me2Si(C9H5CH2CH2-DG)2}RE (DG = NMe2, RE = Yb (6) and Eu (7); DG = CH2NMe2, RE = Yb (8), Eu (9), and Sm (10); DG = OMe, RE = Yb (11) and Eu (12); DG = N(CH2CH2)2O, RE = Yb (13) and Eu (14)). Similarly, the racemic divalent rare-earth metal complexes {η(5):η(1):η(5):η(1)-Me2Si(C9H5CH2CH2CH2NMe2)(C9H5CH2CH2OMe)}RE (RE = Yb (15) and Eu (16)) were also obtained. The reaction of Me2Si(C9H5CH2CH2OMe)2Li2 with NdCl3 gave a racemic dimeric neodymium chloride {η(5):η(1):η(5)-Me2Si(C9H5CH2CH2OMe)2NdCl}2 (17), whereas the reaction of Me2Si(C9H5CH2CH2NMe2)2Li2 with SmCl3 afforded a racemic dinuclear samarium chloride bridged by lithium chloride {η(5):η(1):η(5):η(1)-Me2Si(C9H5CH2CH2NMe2)2SmCl}2(μ-LiCl) (18). Further reaction of complex 18 with LiCH2SiMe3 provided an unexpected rare-earth metal alkyl complex {η(5):η(1):η(5):η(1):σ-Me2Si(C9H5CH2CH2NMe2)[(C9H5CH2CH2N(CH2)Me]}Sm (19) through the activation of an sp(3) C-H bond α-adjacent to the nitrogen atom. Complexes 19 and {η(5):η(1):η(5):η(1):σ-Me2Si(C9H5CH2CH2NMe2)[(C9H5CH2CH2N(CH2)Me]}Y (20) were also obtained by one-pot reactions of Me2Si(C9H5CH2CH2NMe2)2Li2 with RECl3 followed by treatment with LiCH2SiMe3. All compounds were fully characterized by spectroscopic methods and elemental analysis. Complexes 6-10 and 14-20 were further characterized by single-crystal X-ray diffraction analysis. All of the prepared rare-earth metal complexes were racemic, suggesting that racemic organo rare-earth metal complexes could be controllably synthesized by the cooperation between a bridge and the intramolecular coordination of donor atoms.

  1. Ground State Electronic and Magnetic Properties of a μ3-Oxo Bridged Trinuclear Cu(II) Complex: Correlation to the Native Intermediate of the Multicopper Oxidases

    PubMed Central

    Yoon, Jungjoo; Solomon, Edward I.

    2008-01-01

    The ground state electronic and magnetic properties of one of the possible structures of the trinuclear CuII site in the native intermediate (NI) of the multicopper oxidases, the μ3-oxo bridged structure, are evaluated using the C3-symmetric Cu3II complex, μ3O. μ3O is unique in that no ligand, other than the oxo, contributes to the exchange coupling. However, μ3O has a ferromagnetic ground state, inconsistent with that of NI. Therefore, two perturbations have been considered: protonation of the μ3-oxo ligand and relaxation of the μ3-oxo ligand into the Cu3 plane. Notably, when the oxo-ligand is sufficiently close to the Cu3 plane (< 0.3 Å), the ground state of μ3O becomes antiferromagnetic and can be correlated to that of NI. In addition, the ferromagnetic 4A ground state of μ3O is found from variable-temperature EPR to undergo a zero-field splitting (ZFS) of 2D = -5.0 cm-1, which derives from the second-order anisotropic exchange. This allows evaluation of the σ-to-π excited state exchange pathways and provides experimental evidence that the orbitally-degenerate 2E ground state of the antiferromagnetic μ3O would also undergo a ZFS by the first-order antisymmetric exchange that has the same physical origin as the anisotropic exchange. The important contribution of the μ3-oxo bridge to the ground-to-ground and ground-to-excited state superexchange pathways that are responsible for the isotropic, antisymmetric and anisotropic exchange are discussed. PMID:16241158

  2. X-ray characterization and magnetic properties of dioxygen-bridged Cu(II) and Mn(III) Schiff base complexes.

    PubMed

    Yahsi, Yasemin

    2016-07-01

    The coordination chemistry of multinuclear metal compounds is important because of their relevance to the multi-metal active sites of various metalloproteins and metalloenzymes. Multinuclear Cu(II) and Mn(III) compounds are of interest due to their various properties in the fields of coordination chemistry, inorganic biochemistry, catalysis, and optical and magnetic materials. Oxygen-bridged binuclear Mn(III) complexes generally exhibit antiferromagnetic interactions and a few examples of ferromagnetic interactions have also been reported. Binuclear Cu(II) complexes are important due to the fact that they provide examples of the simplest case of magnetic interaction involving only two unpaired electrons. Two novel dioxygen-bridged copper(II) and manganese(III) Schiff base complexes, namely bis(μ-4-bromo-2-{[(3-oxidopropyl)imino]methyl}phenolato)dicopper(II), [Cu2(C10H10BrNO2)2], (1), and bis(diaqua{4,4'-dichloro-2,2'-[(1,1-dimethylethane-1,2-diyl)bis(nitrilomethanylylidene)]diphenolato}manganese(III)) bis{μ-4,4'-dichloro-2,2'-[(1,1-dimethylethane-1,2-diyl)bis(nitrilomethanylylidene)]diphenolato}bis[aquamanganese(III)] tetrakis(perchlorate) ethanol disolvate, [Mn(C18H16Cl2N2O2)(H2O)2]2[Mn2(C18H16Cl2N2O2)2(H2O)2](ClO4)4·2C2H5OH, (2), have been synthesized and single-crystal X-ray diffraction has been used to analyze their crystal structures. The structure analyses of (1) and (2) show that each Cu(II) atom is four-coordinated, with long weak Cu...O interactions of 2.8631 (13) Å linking the dinuclear halves of the centrosymmetric tetranucelar molecules, while each Mn(III) atom is six-coordinated. The shortest intra- and intermolecular nonbonding Mn...Mn separations are 3.3277 (16) and 5.1763 (19) Å for (2), while the Cu...Cu separations are 3.0237 (3) and 3.4846 (3) Å for (1). The magnetic susceptibilities of (1) and (2) in the solid state were measured in the temperature range 2-300 K and reveal the presence of antiferromagnetic spin

  3. Investigating vibrational relaxation in cyanide-bridged transition metal mixed-valence complexes using two-dimensional infrared and infrared pump-probe spectroscopies

    PubMed Central

    Slenkamp, Karla M.; Lynch, Michael S.; Brookes, Jennifer F.; Bannan, Caitlin C.; Daifuku, Stephanie L.; Khalil, Munira

    2016-01-01

    Using polarization-selective two-dimensional infrared (2D IR) and infrared pump-probe spectroscopies, we study vibrational relaxation of the four cyanide stretching (νCN) vibrations found in [(NH3)5RuIIINCFeII(CN)5]− (FeRu) dissolved in D2O or formamide and [(NC)5FeIICNPtIV(NH3)4NCFeII(CN)5]4− (FePtFe) dissolved in D2O. These cyanide-bridged transition metal complexes serve as models for understanding the role high frequency vibrational modes play in metal-to-metal charge transfers over a bridging ligand. However, there is currently little information about vibrational relaxation and dephasing dynamics of the anharmonically coupled νCN modes in the electronic ground state of these complexes. IR pump-probe experiments reveal that the vibrational lifetimes of the νCN modes are ∼2 times faster when FeRu is dissolved in D2O versus formamide. They also reveal that the vibrational lifetimes of the νCN modes of FePtFe in D2O are almost four times as long as for FeRu in D2O. Combined with mode-specific relaxation dynamics measured from the 2D IR experiments, the IR pump-probe experiments also reveal that intramolecular vibrational relaxation is occurring in all three systems on ∼1 ps timescale. Center line slope dynamics, which have been shown to be a measure of the frequency-frequency correlation function, reveal that the radial, axial, and trans νCN modes exhibit a ∼3 ps timescale for frequency fluctuations. This timescale is attributed to the forming and breaking of hydrogen bonds between each mode and the solvent. The results presented here along with our previous work on FeRu and FePtFe reveal a picture of coupled anharmonic νCN modes where the spectral diffusion and vibrational relaxation dynamics depend on the spatial localization of the mode on the molecular complex and its specific interaction with the solvent. PMID:27158634

  4. Myocardial Bridge

    MedlinePlus

    ... artery. See also on this site: Ask a Texas Heart Institute Doctor: Search "myocardial bridge" Updated August ... comments. Terms of Use and Privacy Policy © Copyright Texas Heart Institute All rights reserved.

  5. Bridged bis(beta-cyclodextrin)s possessing coordinated metal center(s) and their inclusion complexation behavior with model substrates: enhanced molecular binding ability by multiple recognition.

    PubMed

    Liu, Y; Chen, Y; Li, L; Zhang, H Y; Liu, S X; Guan, X D

    2001-12-14

    To investigate quantitatively the cooperative binding ability of several beta-cyclodextrin oligomers bearing single or multiligated metal center(s), the inclusion complexation behavior of four bis(beta-cyclodextrin)s (2-5) linked by 2,2'-bipyridine-4,4'-dicarboxy tethers and their copper(II) complexes (6-9) with representative dye guests, i.e., methyl orange (MO), acridine red (AR), rhodamine B (RhB), ammonium 8-anilino-1-naphthalenesulfonic acid (ANS), and sodium 6-(p-toludino)-2-naphthalenesulfonate (TNS), have been examined in aqueous solution at 25 degrees C by means of UV-vis, circular dichroism, fluorescence, and 2D NMR spectroscopy. The results obtained indicate that bis(beta-cyclodextrin)s 2-5 can associate with one or three copper(II) ion(s) producing 2:1 or 2:3 bis(beta-cyclodextrin)-copper(II) complexes. These metal-ligated oligo(beta-cyclodextrin)s can bind two model substrates to form intramolecular 2:2 host-guest inclusion complexes and thus significantly enhance the original binding abilities of parent beta-cyclodextrin and bis(beta-cyclodextrin) toward model substrates through the cooperative binding of two guest molecules by four tethered cyclodextrin moieties, as well as the additional binding effect supplied by ligated metal center(s). Host 6 showed the highest enhancement of the stability constant, up to 38.3 times for ANS as compared with parent beta-cyclodextrin. The molecular binding mode and stability constant of substrates by bridged bis- and oligo(beta-cyclodextrin)s 2-9 are discussed from the viewpoint of the size/shape-fit interaction and molecular multiple recognition between host and guest.

  6. Electronic Structure and Magnetic Properties of Dioxo-Bridged Diuranium Complexes with Diamond-Core Structural Motifs: A Relativistic DFT Study.

    PubMed

    Teyar, Billel; Belkhiri, Lotfi; Costuas, Karine; Boucekkine, Abdou; Meyer, Karsten

    2016-03-21

    Electronic structures and magnetic properties of the binuclear bis(μ-oxo) U(IV)/U(IV) K2[{(((nP,Me)ArO)3tacn)U(IV)}2(μ-O)2] and U(V)/U(V) [{(((nP,Me)ArO)3tacn)U(V)}2(μ-O)2] (tacn = triazacyclononane, nP = neopentyl) complexes, exhibiting [U(μ-O)2U] diamond-core structural motifs, have been investigated computationally using scalar relativistic Density Functional Theory (DFT) combined with the Broken Symmetry (BS) approach for their magnetic properties. Using the B3LYP hybrid functional, the BS ground state of the pentavalent [U(V)(μ-O)2U(V)] 5f(1)-5f(1) complex has been found of lower energy than the high spin (HS) triplet state, thus confirming the antiferromagnetic character in agreement with experimental magnetic susceptibility measurements. The nonmagnetic character observed for the tetravalent K2[U(IV)(μ-O)2U(IV)] 5f(2)-5f(2) species is also predicted by our DFT calculations, which led practically to the same energy for the HS and BS states. As reported for related dioxo diuranium(V) systems, superexchange is likely to be responsible for the antiferromagnetic coupling through the π-network orbital pathway within the (μ-O)2 bridge, the dissymmetrical structure of the U2O2 core playing a determining role. In the case of the U(IV) species, our computations indicate that the K(+) counterions are likely to play a role for the observed magnetic property. Finally, the MO analysis, in conjunction with NPA and QTAIM analyses, clarify the electronic structures of the studied complexes. In particular, the fact that the experimentally attempted chemical oxidation of the U(V) species does not lead straightforwardly to binuclear complexes U(VI) is clarified by the MO analysis.

  7. Jointless bridges

    NASA Astrophysics Data System (ADS)

    Zuk, W.

    1981-06-01

    Various methods states are employing to reduce the number of joints in bridge decks are surveyed. The most common method is the use of integral abutments, where the superstructure is jointed to a flexible type of abutment. New methods of reducing the number of joints in a bridge are analyzed mathematically, and from the analysis conclusions are drawn as to the feasibility of these methods.

  8. Characterization and thermolysis reactions of CO{sub 2} bridged iron-tin and rhenium-tin complexes. Structure-reactivity correlations

    SciTech Connect

    Gibson, D.H.; Ye, M.; Sleadd, B.A.; Mehta, J.M.; Mbadike, O.P.; Richardson, J.F.; Mashuta, M.S.

    1995-03-01

    We report here our studies of the thermolysis behavior of iron-tin complexes and related rhenium-tin complexes and new structural data which allow further correlations to be made between thermolysis activity and bonding parameters involving the CO{sub 2} ligand. All compounds have been characterized by solid-state IR spectral methods which allow a determination of the {mu}{sub 2}-{eta}{sup 2} or {mu}{sub 2}-{eta}{sup 3} bonding mode in each compound when compared with structural data on representative compounds of each type. Factors which control the ease of thermolysis and the mode of decomposition are the bonding type, the presence of electron-donating or electron-withdrawing groups on the tin atom as well as those on iron or rhenium, metal-carbon bond strength, the orientation of the bridging CO{sub 2} ligand between the two metal centers, and, most importantly, the stability of the corresponding metal (iron or rhenium) anion. Reaction mechanisms are proposed which are consistent with structural and electronic differences that lead to separate thermolysis paths. 17 refs., 7 figs., 11 tabs.

  9. Butterfly Deformation Modes in a Photoexcited Pyrazolate-Bridged Pt Complex Measured by Time-Resolved X-Ray Scattering in Solution.

    PubMed

    Haldrup, Kristoffer; Dohn, Asmus O; Shelby, Megan L; Mara, Michael W; Stickrath, Andrew B; Harpham, Michael R; Huang, Jier; Zhang, Xiaoyi; Møller, Klaus B; Chakraborty, Arnab; Castellano, Felix N; Tiede, David M; Chen, Lin X

    2016-09-29

    Pyrazolate-bridged dinuclear Pt(II) complexes represent a series of molecules with tunable absorption and emission properties that can be directly modulated by structural factors, such as the Pt-Pt distance. However, direct experimental information regarding the structure of the emissive triplet excited state has remained scarce. Using time-resolved wide-angle X-ray scattering (WAXS), the excited triplet state molecular structure of [Pt(ppy)(μ-t-Bu2pz)]2 (ppy = 2-phenylpyridine; t-Bu2pz = 3,5-di-tert-butylpyrazolate), complex 1, was obtained in a dilute (0.5 mM) toluene solution utilizing the monochromatic X-ray pulses at Beamline 11IDD of the Advanced Photon Source. The excited-state structural analysis of 1 was performed based on the results from both transient WAXS measurements and density functional theory calculations to shed light on the primary structural changes in its triplet metal-metal-to-ligand charge-transfer (MMLCT) state, in particular, the Pt-Pt distance and ligand rotation. We found a pronounced Pt-Pt distance contraction accompanied by rotational motions of ppy ligands toward one another in the MMLCT state of 1. Our results suggest that the contraction is larger than what has previously been reported, but they are in good agreement with recent theoretical efforts and suggest the ppy moieties as targets for rational synthesis aimed at tuning the excited-state structure and properties. PMID:27569379

  10. Oxygen activation and intramolecular C-H bond activation by an amidate-bridged diiron(II) complex.

    PubMed

    Jones, Matthew B; Hardcastle, Kenneth I; Hagen, Karl S; MacBeth, Cora E

    2011-07-18

    A diiron(II) complex containing two μ-1,3-(κN:κO)-amidate linkages has been synthesized using the 2,2',2''-tris(isobutyrylamido)triphenylamine (H(3)L(iPr)) ligand. The resulting diiron complex, 1, reacts with dioxygen (or iodosylbenzene) to effect intramolecular C-H bond activation at the methine position of the ligand isopropyl group. The ligand-activated product, 2, has been isolated and characterized by a variety of methods including X-ray crystallography. Electrospray ionization mass spectroscopy of 2 prepared from(18)O(2) was used to confirm that the oxygen atom incorporated into the ligand framework is derived from molecular oxygen.

  11. Intramolecular Hgπ interactions of d-character with non-bridging atoms in mercury-aryl complexes.

    PubMed

    Lannes, A; Manceau, A; Rovezzi, M; Glatzel, P; Joly, Y; Gautier-Luneau, I

    2016-09-28

    Mercury 5d-orbitals are involved in intramolecular π-interactions with carbon and sulfur nearest and next-nearest neighbors in mercury-aryl complexes. This unexpected character of the electron cloud of mercury was revealed by high energy-resolution XANES spectroscopy readily interpreted in terms of a final-state local (l,m)-projected density of states (DOS). PMID:27541854

  12. Two ferromagnetic azido-bridged copper(ll) complexes studied by first-principle electronic-structure calculation.

    PubMed

    Zhang, Y S; Yao, K L; Liu, Z L

    2005-09-22

    The electronic structures of two ferromagnetic polynuclear copper(II) complexes, derived from end-to-end azido ligand and tridentate (NNN donor) Schiff base ligand, have been studied using the full-potential linearized augmented plane-wave method based on the density-functional theory. They are [Cu(L1)(micro-1,3-N3)]n(ClO4)n (1) and [Cu(L2)(micro-1,3-N3)]n(ClO4)n (2). The result shows that the spin populations in these two complexes are mainly distributed on the equatorial planes of a square pyramidal that surround the copper(II) ions. There are large and positive spin populations on copper(II) ions, small and positive spin populations on the three nitrogen atoms of tridentate Schiff base ligand, and the two terminal nitrogen atoms of asymmetrical end-to-end azido ligand, while weak and negative spin populations on the central nitrogen atoms of asymmetrical end-to-end azido ligand. Ferromagnetic coupling through the asymmetrical azido ligand in these two complexes has been mainly attributed to the spin delocalization, also with weak spin-polarization effect. PMID:16392483

  13. Two ferromagnetic azido-bridged copper(II) complexes studied by first-principle electronic-structure calculation

    NASA Astrophysics Data System (ADS)

    Zhang, Y. S.; Yao, K. L.; Liu, Z. L.

    2005-09-01

    The electronic structures of two ferromagnetic polynuclear copper(II) complexes, derived from end-to-end azido ligand and tridentate (NNN donor) Schiff base ligand, have been studied using the full-potential linearized augmented plane-wave method based on the density-functional theory. They are [Cu(L1)(μ-1,3-N3)]n(ClO4)n (1) and [Cu(L2)(μ-1,3-N3)]n(ClO4)n (2). The result shows that the spin populations in these two complexes are mainly distributed on the equatorial planes of a square pyramidal that surround the copper(II) ions. There are large and positive spin populations on copper(II) ions, small and positive spin populations on the three nitrogen atoms of tridentate Schiff base ligand, and the two terminal nitrogen atoms of asymmetrical end-to-end azido ligand, while weak and negative spin populations on the central nitrogen atoms of asymmetrical end-to-end azido ligand. Ferromagnetic coupling through the asymmetrical azido ligand in these two complexes has been mainly attributed to the spin delocalization, also with weak spin-polarization effect.

  14. Preparation of Different Substitued Polypyridine Ligands, Ruthenium(II)-Bridged Complexes and Spectoscopıc Studies.

    PubMed

    Obali, Aslihan Yilmaz; Ucan, Halil Ismet

    2016-09-01

    Novel different substitued polypyridine ligands 4-((4-(1H-imidazo[4,5-f][1,10]phenanthroline-2-yl)phenoxy)methyl)benzaldehyde (BA-PPY), (E)-N-(4-((4-(1H-imidazo[4,5-f][1,10]phenanthroline-2-yl)phenoxy)methyl)benzylidene)-pyrene-4-amine (PR-PPY), (E)-N-(4-((4-(1H-imidazo[4,5-f][1,10] phenanthroline-2-yl)phenoxy)methyl)benzylidene)-1,10-phenanthroline-5amine (FN-PPY), 2-(4-(bromomethyl)phenyl)-1H-imidazo[4,5-f][1,10] phenanthroline (BR-PPY), 2-(4-(azidomethyl)phenyl)-1H-imidazo[4,5-f][1,10]phenanthroline (N3-PPY) and triazole containing polypyridine ligand 3,4-bis[(4-(metoxy)-1,2,3-triazole)1-methylphenyl)-1H-imidazo[4,5-f][1,10]phenanthroline)] benzaldehyde (BA-DIPPY) and Ruthenium(II) complexes were synthesized and characterized. Their photopysical properties were investigated. The complexes RuP(PR-PPY), RuB(PR-PPY, RuP(FN-PPY) and RuB(FN-PPY) exhibited a broad absorption bands at 485, 475, 476, and 453 nm, respectively, assignable to the spin-allowed MLCT (dπ-π*) transition. The emission maxima of the pyrene-appended polypyridine ligand PR-PPY was observed at λems = 616 nm and the phenanthroline-appended polypyridine ligand FN-PPY was observed at λems = 668 nm. And the emission maxima of the complexes RuP(PR-PPY), RuB(PR-PPY), RuP(FN-PPY) and RuB(FN-PPY) were observed at λems = 646, 646, 685 and 685 nm, respectively. As seen in fluorescence spectra, the fluorescence intensities of the ligands are higher than their metal complexes. This is because of quenching effect of Ruthenium(II) metal on chromophore groups. PMID:27351670

  15. Heteropentanuclear Oxalato-Bridged nd–4f (n=4, 5) Metal Complexes with NO Ligand: Synthesis, Crystal Structures, Aqueous Stability and Antiproliferative Activity

    PubMed Central

    Kuhn, Paul-Steffen; Cremer, Laura; Gavriluta, Anatolie; Jovanović, Katarina K; Filipović, Lana; Hummer, Alfred A; Büchel, Gabriel E; Dojčinović, Biljana P; Meier, Samuel M; Rompel, Annette; Radulović, Siniša; Tommasino, Jean Bernard; Luneau, Dominique; Arion, Vladimir B

    2015-01-01

    A series of heteropentanuclear oxalate-bridged Ru(NO)-Ln (4d–4f) metal complexes of the general formula (nBu4N)5[Ln{RuCl3(μ-ox)(NO)}4], where Ln=Y (2), Gd (3), Tb (4), Dy (5) and ox=oxalate anion, were obtained by treatment of (nBu4N)2[RuCl3(ox)(NO)] (1) with the respective lanthanide salt in 4:1 molar ratio. The compounds were characterized by elemental analysis, IR spectroscopy, electrospray ionization (ESI) mass spectrometry, while 1, 2, and 5 were in addition analyzed by X-ray crystallography, 1 by Ru K-edge XAS and 1 and 2 by 13C NMR spectroscopy. X-ray diffraction showed that in 2 and 5 four complex anions [RuCl3(ox)(NO)]2− are coordinated to YIII and DyIII, respectively, with formation of [Ln{RuCl3(μ-ox)(NO)}4]5− (Ln=Y, Dy). While YIII is eight-coordinate in 2, DyIII is nine-coordinate in 5, with an additional coordination of an EtOH molecule. The negative charge is counterbalanced by five nBu4N+ ions present in the crystal structure. The stability of complexes 2 and 5 in aqueous medium was monitored by UV/Vis spectroscopy. The antiproliferative activity of ruthenium-lanthanide complexes 2–5 were assayed in two human cancer cell lines (HeLa and A549) and in a noncancerous cell line (MRC-5) and compared with those obtained for the previously reported Os(NO)-Ln (5d–4f) analogues (nBu4N)5[Ln{OsCl3(ox)(NO)}4] (Ln=Y (6), Gd (7), Tb (8), Dy (9)). Complexes 2–5 were found to be slightly more active than 1 in inhibiting the proliferation of HeLa and A549 cells, and significantly more cytotoxic than 5d–4f metal complexes 6–9 in terms of IC50 values. The highest antiproliferative activity with IC50 values of 20.0 and 22.4 μM was found for 4 in HeLa and A549 cell lines, respectively. These cytotoxicity results are in accord with the presented ICP-MS data, indicating five- to eightfold greater accumulation of ruthenium versus osmium in human A549 cancer cells. PMID:26260662

  16. Heteropentanuclear Oxalato-Bridged nd-4f (n=4, 5) Metal Complexes with NO Ligand: Synthesis, Crystal Structures, Aqueous Stability and Antiproliferative Activity.

    PubMed

    Kuhn, Paul-Steffen; Cremer, Laura; Gavriluta, Anatolie; Jovanović, Katarina K; Filipović, Lana; Hummer, Alfred A; Büchel, Gabriel E; Dojčinović, Biljana P; Meier, Samuel M; Rompel, Annette; Radulović, Siniša; Tommasino, Jean Bernard; Luneau, Dominique; Arion, Vladimir B

    2015-09-21

    A series of heteropentanuclear oxalate-bridged Ru(NO)-Ln (4d-4f) metal complexes of the general formula (nBu4N)5[Ln{RuCl3(μ-ox)(NO)}4], where Ln=Y (2), Gd (3), Tb (4), Dy (5) and ox=oxalate anion, were obtained by treatment of (nBu4N)2[RuCl3(ox)(NO)] (1) with the respective lanthanide salt in 4:1 molar ratio. The compounds were characterized by elemental analysis, IR spectroscopy, electrospray ionization (ESI) mass spectrometry, while 1, 2, and 5 were in addition analyzed by X-ray crystallography, 1 by Ru K-edge XAS and 1 and 2 by (13)C NMR spectroscopy. X-ray diffraction showed that in 2 and 5 four complex anions [RuCl3(ox)(NO)](2-) are coordinated to Y(III) and Dy(III), respectively, with formation of [Ln{RuCl3(μ-ox)(NO)}4](5-) (Ln=Y, Dy). While Y(III) is eight-coordinate in 2, Dy(III) is nine-coordinate in 5, with an additional coordination of an EtOH molecule. The negative charge is counterbalanced by five nBu4N(+) ions present in the crystal structure. The stability of complexes 2 and 5 in aqueous medium was monitored by UV/Vis spectroscopy. The antiproliferative activity of ruthenium-lanthanide complexes 2-5 were assayed in two human cancer cell lines (HeLa and A549) and in a noncancerous cell line (MRC-5) and compared with those obtained for the previously reported Os(NO)-Ln (5d-4f) analogues (nBu4N)5[Ln{OsCl3(ox)(NO)}4] (Ln=Y (6), Gd (7), Tb (8), Dy (9)). Complexes 2-5 were found to be slightly more active than 1 in inhibiting the proliferation of HeLa and A549 cells, and significantly more cytotoxic than 5d-4f metal complexes 6-9 in terms of IC50 values. The highest antiproliferative activity with IC50 values of 20.0 and 22.4 μM was found for 4 in HeLa and A549 cell lines, respectively. These cytotoxicity results are in accord with the presented ICP-MS data, indicating five- to eightfold greater accumulation of ruthenium versus osmium in human A549 cancer cells.

  17. Heteropentanuclear Oxalato-Bridged nd-4f (n=4, 5) Metal Complexes with NO Ligand: Synthesis, Crystal Structures, Aqueous Stability and Antiproliferative Activity.

    PubMed

    Kuhn, Paul-Steffen; Cremer, Laura; Gavriluta, Anatolie; Jovanović, Katarina K; Filipović, Lana; Hummer, Alfred A; Büchel, Gabriel E; Dojčinović, Biljana P; Meier, Samuel M; Rompel, Annette; Radulović, Siniša; Tommasino, Jean Bernard; Luneau, Dominique; Arion, Vladimir B

    2015-09-21

    A series of heteropentanuclear oxalate-bridged Ru(NO)-Ln (4d-4f) metal complexes of the general formula (nBu4N)5[Ln{RuCl3(μ-ox)(NO)}4], where Ln=Y (2), Gd (3), Tb (4), Dy (5) and ox=oxalate anion, were obtained by treatment of (nBu4N)2[RuCl3(ox)(NO)] (1) with the respective lanthanide salt in 4:1 molar ratio. The compounds were characterized by elemental analysis, IR spectroscopy, electrospray ionization (ESI) mass spectrometry, while 1, 2, and 5 were in addition analyzed by X-ray crystallography, 1 by Ru K-edge XAS and 1 and 2 by (13)C NMR spectroscopy. X-ray diffraction showed that in 2 and 5 four complex anions [RuCl3(ox)(NO)](2-) are coordinated to Y(III) and Dy(III), respectively, with formation of [Ln{RuCl3(μ-ox)(NO)}4](5-) (Ln=Y, Dy). While Y(III) is eight-coordinate in 2, Dy(III) is nine-coordinate in 5, with an additional coordination of an EtOH molecule. The negative charge is counterbalanced by five nBu4N(+) ions present in the crystal structure. The stability of complexes 2 and 5 in aqueous medium was monitored by UV/Vis spectroscopy. The antiproliferative activity of ruthenium-lanthanide complexes 2-5 were assayed in two human cancer cell lines (HeLa and A549) and in a noncancerous cell line (MRC-5) and compared with those obtained for the previously reported Os(NO)-Ln (5d-4f) analogues (nBu4N)5[Ln{OsCl3(ox)(NO)}4] (Ln=Y (6), Gd (7), Tb (8), Dy (9)). Complexes 2-5 were found to be slightly more active than 1 in inhibiting the proliferation of HeLa and A549 cells, and significantly more cytotoxic than 5d-4f metal complexes 6-9 in terms of IC50 values. The highest antiproliferative activity with IC50 values of 20.0 and 22.4 μM was found for 4 in HeLa and A549 cell lines, respectively. These cytotoxicity results are in accord with the presented ICP-MS data, indicating five- to eightfold greater accumulation of ruthenium versus osmium in human A549 cancer cells. PMID:26260662

  18. Photocatalytic Hydroxylation of Benzene by Dioxygen to Phenol with a Cyano-Bridged Complex Containing Fe(II) and Ru(II) Incorporated in Mesoporous Silica-Alumina.

    PubMed

    Aratani, Yusuke; Oyama, Kohei; Suenobu, Tomoyoshi; Yamada, Yusuke; Fukuzumi, Shunichi

    2016-06-20

    Photocatalytic hydroxylation of benzene to phenol was achieved by using O2 as an oxidant as well as an oxygen source with a cyano-bridged polynuclear metal complex containing Fe(II) and Ru(II) incorporated in mesoporous silica-alumina ([Fe(H2O)3]2[Ru(CN)6]@sAl-MCM-41). An apparent turnover number (TON) of phenol production per the monomer unit of [Fe(H2O)3]2[Ru(CN)6] was 41 for 59 h. The cyano-bridged polynuclear metal complex, [Fe(H2O)3]2[Ru(CN)6], exhibited catalytic activity for thermal hydroxylation of benzene by H2O2 in acetonitrile (MeCN), where the apparent TON of phenol production reached 393 for 60 h. The apparent TON increased to 2500 for 114 h by incorporating [Fe(H2O)3]2[Ru(CN)6] in sAl-MCM-41. Additionally, [Fe(H2O)3]2[Ru(CN)6] acts as a water oxidation catalyst by using [Ru(bpy)3](2+) (bpy = 2,2'-bipyridine) and Na2S2O8 as a photosensitizer and a sacrificial electron acceptor as evidenced by (18)O-isotope labeling experiments. Photoirradiation of an O2-saturated MeCN solution containing [Fe(H2O)3]2[Ru(CN)6]@sAl-MCM-41 and scandium ion provided H2O2 formation, where photoexcited [Ru(CN)6](4-) moiety reduces O2 as indicated by laser flash photolysis measurements. Thus, hydroxylation of benzene to phenol using molecular oxygen photocatalyzed by [Fe(H2O)3]2[Ru(CN)6] occurred via a two-step route; (1) molecular oxygen was photocatalytically reduced to peroxide by using water as an electron donor, and then (2) peroxide thus formed is used as an oxidant for hydroxylation of benzene. PMID:27265780

  19. Synthesis, crystal structures, and luminescent properties of phenoxo-bridged heterometallic trinuclear propeller- and sandwich-like Schiff-base complexes.

    PubMed

    Wang, Hailong; Zhang, Daopeng; Ni, Zhong-Hai; Li, Xiyou; Tian, Laijin; Jiang, Jianzhuang

    2009-07-01

    A series of phenoxo-bridged heterometallic Schiff-base trinuclear complexes Zn-M-Zn [M = Cd(II), Pb(II), Nd(III), Eu(III), Gd(III), Tb(III), and Dy(III)] have been synthesized by a rational structural design based on two symmetrical Schiff-base ligands N,N'-bis(3-methoxysalicylidene)propylene-1,3-diamine (H(2)L(a)) and N,N'-bis(3-methoxysalicylidene)benzene-1,2-diamine (H(2)L(b)). Single X-ray diffraction analysis reveals a similar molecular structure among the eight propeller-like and seven sandwich-type phenoxo-bridged Zn-M-Zn complexes. In the compounds Cd[Zn(L(a))Cl](2) (1), {Cd[Zn(L(b))Cl](2)}.H(2)O (2), {Pb[Zn(L(b))Cl](2)}.2H(2)O (4), {Nd[Zn(L(a))Cl](2)(H(2)O)}.0.5ZnCl(4) .2H(2)O (5), and{M(III)[Zn(L(a))Cl](2)(H(2)O)}.0.5ZnCl(4).2MeOH [M = Eu(7), Gd (9), Tb (11), and Dy (13)], two [Zn(L)Cl](-) units coordinate to the central metal ion as a tetradentate ligand using its four oxygen atoms, forming a two-blade propeller-like left-handed and right-handed chiral Zn-M-Zn configuration despite the racemic nature of the whole complexes. Compounds {Pb[Zn(L(a))Cl](2)}.MeOH (3), {Nd[Zn(L(b))Cl](2)(DMF)(OAc)}.CH(3)CN (6), {Eu[Zn(L(b))Cl](2)(DMF)(OAc)}.CH(3)CN (8), {Gd[Zn(L(b))Cl](2)(DMF)(2)}.Cl.2H(2)O (10), {Tb[Zn(L(b))Cl](2)(DMF)(2)}.Cl.2H(2)O (12), {Dy[Zn(L(b))Cl](2)(DMF)(2)}.Cl.2H(2)O (14), and {Pb[Zn(L(b))Cl](2)}.2H(2)O (15) exhibit a relatively rare sandwich-type structure with a central metal ion clamped by two [Zn(L)Cl](-) units. Photophysical studies indicate that all of the complexes exhibit luminescence both in solution and in solid sate, and there exists an energy transfer from the [Zn(L)Cl](-) unit to the central rare earth ions of Nd(III) (5 and 6), Tb(III) (11), and Dy(III) (for 13). In particular, systematic and comparative investigation of the photophysical properties of these trinuclear complexes reveals that the luminescence properties could easily be tuned by changing the central metal or the Schiff-base ligand.

  20. Synthesis, crystal structure, spectroscopy and magnetic properties of a dinuclear Cu II complex with 3,5-bis(2-pyridyl)pyrazole bridging ligand

    NASA Astrophysics Data System (ADS)

    Du, Miao; Chen, Shen-Tan; Guo, Ya-Mei; Bu, Xian-He; Ribas, Joan

    2005-02-01

    A dinuclear Cu II complex [Cu 2(bpp) 2(H 2O) 2](ClO 4) 2 ( 1) with 3,5-bis(2-pyridyl)pyrazole (Hbpp), has been synthesized and characterized by elemental analyses, thermal analysis, conductance, UV-vis and IR spectra. The crystal structure of 1, determined by X-ray diffraction technique, reveals that two centrosymmetric Cu II centers are bridged by a pair of tetradentate anionic bpp ligands, adopting a square-pyramidal environment with the water ligand occupying the axial site. An interesting feature of this structure is the formation of a two-dimensional supramolecular network through O-H⋯O hydrogen bonds between the water moieties of the cationic [Cu 2(bpp) 2(H 2O) 2] 2+ subunits and perchlorate anions. The magnetic properties of 1 have been investigated by variable-temperature magnetic susceptibility and EPR measurements. Very strong antiferromagnetic interaction between the Cu II centers (with H=- JS1S2, J=-368.3 cm -1) has been observed, and the magneto-structural correlations was analyzed.

  1. β-Cyclodextrin-Based Inclusion Complexation Bridged Biodegradable Self-Assembly Macromolecular Micelle for the Delivery of Paclitaxel.

    PubMed

    Chen, Yanzuo; Huang, Yukun; Qin, Dongdong; Liu, Wenchao; Song, Chao; Lou, Kaiyan; Wang, Wei; Gao, Feng

    2016-01-01

    In this study, a novel adamantanamine-paclitaxel (AD-PTX) incorporated oligochitosan- carboxymethyl-β-cyclodextrin (CSO-g-CM-β-CD) self-assembly macromolecular (CSO-g-CM-β-CD@AD-PTX) micelle was successfully prepared in water through sonication. The formed molecules were characterized by Fourier transform infrared spectroscopy, proton nuclear magnetic resonance (NMR) spectroscopy, two-dimensional NMR, elemental analysis, and liquid chromatography-mass spectrometry, while the correspondent micelles were characterized by dynamic light scattering and transmission electron microscopy. We showed that the macromolecular micelle contained a spherical core-shell structure with a diameter of 197.1 ± 3.3 nm and zeta potential of -19.1 ± 4.3 mV. The CSO-g-CM-β-CD@AD-PTX micelle exhibited a high drug-loading efficacy up to 31.3%, as well as a critical micelle concentration of 3.4 × 10-7 M, which indicated good stability. Additionally, the in vitro release profile of the CSO-g-CM-β-CD@AD-PTX micelle demonstrated a long-term release pattern, 63.1% of AD-PTX was released from the micelle during a 30-day period. Moreover, the CSO-g-CM-β-CD@AD-PTX micelle displayed cytotoxicity at a sub-μM scale similar to PTX in U87 MG cells, and CSO-g-CM-β-CD exhibited a good safety profile by not manifesting significant toxicity at concentrations up to 100 μM. These results indicated that β-CD-based inclusion complexation resulting in biodegradable self-assembled macromolecular micelles can be utilized as nanocarrier, and may provide a promising platform for drug delivery in the future medical applications. PMID:26964047

  2. β-Cyclodextrin-Based Inclusion Complexation Bridged Biodegradable Self-Assembly Macromolecular Micelle for the Delivery of Paclitaxel

    PubMed Central

    Chen, Yanzuo; Huang, Yukun; Qin, Dongdong; Liu, Wenchao; Song, Chao; Lou, Kaiyan; Wang, Wei; Gao, Feng

    2016-01-01

    In this study, a novel adamantanamine-paclitaxel (AD-PTX) incorporated oligochitosan- carboxymethyl-β-cyclodextrin (CSO-g-CM-β-CD) self-assembly macromolecular (CSO-g-CM-β-CD@AD-PTX) micelle was successfully prepared in water through sonication. The formed molecules were characterized by Fourier transform infrared spectroscopy, proton nuclear magnetic resonance (NMR) spectroscopy, two-dimensional NMR, elemental analysis, and liquid chromatography-mass spectrometry, while the correspondent micelles were characterized by dynamic light scattering and transmission electron microscopy. We showed that the macromolecular micelle contained a spherical core-shell structure with a diameter of 197.1 ± 3.3 nm and zeta potential of −19.1 ± 4.3 mV. The CSO-g-CM-β-CD@AD-PTX micelle exhibited a high drug-loading efficacy up to 31.3%, as well as a critical micelle concentration of 3.4 × 10-7 M, which indicated good stability. Additionally, the in vitro release profile of the CSO-g-CM-β-CD@AD-PTX micelle demonstrated a long-term release pattern, 63.1% of AD-PTX was released from the micelle during a 30-day period. Moreover, the CSO-g-CM-β-CD@AD-PTX micelle displayed cytotoxicity at a sub-μM scale similar to PTX in U87 MG cells, and CSO-g-CM-β-CD exhibited a good safety profile by not manifesting significant toxicity at concentrations up to 100 μM. These results indicated that β-CD-based inclusion complexation resulting in biodegradable self-assembled macromolecular micelles can be utilized as nanocarrier, and may provide a promising platform for drug delivery in the future medical applications. PMID:26964047

  3. End-to-End Thiocyanato-Bridged Helical Chain Polymer and Dichlorido-Bridged Copper(II) Complexes with a Hydrazone Ligand: Synthesis, Characterisation by Electron Paramagnetic Resonance and Variable-Temperature Magnetic Studies, and Inhibitory Effects on Human Colorectal Carcinoma Cells.

    PubMed

    Das, Kuheli; Datta, Amitabha; Sinha, Chittaranjan; Huang, Jui-Hsien; Garribba, Eugenio; Hsiao, Ching-Sheng; Hsu, Chin-Lin

    2012-04-01

    The reactions of the tridentate hydrazone ligand, N'-[1-(pyridin-2-yl)ethylidene]acetohydrazide (HL), obtained by condensation of 2-acetylpyridine with acetic hyadrazide, with copper nitrate trihydrate in the presence of thiocyanate, or with CuCl2 produce two distinct coordination compounds, namely a one-dimensional helical coordination chain of [CuL(NCS)] n (1) units, and a doubly chlorido-bridged dinuclear complex [Cu2L2Cl2] (2) (where L=CH3C(O)=N-N=CCH3C5H4N). Single-crystal X-ray structural determination studies reveal that in complex 1, a deprotonated hydrazone ligand L(-) coordinates a copper(II) ion that is bridged to two neighbouring metal centres by SCN(-) anions, generating a one-dimensional helical coordination chain. In complex 2, two symmetry-related, adjacent copper(II) coordination entities are doubly chlorido-bridged, producing a dicopper entity with a Cu⋅⋅⋅Cu distance of 3.402 (1) Å. The two coordination compounds have been fully characterised by elemental analysis, spectroscopic techniques including IR, UV-vis and electron paramagnetic resonance, and variable-temperature magnetic studies. The biological effects of 1 and 2 on the viability of human colorectal carcinoma cells (COLO-205 and HT-29) were evaluated using an MTT assay, and the results indicate that these complexes induce a decrease in cell-population growth of human colorectal carcinoma cells with apoptosis.

  4. Dose-effect relationships of nucleoplasmic bridges and complex nuclear anomalies in human peripheral lymphocytes exposed to 60Co γ-rays at a relatively low dose.

    PubMed

    Tian, Xue-Lei; Zhao, Hua; Cai, Tian-Jing; Lu, Xue; Chen, De-Qing; Li, Shuang; Liu, Qing-Jie

    2016-07-01

    The dose effect between nucleoplasmic bridges (NPB) and relatively low doses of ionising radiation remains unknown. Accordingly, this study investigated the NPB frequencies in human peripheral blood lymphocytes exposed to low-dose (60)Co γ-rays. Complex anomalies, including fused nuclei (FUS), horse-shoe nuclei (HS) and circular nuclei (CIR), which possibly originated from multiple NPBs, were also scored. Human peripheral blood samples were collected from three healthy males and irradiated with 0-1 and 0-0.4 Gy (60)Co γ-rays. A cytokinesis-block micronucleus cytome assay was then conducted to analyse NPB, PFHC (NPB plus three complex nuclear anomalies) and micronucleus (MN) in binucleated cells. All dose-response curves followed the linear model for both NPB frequency and PFHC cell frequency. The dose-response curves between NPB frequency and absorbed dose at 0-1 and 0-0.4 Gy were y = 0.0037x + 0.0005 (R (2) = 0.979, P < 0.05) and y = 0.0043x + 0.0004 (R (2) = 0.941, P < 0.05), respectively. The dose-response curves between PFHC cell frequency and absorbed dose at 0-1 and 0-0.4 Gy were y = 0.0044x + 0.0007 (R (2) = 0.982, P < 0.05) and y = 0.0059x + 0.0005 (R (2) = 0.969, P < 0.05), respectively. The statistical significance of differences between the irradiated groups (0-0.4 Gy) and background levels of NPB, PFHC and MN were also analysed. The lowest analysable doses of NPB, PFHC and MN were 0.12, 0.08 and 0.08 Gy, respectively. In conclusion, NPBs and PFHC positively correlated with the absorbed radiation at a relatively low dose.

  5. Cyanide-bridged Fe(III)-Mn(III) bimetallic complexes with dimeric and chain structures constructed from a newly made mer-Fe tricyanide: structures and magnetic properties.

    PubMed

    Kim, Jae Il; Kwak, Hyun Young; Yoon, Jung Hee; Ryu, Dae Won; Yoo, In Young; Yang, Namgeun; Cho, Beong Ki; Park, Je-Geun; Lee, Hyosug; Hong, Chang Seop

    2009-04-01

    Four cyanide-linked Fe(III)-Mn(III) complexes were prepared by reacting Mn Schiff bases with a new molecular precursor (PPh(4))[Fe(qcq)(CN)(3)] [1; qcq = 8-(2-quinolinecarboxamido)quinoline anion]. They include a dimeric molecule, [Fe(qcq)(CN)(3)][Mn(3-MeOsalen)(H(2)O)] x 2 H(2)O [2 x 2 H(2)O; 3-MeOsalen = N,N'-ethylenebis(3-methoxysalicylideneiminato) dianion], and three 1D zigzag chains, [Fe(qcq)(CN)(3)][Mn(5-Clsalen)] x 3 H(2)O [3 x 2 MeOH; 5-Clsalen = N,N'-ethylenebis(5-chlorosalicylideneiminato) dianion], [Fe(qcq)(CN)(3)][Mn(5-Brsalen)] x 2 MeOH [4 x 2 MeOH; 5-Brsalen = N,N'-ethylenebis(5-bromosalicylideneiminato) dianion], and Fe(qcq)(CN)(3)][Mn(salen)].MeCN x H(2)O [5 x MeCN; salen = N,N'-ethylenebis(salicylideneiminato) dianion]. The complexes consist of extensive hydrogen bonding and pi-pi stacking interactions, generating multidimensional structures. Magnetic studies demonstrate that antiferromagnetic couplings are operative between Fe(III) and Mn(III) centers bridged by cyanide ligands. On the basis of an infinite chain model, magnetic coupling parameters of 2-5 range from -9.3 to -14.1 cm(-1). A long-range order is observed at 2.3 K for 3 and 2.2 K for 4, while compound 5 shows spin glass behavior possibly coupled with magnetic ordering.

  6. Synthesis and spectral characterization of mono- and binuclear copper(II) complexes derived from 2-benzoylpyridine-N4-methyl-3-thiosemicarbazone: Crystal structure of a novel sulfur bridged copper(II) box-dimer

    NASA Astrophysics Data System (ADS)

    Jayakumar, K.; Sithambaresan, M.; Aiswarya, N.; Kurup, M. R. Prathapachandra

    2015-03-01

    Mononuclear and binuclear copper(II) complexes of 2-benzoylpyridine-N4-methyl thiosemicarbazone (HL) were prepared and characterized by a variety of spectroscopic techniques. Structural evidence for the novel sulfur bridged copper(II) iodo binuclear complex is obtained by single crystal X-ray diffraction analysis. The complex [Cu2L2I2], a non-centrosymmetric box dimer, crystallizes in monoclinic C2/c space group and it was found to have distorted square pyramidal geometry (Addison parameter, τ = 0.238) with the square basal plane occupied by the thiosemicarbazone moiety and iodine atom whereas the sulfur atom from the other coordinated thiosemicarbazone moiety occupies the apical position. This is the first crystallographically studied system having non-centrosymmetrical entities bridged via thiolate S atoms with Cu(II)sbnd I bond. The tridentate thiosemicarbazone coordinates in mono deprotonated thionic tautomeric form in all complexes except in sulfato complex, [Cu(HL)(SO4)]·H2O (1) where it binds to the metal centre in neutral form. The magnetic moment values and the EPR spectral studies reflect the binuclearity of some of the complexes. The spin Hamiltonian and bonding parameters are calculated based on EPR studies. In all the complexes g|| > g⊥ > 2.0023 and the g values in frozen DMF are consistent with the dx2-y2 ground state. The thermal stabilities of some of the complexes were also determined.

  7. Bridges, 1999.

    ERIC Educational Resources Information Center

    Zito, Michael, Ed.

    1999-01-01

    This document is comprised of the two issues in volume 4 of "Bridges," a publication produced by the California Head Start-State Collaboration Office to detail the activities of the educational partnership and to provide relevant information to programs participating in the partnership. The spring 1999 issue focuses on the service system for…

  8. Bridges, 2002.

    ERIC Educational Resources Information Center

    Silver, Michael, Ed.; Zito, Michael, Ed.

    2002-01-01

    This document is comprised of the one issue in volume 7 of "Bridges," a publication produced by the California Head Start-State Collaboration Office to detail the activities of the educational partnership and to provide relevant information to programs participating in the partnership. The Summer 2002 issue focuses on several topics of interest to…

  9. Software Bridge

    NASA Technical Reports Server (NTRS)

    1995-01-01

    I-Bridge is a commercial version of software developed by I-Kinetics under a NASA Small Business Innovation Research (SBIR) contract. The software allows users of Windows applications to gain quick, easy access to databases, programs and files on UNIX services. Information goes directly onto spreadsheets and other applications; users need not manually locate, transfer and convert data.

  10. Bridges, 1999.

    ERIC Educational Resources Information Center

    Wilcox, Bonita; Manear, John; Slifkin, Josh M.

    This volume contains articles about writing, best practice, portfolio assessment, and technology, as well as original poetry and book reviews. Articles in the volume are: "Teaching Writing: Making Connections" (Eric Schott); "Empowering Teachers: A Success Story" (Sandra L. Krivak); "Bridging the Gap between the Classroom and Employment" (Linda C.…

  11. Cadmium(II) and mercury(II) complexes of an NO2S2-donor macrocycle and its ditopic xylyl-bridged analogue.

    PubMed

    Jin, Yongri; Yoon, Il; Seo, Joobeom; Lee, Ji-Eun; Moon, Seok-Tae; Kim, Jineun; Han, Sang Woo; Park, Ki-Min; Lindoy, Leonard F; Lee, Shim Sung

    2005-02-21

    The NO2S2-donor macrocycle (L1) was synthesised from the ring closure reaction between Boc-N-protected 2,2'-iminobis(ethanethiol) (3) and 2,2'-(ethylenedioxy)bis(benzyl chloride) (4) followed by deprotection of the Boc-group. alpha,alpha'-Dibromo-p-xylene was employed as a dialkylating agent to bridge two L1 to yield the corresponding N-linked product (L2). The X-ray structure of L2 (as its HBr salt) is described. A range of Cd(II) and Hg(II) complexes of L1 (6-9) and L2 (10-12) were prepared and characterised. Reaction of HgX2 (X = Br or I) with L1 afforded [Hg(L1)Br]2[Hg2Br6].2CH2Cl2 6 and [Hg(L1)I(2)] 7, respectively. For 6, the Hg(II) ion in the complex cation has a distorted tetrahedral coordination environment composed of S2N donor atoms from L1 and a bromo ligand. In 7 the coordination geometry is highly distorted tetrahedral, with the macrocycle coordinating in an exodentate manner via one S and one N atom. The remaining two coordination sites are occupied by iodide ions. [Hg(L1)(ClO4)]ClO4 8 was isolated from the reaction of Hg(ClO4)2 and L1. The X-ray structure reveals that all macrocyclic ring donors bind to the central mercury ion in this case, with the latter exhibiting a highly distorted octahedral coordination geometry. The O2S2-donors from the macrocyclic ring define the equatorial plane while the axial positions are occupied by the ring nitrogen as well as by an oxygen from a monodentate perchlorato ion. Reaction of Cd(NO3)(2).4H2O with L1 afforded [Cd(L1)(NO3)2](.)0.5CH2Cl2 9 in which L1 acts as a tridentate ligand, binding exo-fashion via its S2N donors. The remaining coordination positions are filled by two bidentate nitrate ions such that, overall, the cadmium is seven-coordinate. Reactions of HgX2(X = Br or I) with L2 yielded the isostructural 2 : 1 (metal : ligand) complexes, [Hg2(L2)Br4] 10 and [Hg2(L2)I(4)] 11. Each mercury ion has a distorted tetrahedral environment made up of S and N donors from an exodentate L2 and two coordinated

  12. 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.

  13. The violin bridge as filter.

    PubMed

    Bissinger, George

    2006-07-01

    The violin bridge filter role was investigated using modal and acoustic measurements on 12 quality-rated violins combined with systematic bridge rocking frequency f(rock) and wing mass decrements deltam on four bridges for two other violins. No isolated bridge resonances were observed; bridge motions were complex (including a "squat" mode near 0.8 kHz) except for low frequency rigid body pivot motions, all more or less resembling rocking motion at higher frequencies. A conspicuous broad peak near 2.3 kHz in bridge driving point mobility (labeled BH) was seen for good and bad violins. Similar structure was seen in averaged bridge, bridge feet, corpus mobilities and averaged radiativity. No correlation between violin quality and BH driving point, averaged corpus mobility magnitude, or radiativity was found. Increasing averaged-over-f(rock) deltam(g) from 0 to 0.12 generally increased radiativity across the spectrum. Decreasing averaged-over-deltam f(rock) from 3.6 to 2.6 kHz produced consistent decreases in radiativity between 3 and 4.2 kHz, but only few-percent decreases in BH frequency. The lowest f(rock) values were accompanied by significantly reduced radiation from the Helmholtz A0 mode near 280 Hz; this, combined with reduced high frequency output, created overall radiativity profiles quite similar to "bad" violins among the quality-rated violins. PMID:16875244

  14. The violin bridge as filter.

    PubMed

    Bissinger, George

    2006-07-01

    The violin bridge filter role was investigated using modal and acoustic measurements on 12 quality-rated violins combined with systematic bridge rocking frequency f(rock) and wing mass decrements deltam on four bridges for two other violins. No isolated bridge resonances were observed; bridge motions were complex (including a "squat" mode near 0.8 kHz) except for low frequency rigid body pivot motions, all more or less resembling rocking motion at higher frequencies. A conspicuous broad peak near 2.3 kHz in bridge driving point mobility (labeled BH) was seen for good and bad violins. Similar structure was seen in averaged bridge, bridge feet, corpus mobilities and averaged radiativity. No correlation between violin quality and BH driving point, averaged corpus mobility magnitude, or radiativity was found. Increasing averaged-over-f(rock) deltam(g) from 0 to 0.12 generally increased radiativity across the spectrum. Decreasing averaged-over-deltam f(rock) from 3.6 to 2.6 kHz produced consistent decreases in radiativity between 3 and 4.2 kHz, but only few-percent decreases in BH frequency. The lowest f(rock) values were accompanied by significantly reduced radiation from the Helmholtz A0 mode near 280 Hz; this, combined with reduced high frequency output, created overall radiativity profiles quite similar to "bad" violins among the quality-rated violins.

  15. The Belizean Bridge Activity.

    ERIC Educational Resources Information Center

    Murfin, Brian

    2000-01-01

    Describes the famous swing bridge in Belize. Students build bridges from a variety of materials and answer the questions, What are different types of bridges?, How do bridges work?, How can you tell if a bridge design will be safe?, and What is the best way to build a bridge over a river while still allowing boat traffic? (SAH)

  16. Bridge Inspector's Training Manual.

    ERIC Educational Resources Information Center

    Federal Highway Administration (DOT), Washington, DC. Bureau of Public Roads.

    A guide for the instruction of bridge inspectors is provided in this manual as well as instructions for conducting and reporting on a bridge inspection. The chapters outline the qualifications necessary to become a bridge inspector. The subject areas covered are: The Bridge Inspector, Bridge Structures, Bridge Inspection Reporting System,…

  17. Heterobimetallic oxalato-bridged M(II)Re(IV) complexes (M = Mn, Fe, Co, Ni): synthesis, crystal structure, and magnetic properties.

    PubMed

    Chiozzone, Raúl; González, Ricardo; Kremer, Carlos; De Munno, Giovanni; Armentano, Donatella; Lloret, Francesc; Julve, Miguel; Faus, Juan

    2003-02-24

    Four rhenium(IV)-M(II) bimetallic complexes of formula [ReCl(4)(mu-ox)M(dmphen)(2)].CH(3)CN with M = Mn (1), Fe (2), Co (3), and Ni (4) (ox = oxalate anion, dmphen = 2,9-dimethyl-1,10-phenanthroline) have been synthesized and the crystal structures of 1 and 3 determined by single-crystal X-ray diffraction. 1 and 3 are isostructural and crystallize in the monoclinic system, space group P2(1)/c, with a = 16.008(4) A, b = 12.729(2) A, c = 18.909(5) A, beta = 112.70(2) degrees, and Z = 4 for 1 and a = 15.998(4) A, b = 12.665(2) A, c = 18.693(5) A, beta = 112.33(2) degrees, and Z = 4, for 3. The structure of 1 and 3 is made up of neutral [ReCl(4)(mu-ox)M(dmphen)(2)] bimetallic units (M = Mn (1), Co (3)) and acetonitrile molecules of crystallization. M(II) and Re(IV) metal ions exhibit distorted octahedral coordination geometries being bridged by a bis(bidentate) oxalato ligand. The magnetic behavior of 1-4 has been investigated over the temperature range 2.0-300 K. A very weak antiferromagnetic coupling between Re(IV) and Mn(II) occurs in 1 (J = -0.1 cm(-)(1)), whereas a significant ferromagnetic interaction between Re(IV) and M(II) is observed in 2-4 [J = +2.8 (2), +5.2 (3), and +5.9 cm(-)(1) (4)].

  18. Ferromagnetic vs. antiferromagnetic coupling in bis(mu2-1,1-azido)dinickel(II) complexes with syn- and anti-conformations of the end-on azide bridges.

    PubMed

    Chaudhuri, Phalguni; Wagner, Rita; Khanra, Sumit; Weyhermüller, Thomas

    2006-11-01

    Reaction of a 1 : 1 : 1 molar ratio of NiCl(2), NaN(3) and H(2)L, a tetradentate ligand N-(2-pyridyl)methyl)-N,N-bis(2'-hydroxy-3',5'-dimethylbenzyl)amine in methanol in presence of Et(3)N results in a turquoise precipitate, which affords deep green crystals of [Ni(2)(HL)(2)(N(3))(2)]*1.5CH(2)Cl(2) (1) and [Ni(2)(HL)(2)(N(3))(2)]*H(2)O (2) upon crystallization from CH(2)Cl(2)-MeOH or THF-MeOH, respectively. Both complexes reveal distorted octahedral NiN(4)O(2) coordination environments around the Ni(ii) centers with bis(micro-1,1-azido) bridging ligands. Complex 1 displays an unprecedented small Ni-N-Ni bridge angle of 90.4 degrees , whereas 2 contains the said angle of av. 98.7 degrees lying in the usual range observed for other comparable structures. The variable-temperature magnetic susceptibility together with the variable-field, variable-temperature (VTVH) magnetization measurements discern different ground states of S(t) = 0 for 1 and S(t) = 2 for 2. The magnetic behaviours of these compounds are discussed in the context of the known bis(end-on azido) bridging dinickel(II) complexes.

  19. Synthesis and structure elucidation of new μ-oxamido-bridged dicopper(II) complex with in vitro anticancer activity: A combined study from experiment verification and docking calculation on DNA/protein-binding property.

    PubMed

    Zhu, Ling; Zheng, Kang; Li, Yan-Tuan; Wu, Zhi-Yong; Yan, Cui-Wei

    2016-02-01

    A new oxamido-bridged dicopper(II) complex with formula of [Cu2(deap)(pic)2], where H2deap and pic represent N,N'-bis[3-(diethylamino)propyl]oxamide and picrate, respectively, was synthesized and characterized by elemental analyses, molar conductance measurements, IR and electronic spectral study, and single-crystal X-ray diffraction. The crystal structure analyses revealed that the two copper(II) atoms in the dicopper(II) complex are bridged by the trans-deap(2-) ligand with the distances of 5.2116(17)Å, and the coordination environment around the copper(II) atoms can be described as a square-planar geometry. Hydrogen bonding and π-π stacking interactions link the dicopper(II) complex into a three-dimensional infinite network. The DNA/protein-binding properties of the complex are investigated by molecular docking and experimental assays. The results indicate that the dicopper(II) complex can interact with HS-DNA in the mode of intercalation and effectively quench the intrinsic fluorescence of protein BSA by 1:1 binding with the most possible binding site in the proximity of Trp134. The in vitro anticancer activities suggest that the complex is active against the selected tumor cell lines, and IC50 values for SMMC-7721 and HepG2 are lower than cisplatin. The effects of the electron density distribution of the terminal ligand and the chelate ring arrangement around copper(II) ions bridged by symmetric N,N'-bis(substituted)oxamides on DNA/BSA-binding ability and in vitro anticancer activity are preliminarily discussed.

  20. The crystal structure and magnetic properties of 3-pyridinecarboxylate-bridged Re(II)M(II) complexes (M = Cu, Ni, Co and Mn).

    PubMed

    Pacheco, Mario; Cuevas, Alicia; González-Platas, Javier; Lloret, Francesc; Julve, Miguel; Kremer, Carlos

    2015-07-01

    The novel Re(II) complex NBu4[Re(NO)Br4(Hnic)] (1) and the heterodinuclear compounds [Re(NO)Br4(μ-nic)Ni(dmphen)2]·½CH3CN (2), [Re(NO)Br4(μ-nic)Co(dmphen)2]·½MeOH (3), [Re(NO)Br4(μ-nic)Mn(dmphen)(H2O)2]·dmphen (4), [Re(NO)Br4(μ-nic)Cu(bipy)2] (5) [Re(NO)Br4(μ-nic)Cu(dmphen)2] (5') (NBu4(+) = tetra-n-butylammonium cation, Hnic = 3-pyridinecarboxylic acid, dmphen = 2,9-dimethyl-1,10-phenanthroline, bipy = 2,2'-bipyridine) have been prepared and the structures of 1-5 determined using single crystal X-ray diffraction. The structure of 1 consists of [Re(NO)Br4(Hnic)](-) anions and NBu4(+) cations. Each Re(II) is six-coordinate with four bromide ligands, a linear nitrosyl group and a nitrogen atom from the Hnic molecule, in a distorted octahedral surrounding. The structures of 2-5 are made up of discrete heterodinuclear Re(II)M(II) units where the fully deprotonated [Re(NO)Br4(nic)](2-) entity acts as a didentate ligand through the carboxylate group towards the [Ni(dmphen)2](2+) (2), [Co(dmphen)2](2+) (3), [Mn(dmphen)(H2O)2](2+) (4) and [Cu(bipy)2](2+) (5) fragments, the Re-M separation across the nic bridge being 7.8736(8) (2), 7.9632(10) (3), 7.7600(6) (4) and 8.2148(7) Å (5). The environment of the Re(II) ion in 2-5 is the same as 1 that in and all M(II) are six-coordinate in highly distorted octahedral surroundings, the main source of the distortion being due to the reduced bite of the chelating carboxylate. The magnetic properties of 1-5' were investigated in the temperature range 1.9-300 K. 1 behaves as a quasi-magnetically isolated spin doublet with very weak antiferromagnetic interactions through space Br···Br contacts. Its magnetic susceptibility data were successfully modeled through a deep analysis of the influence of the ligand field, spin-orbit coupling, tetragonal distortion and covalence effects as variable parameters. Compounds 2-5' exhibit weak antiferromagnetic interactions. The intramolecular exchange pathway in this family being

  1. Synthesis, crystal structures and magnetic properties of cyanide- and phenolate-bridged [M(III)NiII]2 tetranuclear complexes (M=Fe and Cr).

    PubMed

    Toma, Liviu; Toma, Luminita Marilena; Lescouëzec, Rodrigue; Armentano, Donatella; De Munno, Giovanni; Andruh, Marius; Cano, Joan; Lloret, Francesc; Julve, Miguel

    2005-04-21

    The binuclear complex NiII2L(H2O)2(ClO4)2(1) and the neutral tetranuclear bimetallic compounds [{M(III)(phen)(CN)4}2{NiII2L(H2O)2}].2CH3CN with M=Fe (2) and Cr (3)[H2L=11,23-dimethyl-3,7,15,19-tetraazatricyclo[19.3.1.1(9,13)]hexacosa-2,7,9,11,13(26),14,19,21(25),22,24-decaene-25,26-diol] have been synthesized and the structures of and determined by single crystal X-ray diffraction. and are isostructural compounds whose structure is made up of centrosymmetric binuclear cations [Ni2(L)(H2O)2]2+ and two peripheral [M(phen)(CN)4]- anions [M=Fe (2) and Cr (3)] acting as monodentate ligands towards the nickel atoms through one of their four cyanide nitrogen atoms. The environment of the metal atoms in 2 and 3 is six-coordinated: two phen-nitrogen and four cyanide-carbon atoms at the iron and chromium atoms and a water molecule, one cyanide-nitrogen and two phenolate-oxygens and two imine-nitrogens from the binucleating ligand L2- at the nickel atom build distorted octahedral surroundings. The values of the FeNi and CrNi separations through the single cyanide bridge are 5.058(1) and 5.174(2)A respectively, whereas the Ni-Ni distances across the double phenolate bridge are 3.098(2)(2) and 3.101(1) A (3). The magnetic properties of have been investigated in the temperature range 1.9-290 K. The magnetic behaviour of corresponds to that of an antiferromagnetically coupled nickel(II) dimer with J=-61.0(1) cm-1, the Hamiltonian being defined as H=-J S(A).S(B). An overall antiferromagnetic behaviour is observed for and with a low-lying singlet spin state. The values of the intramolecular magnetic couplings are J(Fe-Ni)=+17.4(1) cm-1 and J(Ni-Ni(a))=-44.4(1) cm-1 for and J(Cr-Ni)=+11.8(1) cm-1 and J(Ni-Ni(a))=-44.6(1) cm-1 for [H=-J(M-Ni)(S(M).S(Ni)+S(Ma).S(Nia))-J(Ni-Nia)S(Ni)S(Nia)]. Theoretical calculations using methods based on density functional theory (DFT) have been employed on in order to analyze the efficiency of the exchange pathways involved and also to substantiate

  2. Steel bridge retrofit evaluation

    NASA Astrophysics Data System (ADS)

    Prine, David W.

    1998-03-01

    The development of a retrofit design aimed at retarding or eliminating fatigue crack growth in a large bridge can be a very difficult and expensive procedure. Analytical techniques frequently do not provide sufficient accuracy when applied to complex structural details. The Infrastructure Technology Institute (ITI) of Northwestern University, under contract to the California Department of Transportation (Caltrans), recently applied experimental state-of-the-art NDE technology to the Interstate 80 bridge over the Sacramento River near Sacramento, California (Bryte Bend). Acoustic emission monitoring was applied in conjunction with strain gage monitoring to aid in characterizing the retrofits' effect on existing active fatigue cracks. The combined test results clearly showed that one retrofit design was superior to the other.

  3. Synthesis and crystal structure of new dicopper(II) complexes with N,N'-bis-(dipropylenetriamine)oxamide as bridging ligand: effects of the counterions on DNA/protein-binding property and in vitro antitumor activity.

    PubMed

    Zhao, Feng-Jia; Zhao, Hong-Qin; Liu, Fang; Li, Yan-Tuan; Wu, Zhi-Yong; Yan, Cui-Wei

    2015-02-01

    Two new dicopper(II) complexes bridged by N,N'-bis(dipropylenetriamine)oxamide (H2oxdipn), namely, [Cu2(oxdipn)](pic)2(1) and [Cu2(oxdipn)(ClO4)2] (2), where pic represents picrate ion, have been synthesized and characterized by elemental analyses, molar conductance measurements, IR and electronic spectral studies, and X-ray single crystal diffraction. In both dicopper(II) complexes, the two copper(II) ions are bridged by trans-oxdipn ligand with the Cu⋯Cu separations of 5.2536(15) and 5.231(2)Å, respectively. The copper(II) ion in complex 1 has a square-planar coordination geometry, while that in 2, a square-pyramidal. Linked with classical hydrogen bonds, the molecules of complex 1 consist of a one-dimensional chain, while complex 2 molecules result in a two-dimensional structure. Numerous hydrogen bonds link complex 1 or 2 into a 2-D infinite network. In vitro cytotoxicity experiment shows that the two dicopper(II) complexes exhibit cytotoxic effects against the selected tumor cell lines. The reactivity towards herring sperm DNA (HS-DNA) and bovine serum albumin (BSA) reveals that the two dicopper(II) complexes can interact with the DNA in the mode of intercalation, and effectively quench the intrinsic fluorescence of BSA via a static mechanism. The influence of different counterions in this kind of dicopper(II) complexes on DNA/BSA-binding properties, and the in vitro cytotoxic activities was investigated.

  4. 3. ENVIRONMENT, FROM WEST, SHOWING BOSTON STREET BRIDGE CARRYING BOSTON ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    3. ENVIRONMENT, FROM WEST, SHOWING BOSTON STREET BRIDGE CARRYING BOSTON STREET OVER HARRIS CREEK SEWER, WITH PORTION OF AMERICAN CAN COMPANY COMPLEX - Boston Street Bridge, Spanning Harris Creek Sewer at Boston Street, Baltimore, Independent City, MD

  5. 40. VAL CONNECTING BRIDGE AND BARGES FLOATING ON RESERVOIR (PREVIOUSLY ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    40. VAL CONNECTING BRIDGE AND BARGES FLOATING ON RESERVOIR (PREVIOUSLY SUPPORTED MUZZLE END OF LAUNCHER BRIDGE). - Variable Angle Launcher Complex, Variable Angle Launcher, CA State Highway 39 at Morris Reservior, Azusa, Los Angeles County, CA

  6. 46. VAL, DETAIL OF 'PILLOW BLOCK' WHERE LAUNCHER BRIDGE PIN ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    46. VAL, DETAIL OF 'PILLOW BLOCK' WHERE LAUNCHER BRIDGE PIN SAT AT THE TOP OF THE CONNECTING BRIDGE. - Variable Angle Launcher Complex, Variable Angle Launcher, CA State Highway 39 at Morris Reservior, Azusa, Los Angeles County, CA

  7. Fixation of carbon dioxide by macrocyclic lanthanide(III) complexes under neutral conditions producing self-assembled trimeric carbonato-bridged compounds with μ3-η2:η2:η2 bonding.

    PubMed

    Bag, Pradip; Dutta, Supriya; Biswas, Papu; Maji, Swarup Kumar; Flörke, Ulrich; Nag, Kamalaksha

    2012-03-28

    A series of mononuclear lanthanide(III) complexes [Ln(LH(2))(H(2)O)(3)Cl](ClO(4))(2) (Ln = La, Nd, Sm, Eu, Gd, Tb, Lu) of the tetraiminodiphenolate macrocyclic ligand (LH(2)) in 95 : 5 (v/v) methanol-water solution fix atmospheric carbon dioxide to produce the carbonato-bridged trinuclear complexes [{Ln(LH(2))(H(2)O)Cl}(3)(μ(3)-CO(3))](ClO(4))(4)·nH(2)O. Under similar conditions, the mononuclear Y(III) complex forms the dimeric compound [{Y(LH(2))(H(2)O)Cl}(μ(2)-CO(3)){Y(LH(2))(H(2)O)(2)}](ClO(4))(3)·4H(2)O. These complexes have been characterized by their IR and NMR ((1)H, (13)C) spectra. The X-ray crystal structures have been determined for the trinuclear carbonato-bridged compounds of Nd(III), Gd(III) and Tb(III) and the dinuclear compound of Y(III). In all cases, each of the metal centers are 8-coordinate involving two imine nitrogens and two phenolate oxygens of the macrocyclic ligand (LH(2)) whose two other imines are protonated and intramolecularly hydrogen-bonded with the phenolate oxygens. The oxygen atoms of the carbonate anion in the trinuclear complexes are bonded to the metal ions in tris-bidentate μ(3)-η(2):η(2):η(2) fashion, while they are in bis-bidentate μ(2)-η(2):η(2) mode in the Y(III) complex. The magnetic properties of the Gd(III) complex have been studied over the temperature range 2 to 300 K and the magnetic susceptibility data indicate a very weak antiferromagnetic exchange interaction (J = -0.042 cm(-1)) between the Gd(III) centers (S = 7/2) in the metal triangle through the carbonate bridge. The luminescence spectral behaviors of the complexes of Sm(III), Eu(III), and Tb(III) have been studied. The ligand LH(2) acts as a sensitizer for the metal ions in an acetonitrile-toluene glassy matrix (at 77 K) and luminescence intensities of the complexes decrease in the order Eu(3+) > Sm(3+) > Tb(3+).

  8. Synthesis, crystal structure and magnetic properties of three unprecedented tri-nuclear and one very rare tetra-nuclear copper(II) Schiff-base complexes supported by mixed azido/phenoxo/nitrato or acetato bridges.

    PubMed

    Biswas, Chaitali; Drew, Michael G B; Ruiz, Eliseo; Estrader, Marta; Diaz, Carmen; Ghosh, Ashutosh

    2010-08-28

    Three novel mixed bridged trinuclear and one tetranuclear copper(II) complexes of tridentate NNO donor Schiff base ligands [Cu(3)(L(1))(2)(mu(1,1)-N(3))(2)(CH(3)OH)(2)(BF(4))(2)] (1), [Cu(3)(L(1))(2)(mu(1,1)-N(3))(2)(mu-NO(3)-1kappaO:2kappaO')(2)] (2), [Cu(3)(L(2))(2)(mu(1,1)-N(3))(2)(mu-NO(3)-1kappaO:2kappaO')(2)] (3) and [Cu(4)(L(3))(2)(mu(1,1)-N(3))(4)(mu-CH(3)COO-1kappaO:2kappaO')(2)] (4) have been synthesized by reaction of the respective tridentate ligands (L(1) = 2-[1-(2-dimethylamino-ethylimino)-ethyl]-phenol, L(2) = 2-[1-(2-diethylamino-ethylimino)-ethyl]-phenol, L(3) = 2-[1-(2-dimethylamino-ethylimino)-methyl]-phenol) with the corresponding copper(ii) salts in the presence of NaN(3). The complexes are characterized by single-crystal X-ray diffraction analyses and variable-temperature magnetic measurements. Complex 1 is composed of two terminal [Cu(L(1))(mu(1,1)-N(3))] units connected by a central [Cu(BF(4))(2)] unit through nitrogen atoms of end-on azido ligands and a phenoxo oxygen atom of the tridentate ligand. The structures of 2 and 3 are very similar; the only difference is that the central unit is [Cu(NO(3))(2)] and the nitrate group forms an additional mu-NO(3)-1kappaO:2kappaO' bridge between the terminal and central copper atoms. In complex 4, the central unit is a di-mu(1,1)-N(3) bridged dicopper entity, [Cu(2)(mu(1,1)-N(3))(2)(CH(3)COO)(2)] that connects two terminal [Cu(L(3))(mu(1,1)-N(3))] units through end-on azido, phenoxo oxygen and mu-CH(3)COO-1kappaO:2kappaO' triple bridges to result in a tetranuclear unit. Analyses of variable-temperature magnetic susceptibility data indicates that there is a global weak antiferromagnetic interaction between the copper(II) ions in complexes 1-3, with the exchange parameter J of -9.86, -11.6 and -19.98 cm(-1) for 1-3, respectively. In complex 4 theoretical calculations show the presence of an antiferromagnetic coupling in the triple bridging ligands (acetato, phenoxo and azido) while the interaction

  9. THE TRUSS BRIDGE SEGMENT OF THE TRIBOROUGH BRIDGE IN FOREGROUND ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    THE TRUSS BRIDGE SEGMENT OF THE TRIBOROUGH BRIDGE IN FOREGROUND AND THE HELL GATE BRIDGE IN THE BACKGROUND ADJACENT TO THE SUSPENSION SEGMENT OF THE TRIBOROUGH BRIDGE. - Triborough Bridge, Passing through Queens, Manhattan & the Bronx, Queens (subdivision), Queens County, NY

  10. Synthesis and characterization of dinuclear rare-earth complexes supported by amine-bridged bis(phenolate) ligands and their catalytic activity for the ring-opening polymerization of l-lactide.

    PubMed

    Duan, Yu-Lai; He, Jia-Xuan; Wang, Wei; Zhou, Jing-Jing; Huang, Yong; Yang, Ying

    2016-06-28

    Reactions of amine-bridged bis(phenolate) protio-ligands N,N-bis(3,5-di-tert-butyl-2-hydroxybenzyl)aminoacetic acid (L(1)-H3) and N,N-bis[3,5-bis(α,α'-dimethylbenzyl)-2-hydroxybenzyl]aminoacetic acid (L(2)-H3), with 1 equiv. M[N(SiMe3)2]3 (M = La, Nd, Sm, Gd, Y) in THF at room temperature yielded the neutral rare-earth complexes [M2(L)2(THF)4] (L = L(1), M = La (), Nd (), Sm (), Gd (), Y (); L = L(2), M = La (), Nd (), Sm (), Gd (), Y ()). All of these complexes were characterized by single-crystal X-ray diffraction, elemental analysis and in the case of yttrium and lanthanum complexes, (1)H NMR spectroscopy. The molecular structure of revealed dinuclear species in which the eight-coordinate lanthanum centers were bonded to two oxygen atoms of two THF molecules, to three oxygen atoms and one nitrogen atom of one L(1) ligand, and two oxygen atoms of the carboxyl group of another. Complexes were also dinuclear species containing seven-coordinate metal centers similar to , albeit with bonding to one rather than two carboxyl group oxygens of another ligand. Further treatment of with excess benzyl alcohol provided dinuclear complex [La2(L(1))2(BnOH)6] (), in which each lanthanum ion is eight-coordinate, bonded to three oxygen atoms and one nitrogen atom of one ligand, three oxygen atoms of three BnOH molecules, as well as one oxygen atom of bridging carboxyl group of the other ligand. In the presence of BnOH, complexes efficiently catalyzed the ring-opening polymerization of l-lactide in a controlled manner and gave polymers with relatively narrow molecular weight distributions. The kinetic and mechanistic studies associated with the ROP of l-lactide using /BnOH initiating system have been performed. PMID:27294827

  11. Synthesis and characterization of dinuclear rare-earth complexes supported by amine-bridged bis(phenolate) ligands and their catalytic activity for the ring-opening polymerization of l-lactide.

    PubMed

    Duan, Yu-Lai; He, Jia-Xuan; Wang, Wei; Zhou, Jing-Jing; Huang, Yong; Yang, Ying

    2016-06-28

    Reactions of amine-bridged bis(phenolate) protio-ligands N,N-bis(3,5-di-tert-butyl-2-hydroxybenzyl)aminoacetic acid (L(1)-H3) and N,N-bis[3,5-bis(α,α'-dimethylbenzyl)-2-hydroxybenzyl]aminoacetic acid (L(2)-H3), with 1 equiv. M[N(SiMe3)2]3 (M = La, Nd, Sm, Gd, Y) in THF at room temperature yielded the neutral rare-earth complexes [M2(L)2(THF)4] (L = L(1), M = La (), Nd (), Sm (), Gd (), Y (); L = L(2), M = La (), Nd (), Sm (), Gd (), Y ()). All of these complexes were characterized by single-crystal X-ray diffraction, elemental analysis and in the case of yttrium and lanthanum complexes, (1)H NMR spectroscopy. The molecular structure of revealed dinuclear species in which the eight-coordinate lanthanum centers were bonded to two oxygen atoms of two THF molecules, to three oxygen atoms and one nitrogen atom of one L(1) ligand, and two oxygen atoms of the carboxyl group of another. Complexes were also dinuclear species containing seven-coordinate metal centers similar to , albeit with bonding to one rather than two carboxyl group oxygens of another ligand. Further treatment of with excess benzyl alcohol provided dinuclear complex [La2(L(1))2(BnOH)6] (), in which each lanthanum ion is eight-coordinate, bonded to three oxygen atoms and one nitrogen atom of one ligand, three oxygen atoms of three BnOH molecules, as well as one oxygen atom of bridging carboxyl group of the other ligand. In the presence of BnOH, complexes efficiently catalyzed the ring-opening polymerization of l-lactide in a controlled manner and gave polymers with relatively narrow molecular weight distributions. The kinetic and mechanistic studies associated with the ROP of l-lactide using /BnOH initiating system have been performed.

  12. Ammonia binding to the oxygen-evolving complex of photosystem II identifies the solvent-exchangeable oxygen bridge (μ-oxo) of the manganese tetramer.

    PubMed

    Pérez Navarro, Montserrat; Ames, William M; Nilsson, Håkan; Lohmiller, Thomas; Pantazis, Dimitrios A; Rapatskiy, Leonid; Nowaczyk, Marc M; Neese, Frank; Boussac, Alain; Messinger, Johannes; Lubitz, Wolfgang; Cox, Nicholas

    2013-09-24

    The assignment of the two substrate water sites of the tetra-manganese penta-oxygen calcium (Mn4O5Ca) cluster of photosystem II is essential for the elucidation of the mechanism of biological O-O bond formation and the subsequent design of bio-inspired water-splitting catalysts. We recently demonstrated using pulsed EPR spectroscopy that one of the five oxygen bridges (μ-oxo) exchanges unusually rapidly with bulk water and is thus a likely candidate for one of the substrates. Ammonia, a water analog, was previously shown to bind to the Mn4O5Ca cluster, potentially displacing a water/substrate ligand [Britt RD, et al. (1989) J Am Chem Soc 111(10):3522-3532]. Here we show by a combination of EPR and time-resolved membrane inlet mass spectrometry that the binding of ammonia perturbs the exchangeable μ-oxo bridge without drastically altering the binding/exchange kinetics of the two substrates. In combination with broken-symmetry density functional theory, our results show that (i) the exchangable μ-oxo bridge is O5 {using the labeling of the current crystal structure [Umena Y, et al. (2011) Nature 473(7345):55-60]}; (ii) ammonia displaces a water ligand to the outer manganese (MnA4-W1); and (iii) as W1 is trans to O5, ammonia binding elongates the MnA4-O5 bond, leading to the perturbation of the μ-oxo bridge resonance and to a small change in the water exchange rates. These experimental results support O-O bond formation between O5 and possibly an oxyl radical as proposed by Siegbahn and exclude W1 as the second substrate water. PMID:24023065

  13. Salt Bridges: Geometrically Specific, Designable Interactions

    PubMed Central

    Donald, Jason E.; Kulp, Daniel W.; DeGrado, William F.

    2010-01-01

    Salt bridges occur frequently in proteins, providing conformational specificity and contributing to molecular recognition and catalysis. We present a comprehensive analysis of these interactions in protein structures by surveying a large database of protein structures. Salt bridges between Asp or Glu and His, Arg, or Lys display extremely well-defined geometric preferences. Several previously observed preferences are confirmed and others that were previously unrecognized are discovered. Salt bridges are explored for their preferences for different separations in sequence and in space, geometric preferences within proteins and at protein-protein interfaces, cooperativity in networked salt bridges, inclusion within metal-binding sites, preference for acidic electrons, apparent conformational side chain entropy reduction upon formation, and degree of burial. Salt bridges occur far more frequently between residues at close than distant sequence separations, but at close distances there remain strong preferences for salt bridges at specific separations. Specific types of complex salt bridges, involving three or more members, are also discovered. As we observe a strong relationship between the propensity to form a salt bridge and the placement of salt-bridging residues in protein sequences, we discuss the role that salt bridges might play in kinetically influencing protein folding and thermodynamically stabilizing the native conformation. We also develop a quantitative method to select appropriate crystal structure resolution and B-factor cutoffs. Detailed knowledge of these geometric and sequence dependences should aid de novo design and prediction algorithms. PMID:21287621

  14. Salt bridges: geometrically specific, designable interactions.

    PubMed

    Donald, Jason E; Kulp, Daniel W; DeGrado, William F

    2011-03-01

    Salt bridges occur frequently in proteins, providing conformational specificity and contributing to molecular recognition and catalysis. We present a comprehensive analysis of these interactions in protein structures by surveying a large database of protein structures. Salt bridges between Asp or Glu and His, Arg, or Lys display extremely well-defined geometric preferences. Several previously observed preferences are confirmed, and others that were previously unrecognized are discovered. Salt bridges are explored for their preferences for different separations in sequence and in space, geometric preferences within proteins and at protein-protein interfaces, co-operativity in networked salt bridges, inclusion within metal-binding sites, preference for acidic electrons, apparent conformational side chain entropy reduction on formation, and degree of burial. Salt bridges occur far more frequently between residues at close than distant sequence separations, but, at close distances, there remain strong preferences for salt bridges at specific separations. Specific types of complex salt bridges, involving three or more members, are also discovered. As we observe a strong relationship between the propensity to form a salt bridge and the placement of salt-bridging residues in protein sequences, we discuss the role that salt bridges might play in kinetically influencing protein folding and thermodynamically stabilizing the native conformation. We also develop a quantitative method to select appropriate crystal structure resolution and B-factor cutoffs. Detailed knowledge of these geometric and sequence dependences should aid de novo design and prediction algorithms.

  15. Synthesis of the first heterometalic star-shaped oxido-bridged MnCu3 complex and its conversion into trinuclear species modulated by pseudohalides (N3(-), NCS- and NCO-): structural analyses and magnetic properties.

    PubMed

    Biswas, Saptarshi; Naiya, Subrata; Gómez-García, Carlos J; Ghosh, Ashutosh

    2012-01-14

    A tetra-nuclear, star-shaped hetero-metallic copper(II)-manganese(II) complex, [{CuL(H(2)O)}(2)(CuL)Mn](ClO(4))(2) (1) has been synthesized by reacting the "complex as ligand" [CuL] with Mn(ClO(4))(2) where H(2)L is the tetradentate di-Schiff base derived from 1,3-propanediamine and 2-hydroxyacetophenone. Upon treatment with the polyatomic anions azide, cyanate, or thiocyanate in methanol medium, complex 1 transforms into the corresponding trinuclear species [(CuL)(2)Mn(N(3))(2)] (2), [(CuL)(2)Mn(NCO)(2)] (3) and [(CuL)(2)Mn(NCS)(2)] (4). All four complexes have been structurally and magnetically characterized. In complex 1 the central Mn(II) ion is encapsulated by three terminal [CuL] units through the formation of double phenoxido bridges between Mn(II) and each Cu(II). In complexes 2-4 one of the CuL units is replaced by a couple of terminal azide, N-bonded cyanate or N-bonded thiocyanate ions respectively and the central Mn(II) ion is connected to two terminal Cu(II) ions through a double asymmetric phenoxido bridge. Variable temperature magnetic susceptibility measurements show the presence of moderate ferrimagnetic exchange interactions in all the cases mediated through the double phenoxido bridges with J values (H = -JS(i)S(i + 1)) of -41.2, -39.8 and -12.6 cm(-1) (or -40.5 and -12.7 cm(-1) if we use a model with two different exchange coupling constants) for the tetranuclear MnCu(3) cluster in compound 1 and -20.0, -17.3 and -32.5 cm(-1) for the symmetric trinuclear MnCu(2) compounds 2-4. These ferrimagnetic interactions lead to spin ground states of 1 (5/2 - 3*1/2) for compound 1 and 3/2 (5/2 - 2*1/2) for compounds 2-4.

  16. The long and short of it: the influence of N-carboxyethyl versus N-carboxymethyl pendant arms on in vitro and in vivo behavior of copper complexes of cross-bridged tetraamine macrocycles

    PubMed Central

    Heroux, Katie J.; Woodin, Katrina S.; Tranchemontagne, David J.; Widger, Peter C. B.; Southwick, Evan; Wong, Edward H.; Weisman, Gary R.; Tomellini, Sterling A.; Wadas, Thaddeus J.; Anderson, Carolyn J.; Kassel, Scott; Golen, James A.; Rheingold, Arnold L.

    2015-01-01

    A cross-bridged cyclam ligand bearing two N-carboxymethyl pendant arms (1) has been found to form a copper(II) complex that exhibits significantly improved biological behavior in recent research towards 64Cu-based radiopharmaceuticals. Both the kinetic inertness and resistance to reduction of Cu–1 are believed to be relevant to its enhanced performance. To explore the influence of pendant arm length on these properties, new cross-bridged cyclam and cyclen ligands with longer N-carboxyethyl pendant arms, 2 and 4, and their respective copper(II) complexes have been synthesized. Both mono- as well as di-O-protonated forms of Cu–2 have also been isolated and structurally characterized. The spectral and structural properties of Cu–2 and Cu–4, their kinetic inertness in 5 M HCl, and electrochemical behavior have been obtained and compared to those of their N-carboxymethyl-armed homologs, Cu–1 and Cu–3. Only the cyclam-based Cu–1 and Cu–2 showed unusually high kinetic inertness towards acid decomplexation. While both of these complexes also exhibited quasi-reversible Cu(II)/Cu(I) reductions, Cu–2 is easier to reduce by a substantial margin of +400 mV, bringing it within the realm of physiological reductants. Similarly, of the cyclen-based complexes, Cu–4 is also easier to reduce than Cu–3 though both reductions are irreversible. Biodistribution studies of 64Cu-labeled 2 and 4 were performed in Sprague Dawley rats. Despite comparable acid inertness to their shorter-armed congeners, both longer-armed ligand complexes have poorer bio-clearance properties. This inferior in vivo behavior may be a consequence of their higher reduction potentials. PMID:17514336

  17. [Complex control of the source of infection in sepsis : Extracorporeal membrane oxygenation (ECMO) as a bridging concept for tracheal fistula repair in sepsis-associated ARDS].

    PubMed

    Weiterer, S; Schmidt, K; Deininger, M; Ulrich, A; Tochtermann, U; Eberhardt, R; Hofer, S; Weigand, M A; Brenner, T

    2016-09-01

    Here, we present a case of a tracheal fistula due to an anastomotic insufficiency following abdominothoracic esophageal resection. Despite immediate discontinuity resection, the tracheal fistula could not be surgically closed, resulting in incomplete control of the source of infection and an alternative treatment concept in the form of interventional fistula closure using a Y-tracheal stent. However, owing to existing severe acute respiratory distress syndrome (ARDS), which is associated with a considerable risk of peri-interventional hypoxia, a temporary bridging concept using venovenous extracorporeal membrane oxygenation (ECMO) was implemented successfully. PMID:27596367

  18. Crystal structure of a dinuclear Co(II) complex with bridging fluoride ligands: di-μ-fluorido-bis-{tris-[(6-methyl-pyridin-2-yl)meth-yl]amine}-dicobalt(II) bis-(tetra-fluorido-borate).

    PubMed

    Inomata, Masataka; Suenaga, Yusaku

    2014-11-01

    Reaction of Co(BF4)2·6H2O with tris-[(6-methyl-pyridin-2-yl)meth-yl]amiine in methanol results in a fluoride abstraction from BF4 (-), yielding the unexpected title compound, [Co2F2(C21H24N4)2](BF4)2. The complex cation consists of two inversion-related [Co(C21H24N4)](2+) moieties bridged by a pair of fluoride ligands. The Co(II) cation is six-coordinated in a distorted octa-hedral geometry and forms a +II high-spin state. In the crystal, the complex cation and the BF4 (-) anion are connected by C-H⋯F hydrogen bonds, forming a three-dimensional network. An intra-molecular C-H⋯F hydrogen bond is also observed. PMID:25484774

  19. The effect of the nature of peripheral platinated and bridging mercapto ligands on the optical and electrochemical properties of binuclear Pt(II) complexes with a metal-metal chemical bond

    NASA Astrophysics Data System (ADS)

    Katlenok, E. A.; Balashev, K. P.

    2014-09-01

    The effect of heterocyclic metalated and bridging ligands on the optical and electrochemical properties of [Pt(C^N)(μ-N^S)]2 complexes ((C^N)- and (N^S)- are the deprotonated forms of 1-phenylpyrazole, 2-tolylpyridine, benzo[h]quinoline, 2-phenylbenzothiazole and 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptopyridine) is studied by 1H NMR, electronic absorption, and emission spectroscopy, as well as by voltammetry. The long-wavelength spin-allowed (415-540 nm) absorption bands of the complexes are attributed to the metal-metal-to-ligand charge transfer (MMLCT) optical transitions. It is shown that the interaction of the d Z2 and π{(C^N/*)} orbitals of two {Pt(C^N)} fragments of binuclear complexes leads to a cathodic shift (0.5-1.0 V) of their metal-centered oxidation potential and to an anodic shift (0.1-0.2 V) of their ligand-centered reduction potential with respect to [Pt(C^N)En]+ complexes. The luminescence of binuclear complexes in solutions at room temperature is assigned to the spin-forbidden MMLCT transition. It is shown that, in frozen (77 K) solutions, in addition to the MMLCT optical transitions, spin-forbidden radiative processes occur from the intraligand (π(C^N)-π{(C^N)/*}) and metal-to-ligand charge transfer (dPt-π{(C^N)/*}) excited states.

  20. Cis-trans isomerism in diphenoxido bridged dicopper complexes: role of crystallized water to stabilize the cis isomer, variation in magnetic properties and conversion of both into a trinuclear species.

    PubMed

    Biswas, Apurba; Drew, Michael G B; Diaz, Carmen; Bauzá, Antonio; Frontera, Antonio; Ghosh, Ashutosh

    2012-10-21

    The trans-[Cu(2)L(2)Cl(2)] (1), and cis-[Cu(2)L(2)Cl(2)]·H(2)O (2) isomers of a diphenoxido bridged Cu(2)O(2) core have been synthesized using a tridentate reduced Schiff base ligand 2-[(2-dimethylamino-ethylamino)-methyl]-phenol. The geometry around Cu(II) is intermediate between square pyramid and trigonal bipyramid (Addison parameter, τ = 0.463) in 1 but nearly square pyramidal (τ = 0.049) in 2. The chloride ions are coordinated to Cu(II) and are trans oriented in 1 but cis oriented in 2. Both isomers have been optimized using density functional theory (DFT) calculations and it is found that the trans isomer is 7.2 kcal mol(-1) more favorable than the cis isomer. However, the hydrogen bonding interaction of crystallized water molecule with chloride ions compensates for the energy difference and stabilizes the cis isomer. Both complexes have been converted to a very rare phenoxido-azido bridged trinuclear species, [Cu(3)L(2)(μ(1,1)-N(3))(2)(H(2)O)(2)(ClO(4))(2)] (3) which has also been characterized structurally. All the complexes are antiferromagnetically coupled but the magnitude of the coupling constants are significantly different (J = -156.60, -652.31, and -31.54 cm(-1) for 1, 2, 3 and respectively). Density functional theory (DFT) calculations have also been performed to gain further insight into the qualitative theoretical interpretation on the overall magnetic behavior of the complexes.

  1. A series of dinuclear Dy(iii) complexes bridged by 2-methyl-8-hydroxylquinoline: replacement on the periphery coordinated β-diketonate terminal leads to different single-molecule magnetic properties.

    PubMed

    Zhang, Wan-Ying; Tian, Yong-Mei; Li, Hong-Feng; Chen, Peng; Sun, Wen-Bin; Zhang, Yi-Quan; Yan, Peng-Fei

    2016-03-01

    A series of HMq-bridged dinuclear dysprosium complexes, namely, [Dy(acac)2(CH3OH)]2(μ-HMq)2 (1), [Dy(DBM)2]2(μ-HMq)2(n-C6H14) (2), [Dy(hmac)2]2(μ-HMq)2 (3) and [Dy(hfac)3]2(μ-HMq)2 (4) (HMq = 2-methyl-8-hydroxyquinoline, acac = acetylacetone, DBM = dibenzoylmethane, hmac = hexamethylacetylacetonate and hfac = hexafluoroacetylacetonate), were structurally and magnetically characterized. X-ray crystallographic analyses of the structures reveal that HMq serves as the effective bridge to link two Dy(III) centers by means of the phenoxyl oxygen and nitrogen atoms and the periphery β-diketonate ligands complete the coordination sphere by bidentate oxygen atoms. The different substituents on the β-diketonate terminal lead to different coordination models mostly due to the steric hindrance of these substituents, and the electron-withdrawing or donating effects likely influence the strength of the ligand fields and the Dy(III) ion anisotropy. Measurements of alternating-current (ac) susceptibility on complexes 1-4 reveal that complexes 3 and 4 display significant zero-field single-molecule magnetic (SMM) behavior with barrier energy Ueff/kB = 14.8 K, τ0 = 1.8 × 10(-5) s and Ueff/kB = 9.2 K, τ0 = 1.7 × 10(-5) s, respectively, whereas 1 and 2 exhibit field-induced SMM behavior, and these differences are attributed to the alteration on the periphery β-diketonate ligands. Their distinct slow magnetic relaxation behaviors were related to their different individual Dy(III) ion magnetic anisotropy and intramolecular coupling, which were confirmed by ab initio calculations. PMID:26905041

  2. Cis-trans isomerism in diphenoxido bridged dicopper complexes: role of crystallized water to stabilize the cis isomer, variation in magnetic properties and conversion of both into a trinuclear species.

    PubMed

    Biswas, Apurba; Drew, Michael G B; Diaz, Carmen; Bauzá, Antonio; Frontera, Antonio; Ghosh, Ashutosh

    2012-10-21

    The trans-[Cu(2)L(2)Cl(2)] (1), and cis-[Cu(2)L(2)Cl(2)]·H(2)O (2) isomers of a diphenoxido bridged Cu(2)O(2) core have been synthesized using a tridentate reduced Schiff base ligand 2-[(2-dimethylamino-ethylamino)-methyl]-phenol. The geometry around Cu(II) is intermediate between square pyramid and trigonal bipyramid (Addison parameter, τ = 0.463) in 1 but nearly square pyramidal (τ = 0.049) in 2. The chloride ions are coordinated to Cu(II) and are trans oriented in 1 but cis oriented in 2. Both isomers have been optimized using density functional theory (DFT) calculations and it is found that the trans isomer is 7.2 kcal mol(-1) more favorable than the cis isomer. However, the hydrogen bonding interaction of crystallized water molecule with chloride ions compensates for the energy difference and stabilizes the cis isomer. Both complexes have been converted to a very rare phenoxido-azido bridged trinuclear species, [Cu(3)L(2)(μ(1,1)-N(3))(2)(H(2)O)(2)(ClO(4))(2)] (3) which has also been characterized structurally. All the complexes are antiferromagnetically coupled but the magnitude of the coupling constants are significantly different (J = -156.60, -652.31, and -31.54 cm(-1) for 1, 2, 3 and respectively). Density functional theory (DFT) calculations have also been performed to gain further insight into the qualitative theoretical interpretation on the overall magnetic behavior of the complexes. PMID:22930034

  3. Synthesis, spectral characterization, DNA binding ability and antibacterial screening of copper(II) complexes of symmetrical NOON tetradentate Schiff bases bearing different bridges

    NASA Astrophysics Data System (ADS)

    Bahaffi, Saleh O.; Abdel Aziz, Ayman A.; El-Naggar, Maher M.

    2012-08-01

    A novel series of four copper(II) complexes were synthesized by thermal reaction of copper acetate salt with symmetrical tetradentate Schiff bases, N,N'bis(o-vanillin)4,5-dimethyl-l,2-phenylenediamine (H2L1), N,N'bis(salicylaldehyde)4,5-dimethyl-1,2-phenylenediamine (H2L2), N,N'bis(o-vanillin)4,5-dichloro-1,2-phenylenediamine (H2L3) and N,N'bis(salicylaldehyde)4,5-dichloro-1,2-phenylenediamine (H2L4), respectively. All the new synthesized complexes were characterized by using of microanalysis, FT-IR, UV-Vis, magnetic measurements, ESR, and conductance measurements, respectively. The data revealed that all the Schiff bases (H2L1-4) coordinate in their deprotonated forms and behave as tetradentate NOON coordinated ligands. Moreover, their copper(II) complexes have square planar geometry with general formula [CuL1-4]. The binding of the complexes with calf thymus DNA (CT-DNA) was investigated by UV-Vis spectrophotometry, fluorescence quenching and viscosity measurements. The results indicated that the complexes bind to CT-DNA through an intercalative mode. From the biological activity view, the copper(II) complexes and their parent ligands were screened for their in vitro antibacterial activity against the bacterial species Staphylococcus aureus, Staphylococcus epidermidis, Escherichia coli and Pseudomonas aeruginosai by well diffusion method. The complexes showed an increased activity in comparison to some standard drugs.

  4. Heterotetranuclear oxalato-bridged Re(IV)3M(II) (M = Mn, Fe, Co, Ni, Cu) complexes: a new example of a single-molecule magnet (M = Ni).

    PubMed

    Martínez-Lillo, José; Armentano, Donatella; De Munno, Giovanni; Wernsdorfer, Wolfgang; Clemente-Juan, Juan Modesto; Krzystek, J; Lloret, Francesc; Julve, Miguel; Faus, Juan

    2009-04-01

    The use of the mononuclear species (NBu(4))(2)[Re(IV)Cl(4)(ox)] (NBu(4)(+) = tetra-n-butylammonium cation; ox = oxalate dianion) as a ligand toward fully solvated divalent first-row transition-metal ions affords the tetranuclear complexes (NBu(4))(4)[{Re(IV)Cl(4)(mu-ox)}(3)M(II)] with M = Mn (1), Fe (2), Co (3), Ni (4), and Cu (5). Their structure is made up of discrete [{ReCl(4)(mu-ox)}(3)M](4-) anions and bulky NBu(4)(+) cations. The complexes 2-5 crystallize in the triclinic system with space group P1; 2 and 5 as well as 3 and 4 are isostructural. The Re and M atoms exhibit somewhat distorted ReCl(4)O(2) and MO(6) octahedral surroundings, with the oxalate groups adopting the bis-bidentate bridging mode. Magnetic susceptibility measurements on polycrystalline samples of 1-5 in the temperature range 1.9-300 K show the occurrence of intramolecular antiferromagnetic [J = -1.30 cm(-1) (1)] and ferromagnetic couplings [J = +1.62 (2), +3.0 (3), +16.3 (4), and +4.64 cm(-1) (5)], with the Hamiltonian being defined as H = -J[S(M)(S(Re1) + S(Re2) + S(Re3))]. Compound 4 is the first example of an oxalato-bridged heterometallic species that behaves as a single-molecule magnet with a ground-state spin S = (11)/(2) and D = -0.8(1) cm(-1), as shown by the study of its static and dynamic magnetic properties and a high-frequency electron paramagnetic resonance study on polycrystalline samples together with detailed micro-SQUID measurements on single crystals.

  5. A thiocyanato-bridged copper(I) cubane complex and its application in palladium-catalyzed Sonogashira coupling of aryl halides.

    PubMed

    Trivedi, Manoj; Singh, Gurmeet; Kumar, Abhinav; Rath, Nigam P

    2013-09-28

    Reaction of copper(I) thiocyanate with 1,1'-bis(di-tert-butylphosphino) ferrocene (dtbpf) in a 2:1 molar ratio in DCM-MeOH (50:50 V/V) afforded a tetranuclear copper(I) complex [Cu4(μ3-SCN)4(κ(1)-P,P-dtbpf)2] (1) with a cubane-like structure. Complex 1 was shown to be an efficient catalyst in comparison to CuI in the Sonogashira reaction. The coupling products were obtained in high yields by using Pd loadings of 0.2 mol% as well as complex-1 of 0.1 mol%. PMID:23903662

  6. Instability of the capillary bridge

    NASA Astrophysics Data System (ADS)

    Pare, Gounseti; Hoepffner, Jerome

    2014-11-01

    Capillary adhesion is a physical mechanism that maintains two bodies in contact by capillarity through a liquid ligament. The capillary bridge is an idealization of this capillary adhesion. In this study we first focus on the classical case of the stability of the capillary bridge. Secondly we study a slightly more complex configuration, imagining a flow in the capillary bridge as in the case of the dynamics of the neck of a liquid ligament, in its withdrawal under the effect of capillarity. Inspired by the experiments on soap films of Plateau, the configuration analyzed consists of an initially axisymmetric, mass of fluid held by surface tension forces between two parallel, coaxial, solid pipes of the same diameter. The results presented are obtained by numerical simulations using the free software, Gerris Flow Solver. We first focus on the capillary Venturi. In the static configuration the stability diagram of the capillary bridge obtained is in perfect agreement with the results of Lev A. Slobozhanin. In the dynamic case we develop a matlab code based on the one dimensional equations of Eggers and Dupont. The comparison of the bifurcation diagram obtained and the numerical simulations shows a good agreement.

  7. Mononuclear and binuclear wirelike ruthenium(II) complexes with oligo-diethynyl-thiophene bridged back-to-back terpyridine ligands: synthesis and electrochemical and photophysical properties.

    PubMed

    Barbieri, Andrea; Ventura, Barbara; Barigelletti, Francesco; De Nicola, Antoinette; Quesada, Manuel; Ziessel, Raymond

    2004-11-15

    The syntheses, structural features, electrochemical behavior, absorption spectra, and photophysical properties of five mononuclear complexes [(terpy)Ru(terpy-DEDBT(n)-terpy)](2+), RuT(n), and five binuclear complexes [(terpy)Ru(terpy-DEDBT(n)-terpy)Ru(terpy)](4+), RuT(n)Ru, are reported, where n varies from 1 to 5 so that the metal-metal distance is estimated to be 42 A for the largest binuclear complex, RuT(5)Ru (terpy is 2,2':6',2"-terpyridine and DEDBT is 2,5-diethynyl-3,4-dibutylthiophene). The metal-centered oxidation potentials for the mononuclear and binuclear species are slightly more positive than for the reference [Ru(terpy)(2)](2+) complex, owing to the withdrawing nature of the back-to-back terpyridine ligands incorporating the repeat diethynyl-thiophene units. Comparison of the reduction potentials for the mononuclear and binuclear complexes reveals that the reduction steps are localized either at the terpy fragments of the T(n) ligands or at the terpy peripheral ligands. The spectroscopic results (absorption spectra at room temperature, luminescence spectra and lifetimes at room temperature and at 77 K) in acetonitrile solvent are consistent with the establishment of electronic delocalization within the oligomeric diethynyl-thiophene fragments (DEDBT(n)) of the T(n) ligands; however, the results also indicate that the terpy units of these ligands and the DEDBT(n)fragments are not strongly coupled. Both at room temperature and at 77 K, the (3)metal-to-ligand charge-transfer luminescence of RuT(n) and RuT(n)Ru complexes is strongly depressed in the larger species with respect to what happens for n < or = 2 (where the luminescence quantum yield is phi approximately 10(-4)); this is discussed in terms of the possible intervention of triplet levels localized at the oligothiophene DEDBT(n)(fragments. PMID:15530086

  8. A new μ3-oxo-centered tri-nuclear carboxyl bridged iron (III) complex with thio-methyl groups in the periphery: Structural, spectroscopic and electrochemical studies

    NASA Astrophysics Data System (ADS)

    Lu, Maofeng; Chen, Tingting; Wang, Miao; Jiang, Guomin; Lu, Tianhong; Jiang, Guoqing; Du, Jiangyan

    2014-02-01

    A tri-nuclear iron (III) complex [Fe3(μ3-O)(O2CC6H4SCH3)6(Py)3]FeCl4 has been synthesized and characterized by X-ray crystallography, Surface enhanced Raman Scattering (SERS), Fourier Transform Infra Red (FT-IR), Ultraviolet-Visible (UV-Vis) spectroscopy and Thermogravimetric analysis (TGA)/Differential scanning calorimetry (DSC). The functionalized thio-methyl groups around the periphery of the complex 1 may provide binding sites to the surface of some specific materials, such as noble metals. The Ag sols and complex 1-Ag sol had been characterized by SERS and UV-Vis spectroscopy. The complex 1 were also self-assembled on gold electrode by AuS bond, exhibiting an irreversible process at E1/2 = 0.967 V (ΔE = 0.525 V). Meanwhile the Raman spectra were compared with FT-IR, and the results indicated that the strong Raman lines either correspond to weak Infrared absorptions or are absent in the Infrared spectra.

  9. Influence of central metalloligand geometry on electronic communication between metals: syntheses, crystal structures, MMCT properties of isomeric cyanido-bridged Fe2Ru complexes, and TDDFT calculations.

    PubMed

    Ma, Xiao; Lin, Chen-Sheng; Hu, Sheng-Min; Tan, Chun-Hong; Wen, Yue-Hong; Sheng, Tian-Lu; Wu, Xin-Tao

    2014-06-01

    To investigate how the central metalloligand geometry influences distant or vicinal metal-to-metal charge-transfer (MMCT) properties of polynuclear complexes, cis- and trans-isomeric heterotrimetallic complexes, and their one- and two-electron oxidation products, cis/trans-[Cp(dppe)Fe(II)NCRu(II)(phen)2CN-Fe(II)(dppe)Cp][PF6]2 (cis/trans-1[PF6]2), cis/trans-[Cp(dppe)Fe(II)NCRu(II)(phen)2CNFe(III)-(dppe)Cp][PF6]3 (cis/trans-1[PF6]3) and cis/trans-[Cp(dppe)Fe(III)NCRu(II)(phen)2CN-Fe(III)(dppe)Cp][PF6]4 (cis/trans-1[PF6]4) have been synthesized and characterized. Electrochemical measurements show the presence of electronic interactions between the two external Fe(II) atoms of the cis- and trans-isomeric complexes cis/trans-1[PF6]2. The electronic properties of all these complexes were studied and compared by spectroscopic techniques and TDDFT//DFT calculations. As expected, both mixed valence complexes cis/trans-1[PF6]3 exhibited different strong absorption signals in the NIR region, which should mainly be attributed to a transition from an MO that is delocalized over the Ru(II)-CN-Fe(II) subunit to a Fe(III) d orbital with some contributions from the co-ligands. Moreover, the NIR transition energy in trans-1[PF6]3 is lower than that in cis-1[PF6]3, which is related to the symmetry of their molecular orbitals on the basis of the molecular orbital analysis. Also, the electronic spectra of the two-electron oxidized complexes show that trans-1[PF6]4 possesses lower vicinal Ru(II) → Fe(III) MMCT transition energy than cis-1[PF6]4. Moreover, the assignment of MMCT transition of the oxidized products and the differences of the electronic properties between the cis and trans complexes can be well rationalized using TDDFT//DFT calculations. PMID:24771667

  10. Mixed ligand μ-phenoxo-bridged dinuclear copper(II) complexes with diimine co-ligands: efficient chemical nuclease and protease activities and cytotoxicity.

    PubMed

    Loganathan, Rangasamy; Ramakrishnan, Sethu; Suresh, Eringathodi; Palaniandavar, Mallayan; Riyasdeen, Anvarbatcha; Akbarsha, Mohamad Abdulkadhar

    2014-04-28

    The water soluble mixed ligand copper(II) complexes of the type [Cu(sal)(diimine)(ClO4)]21-5, where sal is salicylaldehyde and diimine is 2,2'-bipyridine (bpy, 1), 1,10-phenanthroline (phen, 2), 5,6-dimethyl-1,10-phenanthroline (5,6-dmp, 3), 3,4,7,8-tetramethyl-1,10-phenanthroline (3,4,7,8-tmp, 4) or dipyrido[3,2-d:2',3'-f]quinoxaline (dpq, 5), and [Cu(sal)(phen)(NO3)]2 (2a) have been successfully isolated and characterized by elemental analysis and other spectral techniques. The DNA binding and cleavage properties of 1-5 have been explored by using various physical and biochemical methods. The coordination geometry around copper(II) in the X-ray structures of 1, 2, 2a and 4 is described as an elongated octahedron. The UV-Vis and EPR spectral and ESI-MS studies reveal that in solution the dinuclear complexes dissociate into essentially mononuclear [Cu(sal)(diimine)]+ species with square-based geometry. The absorption spectral titrations and competitive DNA binding studies reveal that the intrinsic DNA binding affinity of the complexes depends upon the diimine co-ligand and is of the order of dpq (5) > 3,4,7,8-tmp (4) > 5,6-dmp (3) > phen (2) > bpy (1). The complexes 2 and 5 are involved in a partial intercalative interaction with DNA base pairs, while 3 and 4 are involved in a hydrophobic interaction with DNA and 1 is involved in an electrostatic interaction with DNA, which is supported by viscosity studies. Interestingly, only 3 and 4 are selective in exhibiting a positive induced CD band (ICD) upon binding to DNA suggesting that they induce a B to A conformational change in DNA. All the complexes exhibit an oxidative DNA cleavage ability, which varies as 5 > 4 > 3 > 2 > 1. While 4 and 5 are unique in displaying prominent double-strand DNA cleavage even in the absence of an activator, 2 and 3 display only single-strand DNA cleavage. Interestingly, all the complexes exhibit oxidative double-strand DNA cleavage in the presence of ascorbic acid, with 4 and 5 showing

  11. Cadmium(II) chloride, bromide and iodide complexes with 4,4'-bipyridazine: when are diazine and halide bridges (in)compatible?

    PubMed

    Domasevitch, Konstantin V; Rusanova, Julia A; Gural'skiy, Ilya A; Solntsev, Pavlo V

    2012-11-01

    In poly[di-μ-chlorido-μ-(4,4'-bipyridazine)-κ(2)N(1):N(1')-cadmium(II)], [CdCl(2)(C(8)H(6)N(4))](n), (I), and its isomorphous bromide analogue, [CdBr(2)(C(8)H(6)N(4))](n), (II), the halide atom lies on a mirror plane and the Cd(II) ion resides at the intersection of two perpendicular mirror planes with m2m site symmetry. The pyridazine rings of the ligand lie in a mirror plane and are related to each other by a second mirror plane perpendicular to the first. The compounds adopt the characteristic structure of the [M(II)X(2)(bipy)] type (bipy is bipyridine) based on crosslinking of [Cd(μ-X)(2)](n) chains [Cd-Cl = 2.5955 (9) and 2.6688 (9) Å; Cd-Br = 2.7089 (4) and 2.8041 (3) Å] by bitopic rod-like organic ligands [Cd-N = 2.368 (3)-2.380 (3) Å]. This feature is discussed in terms of supramolecular stabilization, implying that the periodicity of the inorganic chain [Cd···Cd = 3.7802 (4) Å in (I) and 3.9432 (3) Å in (II)] is favourable for extensive parallel π-π stacking of monodentate pyridazine rings, with centroid-centroid distances of 3.7751 (4) Å in (I) and 3.9359 (4) Å in (II). This is not the case for the longer iodide bridges, which cannot stabilize such a pattern. In poly[tetra-μ-iodido-μ(4)-(4,4'-bipyridazine)-κ(4)N(1):N(2):N(1'):N(2')-dicadmium(II)], [Cd(2)I(4)(C(8)H(6)N(4))](n), (III), the ligands are situated across a centre of inversion; they are tetradentate [Cd-N = 2.488 (2) and 2.516 (2) Å] and link successive [Cd(μ-I)(2)](n) chains [Cd-I = 2.8816 (3)-3.0069 (4) Å] into corrugated layers.

  12. Mono- and binuclear cyclometallated palladium(II) complexes containing bridging (N,O-) and terminal (N-) imidate ligands: air stable, thermally robust and recyclable catalysts for cross-coupling processes.

    PubMed

    Fairlamb, Ian J S; Kapdi, Anant R; Lee, Adam F; Sánchez, Gregorio; López, Gregorio; Serrano, José Luis; García, Luis; Pérez, José; Pérez, Eduardo

    2004-12-01

    Novel dinuclear cyclometallated palladium complexes [{Pd(mu-NCO)(C circumflex accent N)}(2)], containing asymmetric imidato -NCO- bridging units have been synthesised [C circumflex accent N = 7,8-benzoquinolyl; -NCO- = succinimidate (1c), phthalimidate (1a-3a) or maleimidate (3c)]. The reaction of these complexes, and the previously reported analogous imidate precursors containing a phenylazophenyl (1a-3a) or 2-pyridylphenyl (1b-3b) backbone, with tertiary phosphines provides novel mononuclear N-bonded imidate derivatives of the general formula [Pd(C circumflex accent N)(imidate)(L)][L = PPh(3), P(4-F-C(6)H(4))(3) or P(4-MeO-C(6)H(4))(3)]. The single crystal structures of [Pd(azb)(phthalimidate)(P(4-MeO-C(6)H(4))(3))](9a) and [Pd(bzq)(phthalimidate)(PPh(3))](7c) have been established. Dinuclear complexes (1a-3a, 1b-3b, 1c-3c) demonstrate outstanding thermal stability in the solid-state, as shown by thermoanalytical techniques. A marked influence of bridging imidate groups on the initial decomposition temperature is observed. The dinuclear and mononuclear derivatives are shown to be active catalysts/precatalysts for the Suzuki-Miyaura cross-coupling reactions of aryl bromides with aryl boronic acids, and the Sonogashira reactions of aryl halides with phenyl acetylene (in the presence and absence of Cu(I) salts). The conversions appear to be dependent, to some extent, on the type of imidate ligand, suggesting a role for these pseudohalides in the catalytic cycle in both cross-coupling processes. Lower catalyst loadings in 'copper-free' Sonogashira cross-couplings favour higher turnover frequencies. We have further determined that these catalysts may be recycled using a poly(ethylene oxide)(PEO)/methanol solvent medium in Suzuki-Miyaura cross-coupling. Once the reaction is complete, product extraction into a hexane/diethyl ether mixture (1 : 1, v/v) gives cross-coupled products in good yields (with purity > 95%). The polar phase can then be re-used several times

  13. Synthesis and molecular recognition of novel oligo(ethylenediamino) bridged bis(beta-cyclodextrin)s and their copper(II) complexes: enhanced molecular binding ability and selectivity by multiple recognition.

    PubMed

    Liu, Y; You, C C; Li, B

    2001-03-16

    Four bridged bis(beta-cyclodextrin)s tethered by different lengths of oligo(ethylenediamine)s have been synthesized and their inclusion complexation behavior with selected substrates elucidated by circular dichroism spectroscopy and fluorescence decay. In order to study their binding ability quantitatively, inclusion complexation stability constants with four dye guests, that is, brilliant green (BG), methyl orange (MO), ammonium 8-anilino-1-naphthalenesulfonic acid (ANS), and sodium 6-(p-toluidino)-2-naphthalenesulfonate (TNS), have been determined in aqueous solution at 25 degrees C with spectrophotometric, spectropolarimetric, or spectrofluorometric titrations. The results obtained indicate that the two tethered cyclodextrin units might cooperatively bind to a guest, and the molecular binding ability toward model substrates, especially linear guests such as TNS and MO, could be extended. The tether length plays a crucial role in the molecular recognition, the binding constants for ANS and TNS decrease linearly with an increase in the tether length of dimeric cyclodextrin. The Gibbs free energy changes (-deltaGo) for the unit increment per ethylene are 0.99 kJ mol(-1) for ANS and 0.44 kJmol(-1) for TNS, respectively. On the other hand, the presence of a copper(II) ion in metallobis(beta-cyclodextrin)s oligo(ethylenediamino) tethers enhances not only the original binding ability, but also the molecular selectivity through triple or multiple recognition, as compared with the parent bis(beta-cyclodextrin)s.

  14. Synthesis, Characterization and DFT-Based Investigation of a Novel Trinuclear Singly-Chloro-Bridged Copper(II)-1-Vinylimidazole Complex.

    PubMed

    Yolcu, Zuhal; Demir, Serkan; Andaç, Ömer; Büyükgüngör, Orhan

    2016-01-01

    A novel trinuclear copper(II) complex [Cu3(μ-Cl)2Cl4(1-Vim)6] with monodentate 1-vinylimidazole (1-Vim) and chloro ligands has been prepared and experimentally characterized by elemental analysis, thermogravimetry (TGA, DTG, DTA), X-ray single crystal diffractometry, TOF-MS and FT-IR spectroscopies. The electronic and structural properties of the complex were further investigated by DFT/TD-DFT methods. Density functional hybrid method (B3LYP) was applied throughout the calculations. The calculated UV-Vis results based on TD-DFT approach were simulated and compared with experimental spectrum. Based on the data obtained, DFT calculations have been found in reasonable accordance with experimental data. PMID:27640392

  15. 1. WESTERN VIEW OF BRIDGE PLAZA, SHOWING MEMORIAL BRIDGE AT ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    1. WESTERN VIEW OF BRIDGE PLAZA, SHOWING MEMORIAL BRIDGE AT LEFT AND THE ROCK CREEK AND POTOMAC PARKWAY RAMP AT RIGHT. VIEW TAKEN FROM THE REAR OF THE LINCOLN MEMORIAL. - Arlington Memorial Bridge, Watergate & Bridge Plaza, Adjacent to Arlington Memorial Bridge & Lincoln Memorial, Washington, District of Columbia, DC

  16. [Composite (etched) bridge].

    PubMed

    de Kloet, H J; van Pelt, A W

    1996-11-01

    An adhesive or resin-bonded bridge is a tooth saving construction for the replacement of a lost tooth, especially when the abutment teeth are relatively sound. In this article an overview is presented of the different types of resin-bonded bridges, their advantages and disadvantages and their indications. The direct methods are very suited for the immediate replacement of a lost anterior tooth. The all composite adhesive bridge has a survival rate that is surprisingly good.

  17. Semiconductor bridge (SCB) detonator

    DOEpatents

    Bickes, Jr., Robert W.; Grubelich, Mark C.

    1999-01-01

    The present invention is a low-energy detonator for high-density secondary-explosive materials initiated by a semiconductor bridge igniter that comprises a pair of electrically conductive lands connected by a semiconductor bridge. The semiconductor bridge is in operational or direct contact with the explosive material, whereby current flowing through the semiconductor bridge causes initiation of the explosive material. Header wires connected to the electrically-conductive lands and electrical feed-throughs of the header posts of explosive devices, are substantially coaxial to the direction of current flow through the SCB, i.e., substantially coaxial to the SCB length.

  18. Semiconductor bridge (SCB) detonator

    DOEpatents

    Bickes, R.W. Jr.; Grubelich, M.C.

    1999-01-19

    The present invention is a low-energy detonator for high-density secondary-explosive materials initiated by a semiconductor bridge (SCB) igniter that comprises a pair of electrically conductive lands connected by a semiconductor bridge. The semiconductor bridge is in operational or direct contact with the explosive material, whereby current flowing through the semiconductor bridge causes initiation of the explosive material. Header wires connected to the electrically-conductive lands and electrical feed-throughs of the header posts of explosive devices, are substantially coaxial to the direction of current flow through the SCB, i.e., substantially coaxial to the SCB length. 3 figs.

  19. Designing the ideal uranyl ligand: a sterically induced speciation change in complexes with thiophene-bridged bis(3-hydroxy-n-methylpyridin-2-one).

    PubMed

    Szigethy, Géza; Raymond, Kenneth N

    2009-12-21

    Structural characterization of a mononuclear uranyl complex with a tetradentate, thiophene-linked bis(3-hydroxy-N-methylpyridin-2-one) ligand reveals the most planar coordination geometry yet observed with this ligand class. The introduction of ethylsulfanyl groups onto the thiophene linker disrupts this planar, conjugated ligand arrangement, resulting in the formation of dimeric (UO(2))(2)L(2) species in which each ligand spans two uranyl centers. Relative energy calculations reveal that this tendency toward dimer formation is the result of steric interference between ethylsulfanyl substitutents and linking amides. PMID:19928845

  20. Designing the Ideal Uranyl Ligand: a Sterically-Induced Speciation Change in Complexes with Thiophene-Bridged Bis(3-hydroxy-N-methylpyridin-2-one)

    SciTech Connect

    Szigethy, Geza; Raymond, Kenneth N.

    2009-09-11

    Structural characterization of a mononuclear uranyl complex with a tetradentate, thiophene-linked bis(3-hydroxy-N-methylpyridin-2-one) ligand reveals the most planar coordination geometry yet observed with this ligand class. The introduction of ethylsulfanyl groups onto the thiophene linker disrupts this planar, conjugated ligand arrangement, resulting in the formation of dimeric (UO{sub 2}){sub 2}L{sub 2} species in which each ligand spans two uranyl centers. Relative energy calculations reveal that this tendency toward dimer formation is the result of steric interference between ethylsulfanyl substituents and linking amides.

  1. Electronic communication across diamagnetic metal bridges: a homoleptic gallium(III) complex of a redox-active diarylamido-based ligand and its oxidized derivatives

    PubMed Central

    Liddle, Brendan J.; Wanniarachchi, Sarath; Hewage, Jeewantha S.; Lindeman, Sergey V.; Bennett, Brian; Gardinier, James R.

    2012-01-01

    Complexes with cations of the type [Ga(L)2]n+ where L = bis(4-methyl-2-(1H-pyrazol-1-yl)phenyl)amido and n = 1, 2, 3 have been prepared and structurally characterized. The electronic properties of each were probed by electrochemical and spectroscopic means and were interpreted with the aid of DFT calculations. The dication, best described as [Ga(L−)(L0)]2+, and is a Robin-Day class II mixed-valence species. As such, a broad, weak, solvent-dependent intervalence charge transfer (IVCT) band was found in the NIR spectrum in the range 6390 to 6925 cm−1, depending on solvent. Band shape analyses and the use of Hush and Marcus relations revealed a modest electronic coupling, Hab of about 200 cm−1, and a large rate constant for electron transfer, ket, on the order of 1010 s−1 between redox active ligands. The di-oxidized complex [Ga(L0)2]3+ shows a half-field ΔMs = 2 transition in its solid-state X-Band EPR spectrum at 5 K which indicates that the triplet state is thermally populated. DFT calculations (M06/Def2-SV(P)) suggest that the singlet state is 21.7 cm−1 lower in energy than the triplet state. PMID:23163736

  2. The structure, magnetism and EPR spectra of a (μ-thiophenolato)(μ-pyrazolato-N,N') double bridged dicopper(II) complex.

    PubMed

    Khadir, Narjes; Boghaei, Davar M; Assoud, Abdeljalil; Nascimento, Otaciro R; Nicotina, Amanda; Ghivelder, Luis; Calvo, Rafael

    2015-02-01

    A new binuclear copper(ii) complex, namely [Cu2L(pz)(DMSO)], where L = 2,6-bis[(2-phenoxy)iminomethyl]-4-methylthiophenolate(3-) and pz = pyrazolate ligand, has been synthesized by a one-pot synthesis involving copper(ii) acetate monohydrate, the S-protected ligand precursor 2-(N,N-dimethylthiocarbamato)-5-methylisophthalaldehyde di-2'-hydroxy anil, (), and pyrazole, in which a metal-promoted S-deprotection reaction occurs during the formation of the complex. This was characterized by routine physicochemical studies, single crystal X-ray diffraction and electron paramagnetic resonance (EPR) techniques. The structure analysis reveals that there are copper centres in two different environments, a slightly distorted square planar and a distorted square-pyramidal, arranged in binuclear units. The EPR study of these binuclear units performed at 9.4 GHz in the temperature range between 4 and 293 K shows an antiferromagnetic interaction between Cu(II) ions, and allows evaluating g factors gx = 2.068(1), gy = 2.091(1) and gz = 2.165(1), with = 2.108(1), an exchange coupling parameter J0 = -26(1) cm(-1) (defined as ), and a zero field splitting of the ground triplet state described by D = 86(2) × 10(-4) cm(-1) and E = -48(3) × 10(-4) cm(-1). These results are discussed and compared with the existing literature.

  3. Electronic communication across diamagnetic metal bridges: a homoleptic gallium(III) complex of a redox-active diarylamido-based ligand and its oxidized derivatives.

    PubMed

    Liddle, Brendan J; Wanniarachchi, Sarath; Hewage, Jeewantha S; Lindeman, Sergey V; Bennett, Brian; Gardinier, James R

    2012-12-01

    Complexes with cations of the type [Ga(L)(2)](n+) where L = bis(4-methyl-2-(1H-pyrazol-1-yl)phenyl)amido and n = 1, 2, 3 have been prepared and structurally characterized. The electronic properties of each were probed by electrochemical and spectroscopic means and were interpreted with the aid of density functional theory (DFT) calculations. The dication, best described as [Ga(L(-))(L(0))](2+), is a Robin-Day class II mixed-valence species. As such, a broad, weak, solvent-dependent intervalence charge transfer (IVCT) band was found in the NIR spectrum in the range 6390-6925 cm(-1), depending on the solvent. Band shape analyses and the use of Hush and Marcus relations revealed a modest electronic coupling, H(ab) of about 200 cm(-1), and a large rate constant for electron transfer, k(et), on the order of 10(10) s(-1) between redox active ligands. The dioxidized complex [Ga(L(0))(2)](3+) shows a half-field ΔM(s) = 2 transition in its solid-state X-band electron paramagnetic resonance (EPR) spectrum at 5 K, which indicates that the triplet state is thermally populated. DFT calculations (M06/Def2-SV(P)) suggest that the singlet state is 21.7 cm(-1) lower in energy than the triplet state.

  4. Two-Component Polymeric Materials of Fullerenes and the Transition Metal Complexes: A Bridge between Metal-Organic Frameworks and Conducting Polymers.

    PubMed

    Balch, Alan L; Winkler, Krzysztof

    2016-03-23

    In this review, we examined the interactions of metal complexes and metal surfaces with fullerenes. That information has been related to the formation of redox-active materials produced by electrochemical reduction of solutions of various transition metal complexes and fullerene or fullerene adducts. These redox-active polymers are strongly bound to electrode surfaces and display electrochemical activity in solutions containing only supporting electrolyte. Extensive studies of the electrochemical behavior of these films have been used to characterize their properties and structure. The process that produces these poly-Pd(n)C60 and poly-Pt(n)C60 films can also produce composite materials that consist of metal nanoparticles interspersed with the poly-Pd(n)C60 and poly-Pt(n)C60 materials. The relationship between these redox-active films and conducting metal organic framework materials has been examined. These insoluble, redox-active polymers have potential utility for the adsorption of various gases, for the construction of capacitors, for sensing, for the preparation of metal-containing heterofullerenes, and for catalysis.

  5. 11. Southern bridge abutment and arches, taken from old bridge ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    11. Southern bridge abutment and arches, taken from old bridge abutment looking south. - Presumpscot Falls Bridge, Spanning Presumptscot River at Allen Avenue extension, 0.75 mile west of U.S. Interstate 95, Falmouth, Cumberland County, ME

  6. GOETHALS BRIDGE FROM NORTH SIDE OVER ARTHUR KILL. RAILROAD BRIDGE ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    GOETHALS BRIDGE FROM NORTH SIDE OVER ARTHUR KILL. RAILROAD BRIDGE IN FOREGROUND - Goethals Bridge, Spanning Arthur Kill from New Jersey to Staten Island, Staten Island (subdivision), Richmond County, NY

  7. 4. View of Clark Fork Vehicle Bridge facing northeast. Bridge ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    4. View of Clark Fork Vehicle Bridge facing northeast. Bridge from south shoreof Clark Fork River showing 4 spans. - Clark Fork Vehicle Bridge, Spanning Clark Fork River, serves Highway 200, Clark Fork, Bonner County, ID

  8. 2. View of Clark Fork Vehicle Bridge facing northeast. Bridge ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    2. View of Clark Fork Vehicle Bridge facing northeast. Bridge from south shore of Clark Fork River showing 4 1/2 spans. - Clark Fork Vehicle Bridge, Spanning Clark Fork River, serves Highway 200, Clark Fork, Bonner County, ID

  9. 7. View of Clark Fork Vehicle Bridge facing northwest. Bridge ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    7. View of Clark Fork Vehicle Bridge facing northwest. Bridge from south shore of Clark Fork River showing 4 1/2 spans. - Clark Fork Vehicle Bridge, Spanning Clark Fork River, serves Highway 200, Clark Fork, Bonner County, ID

  10. 3. View of Clark Fork Vehicle Bridge facing southwest. Bridge ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    3. View of Clark Fork Vehicle Bridge facing southwest. Bridge from north shore of Clark Fork River. - Clark Fork Vehicle Bridge, Spanning Clark Fork River, serves Highway 200, Clark Fork, Bonner County, ID

  11. Plans: Poop Deck, Boat Deck, Housetop, Bridge Deck, Upper Bridge ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    Plans: Poop Deck, Boat Deck, Housetop, Bridge Deck, Upper Bridge Deck, Navigating Bridge, Forecastle Deck, Upper Deck, Second Deck and Hold - Saugatuck, James River Reserve Fleet, Newport News, Newport News, VA

  12. APPROACH BRIDGE PORTION OF VALVE TOWER FOOT BRIDGE, AS SEEN ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    APPROACH BRIDGE PORTION OF VALVE TOWER FOOT BRIDGE, AS SEEN FROM ENTRY. VIEW FACING NORTHWEST - Schofield Barracks Military Reservation, Ku Tree Reservoir, Valve Tower Foot Bridge, Kalakoa Stream, East Range, Wahiawa, Honolulu County, HI

  13. APPROACH BRIDGE PORTION OF VALVE TOWER FOOT BRIDGE, AS SEEN ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    APPROACH BRIDGE PORTION OF VALVE TOWER FOOT BRIDGE, AS SEEN FROM BELOW, SHOWING VALVE TOWER TO RIGHT. VIEW FACING NORTH - Schofield Barracks Military Reservation, Ku Tree Reservoir, Valve Tower Foot Bridge, Kalakoa Stream, East Range, Wahiawa, Honolulu County, HI

  14. LOOKING WEST, BETWEEN READING DEPOT BRIDGE AND SKEW ARCH BRIDGE ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    LOOKING WEST, BETWEEN READING DEPOT BRIDGE AND SKEW ARCH BRIDGE (HAER No. PA-116). - Philadelphia & Reading Railroad, Reading Depot Bridge, North Sixth Street at Woodward Street, Reading, Berks County, PA

  15. Violin bridge-hill to radiation: The energy trail

    NASA Astrophysics Data System (ADS)

    Bissinger, George

    2005-09-01

    Simultaneous experimental modal and acoustical analysis in an anechoic chamber was used to track energy flow through quality-rated violins to clarify the link between the mechanical motions at a driving point on the G-corner of the bridge, and subsequent radiation from the violin. The 0-4-kHz range covered included a broad hump near 2.4 kHz in driving point mobility generally labeled the bridge-hill and thought to be related to violin quality and radiativity (and sound). The bridge-hill enhancement showed up successively in the averaged mobility of the bridge, at the bridge feet, and over the corpus; a corresponding peak was also seen in the radiativity, indicating that enhanced radiation accompanied enhanced bridge motion. All bridge motions except low-frequency rigid-body motions were complex, and generally showed some semblance of rocking motion at higher frequencies. No evidence was observed for any bridge resonance separate from string or corpus resonances, although most bridges showed a complex squat mode near 0.8 kHz (not accompanied by enhanced radiation) that is likely an out-of-plane bending mode falling far below the rocking mode. Bridge-hill magnitude was not found to correlate well with violin quality, or averaged corpus mobility, or averaged radiativity.

  16. Insertion and [beta]-hydride elimination reactions of ruthenium/zirconium complexes containing C[sub 2] bridges with bond orders of 1, 2, and 3

    SciTech Connect

    Lemke, F.R.; Bullock, R.M. )

    1992-12-01

    Carbon dioxide inserts into the Zr-C bond of Cp(PMe[sub 3])[sub 2]RuCH[double bond]CHZrClCp[sub 2], producing the carboxylate complex Cp(PMe[sub 3])[sub 2]RuCH[double bond]CHCO[sub 2]ZrClCp[sub 2]. An [eta][sup 2]-iminoacyl insertion product, Cp(PMe[sub 3])[sub 2]Ru-C[triple bond]C-C(N[sub t]Bu)ZrClCp[sub 2], results from insertion of [sup t]BuNC into the Zr-C bond of the dimetalloalkyne complex Cp(PMe[sub 3])[sub 2]Ru-C[triple bond]C-ZrClCp[sub 2]. The reaction of Cp(PMe[sub 3])[sub 2]RuCH[sub 2]CH[sub 2]ZrClCp[sub 2] with high concentrations of [sup t]BuNC also produces an [eta][sup 2]-iminoacyl insertion product, Cp(PMe[sub 3])[sub 2]RuCH[sub 2]CH[sub 2]C(N[sup t]Bu)ZrClCp[sub 2]. At low concentrations of [sup t]BuNC, a competing reaction is [beta]-hydride elimination from Cp(PMe[sub 3])[sub 2]RuCH[sub 2]CH[sub 2]ZrClCp[sub 2] to give Cp(PMe[sub 3])[sub 2]RuCH[double bond]CH[sub 2] and Cp[sub 2]Zr(H)Cl, which is trapped by [sup t]BuNC under these conditions to give Cp[sub 2]ZrCl([eta][sup 2]-[sup t]BuN[double bond]CH). The reaction of benzophenone with Cp(PMe[sub 3])[sub 2]RuCH[sub 2]CH[sub 2]ZrClCp[sub 2] gives the insertion product Cp(PMe[sub 3])[sub 2]RuCH[sub 2]CH[sub 2]CPh[sub 2]OZrClCp[sub 2]. [beta]-Hydride elimination is also observed from Cp(PMe[sub 3])[sub 2]RuCH[double bond]CHZrClCp[sub 2]; in the presence of excess [sup n]BuC[triple bond]CH, the products are Cp(PMe[sub 3])[sub 2]Ru-C[triple bond]C-H and the zirconium vinyl complex Cp[sub 2]Zr(Cl)CH[double bond]CH[sup n]Bu. 25 refs.

  17. Excitation photon energy dependence of the relaxation processes of the photoexcited states in a quasi-one-dimensional halogen bridged Pt complex

    NASA Astrophysics Data System (ADS)

    Wada, Y.; Matsushita, N.; Ohashi, N.

    Excitation photon energy dependence of the relaxation processes of the photoexcited states in a quasi-one-dimensional halogenbridged platinum complex has been investigated by femto second transient absorption measurements. In a Pt complex, [Pt(en)2][Pt(en)2I2](SO4)2.6H2O (Pt-I-SO4), a photo-induced absorption (PA) band caused by self trapped excitons (STE's) has been observed when the excitation photon energy is close to the peak energy, 1.44 eV, of the absorption band of the one photon allowed charge transfer (CT) exciton with odd parity. In addition, a long lived PA bands caused by charged solitons (CS's) has been observed. The intensity of these long lived CS absorption band shows quadratic excitation power dependence. This shows that CS's pairs are not generated from odd-CT-excitons but from the higher energy two photon excited states. When the excitation photon energy is close to a half of the of the even CT- exciton energy, 1.84 eV, PA bands caused by STE's and CS's have been observed. These states are generated from the two photon excited even CT-excitons. When the excitation photon energy is much higher than the energy of the odd CT-exciton, PA bands caused by CS's and polarons have been observed. The intensities of these PA bands show linear excitation power dependences. Photo-generated free electron hole pairs are considered to relax into CS's and polarons.

  18. Sulphite Railroad Bridge1896, Title Sheet Sulphite Railroad Bridge, Former ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    Sulphite Railroad Bridge-1896, Title Sheet - Sulphite Railroad Bridge, Former Boston & Maine Railroad (originally Tilton & Franklin Railroad) spanning Winnipesautee River, Franklin, Merrimack County, NH

  19. LODGEPOLE BRIDGE, FACING NORTHWEST Generals Highway, Lodge Pole Bridge, ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    LODGEPOLE BRIDGE, FACING NORTHWEST - Generals Highway, Lodge Pole Bridge, Spanning Marble Fork of Kaweah River, approximately 21 miles northwest of Ash Mountain Entrance, Three Rivers, Tulare County, CA

  20. LODGEPOLE BRIDGE, FACING SOUTHEAST Generals Highway, Lodge Pole Bridge, ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    LODGEPOLE BRIDGE, FACING SOUTHEAST - Generals Highway, Lodge Pole Bridge, Spanning Marble Fork of Kaweah River, approximately 21 miles northwest of Ash Mountain Entrance, Three Rivers, Tulare County, CA

  1. Precision bolometer bridge

    NASA Technical Reports Server (NTRS)

    White, D. R.

    1968-01-01

    Prototype precision bolometer calibration bridge is manually balanced device for indicating dc bias and balance with either dc or ac power. An external galvanometer is used with the bridge for null indication, and the circuitry monitors voltage and current simultaneously without adapters in testing 100 and 200 ohm thin film bolometers.

  2. Active-bridge oscillator

    DOEpatents

    Wessendorf, Kurt O.

    2001-01-01

    An active bridge oscillator is formed from a differential amplifier where positive feedback is a function of the impedance of one of the gain elements and a relatively low value common emitter resistance. This use of the nonlinear transistor parameter h stabilizes the output and eliminates the need for ALC circuits common to other bridge oscillators.

  3. Virtual Bridge Design Challenge

    ERIC Educational Resources Information Center

    Mitts, Charles R.

    2013-01-01

    This design/problem-solving activity challenges students to design a replacement bridge for one that has been designated as either structurally deficient or functionally obsolete. The Aycock MS Technology/STEM Magnet Program Virtual Bridge Design Challenge is an authentic introduction to the engineering design process. It is a socially relevant…

  4. Modelling a Suspension Bridge.

    ERIC Educational Resources Information Center

    Rawlins, Phil

    1991-01-01

    The quadratic function can be modeled in real life by a suspension bridge that supports a uniform weight. This activity uses concrete models and computer generated graphs to discover the mathematical model of the shape of the main cable of a suspension bridge. (MDH)

  5. 1. VIEW ALONG APPROXIMATE CENTERLINE OF PROPOSED NEW BRIDGE. FLUME ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    1. VIEW ALONG APPROXIMATE CENTERLINE OF PROPOSED NEW BRIDGE. FLUME AT RIGHT CENTER IS FED FROM SMALL DIVERSION DAM ON MIDDLE FORK OF TULE RIVER, LOOKING SOUTH. (65mm lens) - Tule River Hydroelectric Complex, Tule River Bridge, Spanning North Fork of Middle Fork of Tule River, Springville, Tulare County, CA

  6. 3. VIEW ALONG FLUME TOWARD DOWNSTREAM SIDE OF BRIDGE AND ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    3. VIEW ALONG FLUME TOWARD DOWNSTREAM SIDE OF BRIDGE AND POWERHOUSE. FLUME IS FED FROM AFTERBAY OF POWERHOUSE. LOOKING NEAST-NORTHEAST. 90mm lens - Tule River Hydroelectric Complex, Tule River Bridge, Spanning North Fork of Middle Fork of Tule River, Springville, Tulare County, CA

  7. 13. VIEW OF UNDERSIDE OF BRIDGE, SHOWING TENSION RODS, SWAY ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    13. VIEW OF UNDERSIDE OF BRIDGE, SHOWING TENSION RODS, SWAY BRACING TIMBER STRINGERS CARRYING CORRUGATED METAL DECK. LOOKING NORTH-NORTHWEST. 65mm lens - Tule River Hydroelectric Complex, Tule River Bridge, Spanning North Fork of Middle Fork of Tule River, Springville, Tulare County, CA

  8. Evaluation of a bridge using simplified element modeling

    SciTech Connect

    Farrar, C.R.; Duffey, T.A.

    1995-02-01

    An experimental-numerical comparison of the forced and ambient vibrations Of a multi-span composite plate-girder bridge was performed. The bridge was modeled using a finite element program at three levels of complexity, including a simple 250 DOF model that utilizes a single beam element to represent the entire bridge cross section. Difficulties encountered in the development of the simple model are discussed. The dynamic properties predicted by the simple model were consistent with these measured on the bridge and computed using more detailed finite element models.

  9. 5. View of Clark Fork Vehicle Bridge facing east. Bridge ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    5. View of Clark Fork Vehicle Bridge facing east. Bridge from south shore of Clark Fork River-southernmost span. 1900-era Northern Pacific Railway Bridge in background. - Clark Fork Vehicle Bridge, Spanning Clark Fork River, serves Highway 200, Clark Fork, Bonner County, ID

  10. VIEW OF BRIDGE, LOOKING SOUTHWEST, WITH SOUTHERN PACIFIC RAILROAD BRIDGE ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    VIEW OF BRIDGE, LOOKING SOUTHWEST, WITH SOUTHERN PACIFIC RAILROAD BRIDGE IN BACKGROUND. THE PAVEMENT OF THE NORTH APPROACH IS SEEN BURIED ON THE RIGHT. ROADWAY (CENTER) CROSSES THE USUALLY DRY CHANNEL OF THE SALT RIVER. A BALUSTRADE OF THE MILL AVENUE BRIDGE IS SEEN AT THE LOWER LEFT CORNER - Ash Avenue Bridge, Spanning Salt River at Foot of Ash Avenue, Tempe, Maricopa County, AZ

  11. Bridging Humanism and Behaviorism.

    ERIC Educational Resources Information Center

    Chu, Lily

    1980-01-01

    Humanistic behaviorism may provide the necessary bridge between behaviorism and humanism. Perhaps the most humanistic approach to teaching is to learn how certain changes will help students and how these changes can be accomplished. (Author/MLF)

  12. Mineral bridges in nacre.

    PubMed

    Checa, Antonio G; Cartwright, Julyan H E; Willinger, Marc-Georg

    2011-12-01

    We confirm with high-resolution techniques the existence of mineral bridges between superposed nacre tablets. In the towered nacre of both gastropods and the cephalopod Nautilus there are large bridges aligned along the tower axes, corresponding to gaps (150-200nm) in the interlamellar membranes. Gaps are produced by the interaction of the nascent tablets with a surface membrane that covers the nacre compartment. In the terraced nacre of bivalves bridges associated with elongated gaps in the interlamellar membrane (>100nm) have mainly been found at or close to the edges of superposed parental tablets. To explain this placement, we hypothesize that the interlamellar membrane breaks due to differences in osmotic pressure across it when the interlamellar space below becomes reduced at an advanced stage of calcification. In no cases are the minor connections between superimposed tablets (<60nm), earlier reported to be mineral bridges, found to be such.

  13. Enhancing the magnetic coupling of oxalato-bridged Re(IV)2M(II) (M=Mn, Co, Ni, and Cu) trinuclear complexes via peripheral halide ligand effects.

    PubMed

    Martínez-Lillo, José; Mastropietro, Teresa F; De Munno, Giovanni; Lloret, Francesc; Julve, Miguel; Faus, Juan

    2011-06-20

    Four heterotrinuclear Re(IV)(2)M(II) compounds of general formula (NBu(4))(2)[{Re(IV)Br(4)(μ-ox)}(2)M(II)(Him)(2)] [NBu(4)(+) = tetra-n-butylammonium cation, ox = oxalate, Him = imidazole; M = Mn (1), Co (2), Ni (3), and Cu (4)] have been synthesized by using the novel mononuclear complex [Re(IV)Br(4)(ox)](2-) as a ligand toward divalent first-row transition metal ions in the presence of imidazole. Compounds 1-4 are isostructural complexes whose structure contains discrete trinuclear [{Re(IV)Br(4)(μ-ox)}(2)M(II)(Him)(2)](2-) anions and bulky NBu(4)(+) cations. The Re and M atoms are six-coordinated: four peripheral bromo and two oxalate-oxygens (at Re), and two cis-coordinated imidazole molecules and four oxygen atoms from two oxalate ligands (at M), build distorted octahedral surroundings. Two peripheral [ReBr(4)(ox)](2-) units act as bidentate ligands through the oxalate group toward the central [M(II)(Him)(2)] fragment affording the trinuclear entities. The values of the intramolecular Re···M separation are 5.62(1) (1), 5.51(1) (2), 5.46(1) (3), and 5.55(1) Å (4). Magnetic susceptibility measurements on polycrystalline samples of 1-4 in the temperature range of 1.9-300 K show the occurrence of intramolecular antiferro- [J = -1.1 cm(-1) (1)] and ferromagnetic interactions [J = +3.9 (2), +19.7 (3), and +14.4 cm(-1) (4)], the Hamiltonian being defined as Ĥ = -J [Ŝ(M)(Ŝ(Re1) + Ŝ(Re2))]. The larger spin delocalization on the oxalato bridge in 1-4 when compared to the trinuclear Re(IV)(2)M(II) complexes with chloro instead of bromo as peripheral ligands (1'-4') accounts for the strengthening of the magnetic interactions in 1-4 [J = -0.35 (1'), +14.2 (3'), and +7.7 cm(-1) (4')]. An incipient frequency dependence of the out-of-phase ac signals of 3 at very low temperatures is reminiscent of a system with slow relaxation of the magnetization, a phenomenon characteristic of single-molecule magnet behavior.

  14. Multivariate Feature Selection for Predicting Scour-Related Bridge Damage using a Genetic Algorithm

    NASA Astrophysics Data System (ADS)

    Anderson, I.

    2015-12-01

    Scour and hydraulic damage are the most common cause of bridge failure, reported to be responsible for over 60% of bridge failure nationwide. Scour is a complex process, and is likely an epistatic function of both bridge and stream conditions that are both stationary and in dynamic flux. Bridge inspections, conducted regularly on bridges nationwide, rate bridge health assuming a static stream condition, and typically do not include dynamically changing geomorphological adjustments. The Vermont Agency of Natural Resources stream geomorphic assessment data could add value into the current bridge inspection and scour design. The 2011 bridge damage from Tropical Storm Irene served as a case study for feature selection to improve bridge scour damage prediction in extreme events. The bridge inspection (with over 200 features on more than 300 damaged and 2,000 non-damaged bridges), and the stream geomorphic assessment (with over 300 features on more than 5000 stream reaches) constitute "Big Data", and together have the potential to generate large numbers of combined features ("epistatic relationships") that might better predict scour-related bridge damage. The potential combined features pose significant computational challenges for traditional statistical techniques (e.g., multivariate logistic regression). This study uses a genetic algorithm to perform a search of the multivariate feature space to identify epistatic relationships that are indicative of bridge scour damage. The combined features identified could be used to improve bridge scour design, and to better monitor and rate bridge scour vulnerability.

  15. DETAIL VIEW OF BRIDGE CRANE USED TO LIFT DOMED LIDS ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    DETAIL VIEW OF BRIDGE CRANE USED TO LIFT DOMED LIDS OF THE ALTITUDE CHAMBERS, FACING SOUTHWEST - Cape Canaveral Air Force Station, Launch Complex 39, Altitude Chambers, First Street, between Avenue D and Avenue E, Cape Canaveral, Brevard County, FL

  16. 67. VAL BRIDGE AND BARGES PRIOR TO CONNECTING TO SUPPORT ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    67. VAL BRIDGE AND BARGES PRIOR TO CONNECTING TO SUPPORT CARRIAGE, April 12, 1948. - Variable Angle Launcher Complex, Variable Angle Launcher, CA State Highway 39 at Morris Reservior, Azusa, Los Angeles County, CA

  17. 68. COMPLETED ASSEMBLY SHOWING BARGES, BRIDGE AND SUPPORT CARRIAGE AT ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    68. COMPLETED ASSEMBLY SHOWING BARGES, BRIDGE AND SUPPORT CARRIAGE AT THE BASE OF THE LAUNCHING SLAB LOOKING EAST, April 26, 1948. - Variable Angle Launcher Complex, Variable Angle Launcher, CA State Highway 39 at Morris Reservior, Azusa, Los Angeles County, CA

  18. 26. VAL, DETAIL OF CONTROL PANEL FOR LAUNCHER BRIDGE, COUNTERWEIGHT ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    26. VAL, DETAIL OF CONTROL PANEL FOR LAUNCHER BRIDGE, COUNTERWEIGHT CAR AND WINDSTAY WINCHES. - Variable Angle Launcher Complex, Variable Angle Launcher, CA State Highway 39 at Morris Reservior, Azusa, Los Angeles County, CA

  19. 24. VAL, CONTROL PANELS FOR LAUNCHER BRIDGE COUNTERWEIGHT CAR AND ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    24. VAL, CONTROL PANELS FOR LAUNCHER BRIDGE COUNTERWEIGHT CAR AND WINDSTAY WINCHES OVERLOOKING FIRING RANGE AND MORRIS DAM LOOKING SOUTHWEST. - Variable Angle Launcher Complex, Variable Angle Launcher, CA State Highway 39 at Morris Reservior, Azusa, Los Angeles County, CA

  20. 43. VAL, DETAIL OF CAMERA STATION ON CONNECTING BRIDGE SHOWING ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    43. VAL, DETAIL OF CAMERA STATION ON CONNECTING BRIDGE SHOWING SIDE THAT FACED THE VAL. - Variable Angle Launcher Complex, Variable Angle Launcher, CA State Highway 39 at Morris Reservior, Azusa, Los Angeles County, CA

  1. 3. VAL PROJECTILE LOADING DECK, SUPPORT CARRIAGE AND LAUNCHING BRIDGE ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    3. VAL PROJECTILE LOADING DECK, SUPPORT CARRIAGE AND LAUNCHING BRIDGE LOOKING SOUTHWEST. - Variable Angle Launcher Complex, Variable Angle Launcher, CA State Highway 39 at Morris Reservior, Azusa, Los Angeles County, CA

  2. 42. VAL, DETAIL OF CONNECTING BRIDGE SHOWING SIDE THAT FACED ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    42. VAL, DETAIL OF CONNECTING BRIDGE SHOWING SIDE THAT FACED THE VAL TAKEN FROM BARGE DECK. - Variable Angle Launcher Complex, Variable Angle Launcher, CA State Highway 39 at Morris Reservior, Azusa, Los Angeles County, CA

  3. 41. VAL, DETAIL OF CONNECTING BRIDGE SHOWING SIDE THAT FACED ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    41. VAL, DETAIL OF CONNECTING BRIDGE SHOWING SIDE THAT FACED THE FIRING RANGE TAKEN FROM THE BARGE DECK. - Variable Angle Launcher Complex, Variable Angle Launcher, CA State Highway 39 at Morris Reservior, Azusa, Los Angeles County, CA

  4. 44. VAL, DETAIL LOOKING THROUGH THE CONNECTING BRIDGE FROM BARGE ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    44. VAL, DETAIL LOOKING THROUGH THE CONNECTING BRIDGE FROM BARGE TO BARGE. - Variable Angle Launcher Complex, Variable Angle Launcher, CA State Highway 39 at Morris Reservior, Azusa, Los Angeles County, CA

  5. 25. VAL, DETAIL OF CONTROL PANEL FOR LAUNCHER BRIDGE, COUNTERWEIGHT ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    25. VAL, DETAIL OF CONTROL PANEL FOR LAUNCHER BRIDGE, COUNTERWEIGHT CAR AND WINDSTAY WINCHES. - Variable Angle Launcher Complex, Variable Angle Launcher, CA State Highway 39 at Morris Reservior, Azusa, Los Angeles County, CA

  6. 5. VAL LAUNCHER BRIDGE OVER LAUNCHER SLAB TAKEN FROM RESERVOIR ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    5. VAL LAUNCHER BRIDGE OVER LAUNCHER SLAB TAKEN FROM RESERVOIR LOOKING NORTH. - Variable Angle Launcher Complex, Variable Angle Launcher, CA State Highway 39 at Morris Reservior, Azusa, Los Angeles County, CA

  7. 18. VAL, DETAIL OF LAUNCHER BRIDGE ALONG THE SIDE OF ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    18. VAL, DETAIL OF LAUNCHER BRIDGE ALONG THE SIDE OF THE 32' DIAMETER LAUNCHING TUBE LOOKING SOUTHWEST. - Variable Angle Launcher Complex, Variable Angle Launcher, CA State Highway 39 at Morris Reservior, Azusa, Los Angeles County, CA

  8. 6. VAL LAUNCHER BRIDGE, CARRIAGE SUPPORT, CONCRETE 'A' FRAME STRUCTURE ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    6. VAL LAUNCHER BRIDGE, CARRIAGE SUPPORT, CONCRETE 'A' FRAME STRUCTURE AND CAMERA TOWER LOOKING NORTHWEST. - Variable Angle Launcher Complex, Variable Angle Launcher, CA State Highway 39 at Morris Reservior, Azusa, Los Angeles County, CA

  9. 31. VAL, DETAIL OF LOADING PLATFORM ADJACENT TO LAUNCHER BRIDGE ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    31. VAL, DETAIL OF LOADING PLATFORM ADJACENT TO LAUNCHER BRIDGE LOOKING WEST. - Variable Angle Launcher Complex, Variable Angle Launcher, CA State Highway 39 at Morris Reservior, Azusa, Los Angeles County, CA

  10. 21. VAL, DETAIL OF MUZZLE END OF LAUNCHER BRIDGE SHOWING ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    21. VAL, DETAIL OF MUZZLE END OF LAUNCHER BRIDGE SHOWING BOTH LAUNCHER TUBES TAKEN FROM RESERVOIR LOOKING NORTH. - Variable Angle Launcher Complex, Variable Angle Launcher, CA State Highway 39 at Morris Reservior, Azusa, Los Angeles County, CA

  11. Synthesis and Characterization of a Ditriflate-Bridged, Diiron(II) Complex with Syn-N-Donor Ligands: [Fe(2)(μ-OTf)(2)(PIC(2)DET)(2)](BARF)(2).

    PubMed

    Kodanko, Jeremy J; Lippard, Stephen J

    2008-03-01

    The synthesis and characterization of the diiron(II) complex [Fe(2)(μ-OTf)(2)-(PIC(2)DET)(2)](BARF)(2) (2), where PIC(2)DET is a 2,3-diethynyltriptycene-linked dipicolinic methyl ester ligand, are described. The dication in 2, contains, [Fe(2)(μ-OTf)(2)(PIC(2)DET)(2)](2+) two symmetry-equivalent iron atoms with octahedral coordination geometries. Each metal ion has a N(2)O(4) atom donor set that includes four atoms from two picolinic ester N,O chelate rings, as well as two oxygen atoms from the bridging trifluoromethanesulfonate groups. The Fe(2)(μ-OTf)(2) core of 2 is stabilized by two PIC(2)DET ligands that bind the two metal ions in a head-to-head fashion, leading to an Fe···Fe distance of 5.173(1)Å. Molar conductivity data for 2 are consistent with Fe(2)(μ-OTf)(2)(PIC(2)DET)(2)](2+) retaining its identity in acetone solutions, where it behaves as a 2:1 electrolyte. (1)H NMR spectroscopic, solution (d(6)-acetone) and solid-state magnetic susceptibility data all indicate that the iron atoms of 2 are high-spin (S = 2). A fit of the magnetic data (2 - 300K) to a spin-only isotropic exchange Hamiltonian H = -2JS(1)·S(2) are consistent with weak antiferromagnetic coupling between the two iron atoms with J ~ -0.99(2) cm(-1) and g = 2.10(1). PMID:18458751

  12. Copper(II) coordination chain complex with the 2,5-bis(2-pyridyl)-1,3,4-thiadiazole ligand and an asymmetric μ2-1,1-azido double-bridged: Synthesis, crystal structure and magnetic properties

    NASA Astrophysics Data System (ADS)

    Laachir, Abdelhakim; Guesmi, Salaheddine; Saadi, Mohamed; El Ammari, Lahcen; Mentré, Olivier; Vezin, Hervé; Colis, Silviu; Bentiss, Fouad

    2016-11-01

    A new asymmetric μ2-1,1-azido double bridged cooper (II), with 2,5-bis(2-pyridyl)-1,3,4-thiadiazole (L), has been synthesized and characterized using single crystal X-ray diffraction, FT-IR, UV-Visible spectroscopic and magnetic measurements. The asymmetric unit of the title compound contains half molecule of formula, C12H8CuN10S, which crystallizes in the triclinic system, space group P 1 bar , with a = 6.5916 (4)Å, b = 10.6905 (7) Å, c = 11.5037 (7) Å, α = 106.508 (3)°, β = 105.538 (3)°, γ = 90.233 (4)°, V = 745.99 (8) Å3 and Z = 2. The structure consists of two [CuN5] prismatic polyhedra linked together by edge-sharing to build up a [Cu2N8] dimer arranged in chain. The connectivity along the chain is performed by Nsbnd N edge sharing between dimers. In the crystal, the molecules are linked together by Csbnd H⋯N hydrogen bonds and by π---π interactions between parallel pyridyl rings of neighboring molecules. The interpretation of FT-IR and UV-Vis spectra is consistent with the crystal structure determined by X-ray diffraction. The magnetic properties of the complex confirm the picture of an alternated … Cu-J1-Cu ….J2 … Cu-J1-Cu … magnetic chains. We found in the dimers weak antiferromagnetic exchange interactions J1/k = -5.9 (1) k and between them J2/k = -2.3 k.

  13. Synthesis and Characterization of a Ditriflate-Bridged, Diiron(II) Complex with Syn-N-Donor Ligands: [Fe(2)(μ-OTf)(2)(PIC(2)DET)(2)](BARF)(2).

    PubMed

    Kodanko, Jeremy J; Lippard, Stephen J

    2008-03-01

    The synthesis and characterization of the diiron(II) complex [Fe(2)(μ-OTf)(2)-(PIC(2)DET)(2)](BARF)(2) (2), where PIC(2)DET is a 2,3-diethynyltriptycene-linked dipicolinic methyl ester ligand, are described. The dication in 2, contains, [Fe(2)(μ-OTf)(2)(PIC(2)DET)(2)](2+) two symmetry-equivalent iron atoms with octahedral coordination geometries. Each metal ion has a N(2)O(4) atom donor set that includes four atoms from two picolinic ester N,O chelate rings, as well as two oxygen atoms from the bridging trifluoromethanesulfonate groups. The Fe(2)(μ-OTf)(2) core of 2 is stabilized by two PIC(2)DET ligands that bind the two metal ions in a head-to-head fashion, leading to an Fe···Fe distance of 5.173(1)Å. Molar conductivity data for 2 are consistent with Fe(2)(μ-OTf)(2)(PIC(2)DET)(2)](2+) retaining its identity in acetone solutions, where it behaves as a 2:1 electrolyte. (1)H NMR spectroscopic, solution (d(6)-acetone) and solid-state magnetic susceptibility data all indicate that the iron atoms of 2 are high-spin (S = 2). A fit of the magnetic data (2 - 300K) to a spin-only isotropic exchange Hamiltonian H = -2JS(1)·S(2) are consistent with weak antiferromagnetic coupling between the two iron atoms with J ~ -0.99(2) cm(-1) and g = 2.10(1).

  14. Synthesis and Reactivity of (Pentafluorophenyl)platinate(II) Complexes with Bridging 1,8-Naphthyridine (napy) and X Ligands (X = C(6)F(5), OH, Cl, Br, I, SPh). Crystal Structure of [NBu(4)][Pt(2)(&mgr;-napy)(&mgr;-OH)(C(6)F(5))(4)].CHCl(3).

    PubMed

    Ara, Irene; Casas, José M.; Forniés, Juan; Rueda, Angel J.

    1996-12-01

    By reaction of [NBu(4)](2)[Pt(2)(&mgr;-C(6)F(5))(2)(C(6)F(5))(4)] with 1,8-naphthyridine (napy), [NBu(4)][Pt(C(6)F(5))(3)(napy)] (1) is obtained. This compound reacts with cis-[Pt(C(6)F(5))(2)(THF)(2)] to give the dinuclear derivative [NBu(4)][Pt(2)(&mgr;-napy)(&mgr;-C(6)F(5))(C(6)F(5))(4)] (2). The reaction of several HX species with 2 results in the substitution of the bridging C(6)F(5) by other ligands (X) such as OH (3), Cl (4), Br (5), I (6), and SPh (7), maintaining in all cases the naphthyridine bridging ligand. The structure of 3 was determined by single-crystal X-ray diffraction. The compound crystallizes in the monoclinic system, space group P2(1)/n, with a = 12.022(2) Å, b = 16.677(3) Å, c = 27.154(5) Å, beta = 98.58(3) degrees, V = 5383.2(16) Å(3), and Z = 4. The structure was refined to residuals of R = 0.0488 and R(w) = 0.0547. The complex consists of two square-planar platinum(II) fragments sharing a naphthyridine and OH bridging ligands, which are in cis positions. The short Pt-Pt distance [3.008(1) Å] seems to be a consequence of the bridging ligands.

  15. 4. VIEW OF SILVER BRIDGE (ST. MARY'S BRIDGE), CARRYING COUNTY ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    4. VIEW OF SILVER BRIDGE (ST. MARY'S BRIDGE), CARRYING COUNTY ROAD OVER SOURIS RIVER NEAR SOUTH END OF REFUGE, LOOKING NORTHEAST - Upper Souris National Wildlife Refuge Dams, Souris River Basin, Foxholm, Surrey (England), ND

  16. Axionometric Cutaway of Bridge Structure Shoreham Railroad Bridge, Former ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    Axionometric Cutaway of Bridge Structure - Shoreham Railroad Bridge, Former Addison County Railroad (later, Rutland Railroad, Addison Branch), spanning Lemon Fair River above Richville Pond, west of East Shoreham Road, Shoreham, Addison County, VT

  17. Shoreham Railroad Bridge, Title Sheet Shoreham Railroad Bridge, Former ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    Shoreham Railroad Bridge, Title Sheet - Shoreham Railroad Bridge, Former Addison County Railroad (later, Rutland Railroad, Addison Branch), spanning Lemon Fair River above Richville Pond, west of East Shoreham Road, Shoreham, Addison County, VT

  18. Dog Bridge, view of the deck of the bridge and ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    Dog Bridge, view of the deck of the bridge and rails looking from Linden Lane - National Park Seminary, Bounded by Capitol Beltway (I-495), Linden Lane, Woodstove Avenue, & Smith Drive, Silver Spring, Montgomery County, MD

  19. Tetranuclear hetero-metal [Co(II)2Ln(III)2] (Ln = Gd, Tb, Dy, Ho, La) complexes involving carboxylato bridges in a rare μ4-η(2):η(2) mode: synthesis, crystal structures, and magnetic properties.

    PubMed

    Abtab, Sk Md Towsif; Majee, Mithun Chandra; Maity, Manoranjan; Titiš, Ján; Boča, Roman; Chaudhury, Muktimoy

    2014-02-01

    A new family of 3d-4f heterometal 2 × 2 complexes [Co(II)2(L)2(PhCOO)2Ln(III)2(hfac)4] (1-5) (Ln = Gd (compound 1), Tb (compound 2), Dy (compound 3), Ho (compound 4), and La (compound 5)) have been synthesized in moderate yields (48-63%) following a single-pot protocol using stoichiometric amounts (1:1 mol ratio) of [Co(II)(H2L)(PhCOO)2] (H2L = N,N'-dimethyl-N,N'-bis(2-hydroxy-3,5-dimethylbenzyl)ethylenediamine) as a metalloligand and [Ln(III)(hfac)3(H2O)2] (Hhfac = hexafluoroacetylacetone) as a lanthanide precursor compound. Also reported with this series is the Zn-Dy analog [Zn(II)2(L)2(PhCOO)2Dy(III)2(hfac)4] 6 to help us in understanding the magnetic properties of these compounds. The compounds 1-6 are isostructural. Both hexafluoroacetylacetonate and benzoate play crucial roles in these structures as coligands in generating a tetranuclear core of high thermodynamic stability through a self-assembly process. The metal centers are arranged alternately at the four corners of this rhombic core, and the carboxylato oxygen atoms of each benzoate moiety bind all of the four metal centers of this core in a rare μ4-η(2):η(2) bridging mode as confirmed by X-ray crystallography. The magnetic susceptibility and magnetization data confirm a paramagnetic behavior, and no remnant magnetization exists in any of these compounds at vanishing magnetic field. The metal centers are coupled in an antiferromagnetic manner in these compounds. The [Co(II)2Dy(III)2] compound exhibits a slow magnetic relaxation below 6 K, as proven by the AC susceptibility measurements; the activation energy reads U/kB = 8.8 K (τ0 = 2.0 × 10(-7) s) at BDC = 0, and U/kB = 7.8 K (τ0 = 3.9 × 10(-7) s) at BDC = 0.1 T. The [Zn(II)2Dy(III)2] compound also behaves as a single-molecule magnet with U/kB = 47.9 K and τ0 = 2.75 × 10(-7) s.

  20. 1. WESTERN VIEW OF BRIDGE PLAZA, SHOWING MEMORIAL BRIDGE AT ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    1. WESTERN VIEW OF BRIDGE PLAZA, SHOWING MEMORIAL BRIDGE AT LEFT AND THE ROCK CREEK AND POTOMAC PARKWAY RAMP AT RIGHT. VIEW TAKEN FROM THE REAR OF THE LINCOLN MEMORIAL. - Arlington Memorial Bridge, Boundary Channel Extension, Spanning Mount Vernon Memorial Highway & Boundary Channel, Washington, District of Columbia, DC

  1. Bridge Types: Suspension Bridge Spans, Section AA; Cantilever Truss Spans, ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    Bridge Types: Suspension Bridge Spans, Section A-A; Cantilever Truss Spans, Section B-B; Through Truss Spans, Section C-C; Deck Truss Spans, Section D-D - San Francisco Oakland Bay Bridge, Spanning San Francisco Bay, San Francisco, San Francisco County, CA

  2. Vibration characteristics and damage detection in a suspension bridge

    NASA Astrophysics Data System (ADS)

    Wickramasinghe, Wasanthi R.; Thambiratnam, David P.; Chan, Tommy H. T.; Nguyen, Theanh

    2016-08-01

    Suspension bridges are flexible and vibration sensitive structures that exhibit complex and multi-modal vibration. Due to this, the usual vibration based methods could face a challenge when used for damage detection in these structures. This paper develops and applies a mode shape component specific damage index (DI) to detect and locate damage in a suspension bridge with pre-tensioned cables. This is important as suspension bridges are large structures and damage in them during their long service lives could easily go un-noticed. The capability of the proposed vibration based DI is demonstrated through its application to detect and locate single and multiple damages with varied locations and severity in the cables of the suspension bridge. The outcome of this research will enhance the safety and performance of these bridges which play an important role in the transport network.

  3. BUILDING "BRIDGES" WITH QUALITY ASSURANCE

    EPA Science Inventory

    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...

  4. The Bridges Program.

    ERIC Educational Resources Information Center

    Bohnen, Elizabeth; Klie, Judy

    This report describes BRIDGES, an employment equity special measures training program developed by the City of Toronto (Ontario, Canada). It was designed to help women employees move from their traditional jobs into trades, technical or operation (TTO) jobs within their own organization. The program is a combination of classroom sessions, shop…

  5. Building Bridges to China.

    ERIC Educational Resources Information Center

    Wasta, Stephanie; Scott, Margaret

    1998-01-01

    Describes a theme cycle called "Building Bridges to China" developed for third grade students that focuses on the similarities between the lives of children and families in China and the United States. Explains that the theme cycle addresses the National Geography Standards and three of the National Council for the Social Studies standards. (CMK)

  6. Building a Straw Bridge

    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,…

  7. Tech Prep Bridge Programs.

    ERIC Educational Resources Information Center

    Gohdes, William

    1995-01-01

    Although tech prep is still in its infancy in Georgia, increasing numbers of students are entering technical institutes after having completed the secondary-level component of tech prep programs. Georgia's technical institutes must begin the process of developing bridge programs to help adult students with no tech prep experience develop academic…

  8. Bridging the Gap?

    ERIC Educational Resources Information Center

    Salter, Colin

    2009-01-01

    The political context of the conversion of the Historic Tramway Bridge, adjacent to Sandon Point in Bulli (NSW, Australia), and how this was exploited to serve predetermined ends, illustrates that technologies can be designed to have particular social (and political) effects. Through reflection on this relatively small engineering project, this…

  9. Bridging the Abyss

    ERIC Educational Resources Information Center

    Olcott, Marianina

    2007-01-01

    This paper seeks to explain the epistemological bases for the two cultures and to show why this disciplinary divide continues to plague American academic culture. Next, we discuss strategies for bridging the two cultures through general education curricula which promote mutual understanding of the two cultures while educating students in basic…

  10. Bridging Disciplinary Boundaries

    ERIC Educational Resources Information Center

    Mei, Linda

    2009-01-01

    Interdisciplinary education promotes the unity of knowledge by bridging the cultural divide between the social constructs of disciplines and encourages the development of knowledge to enhance society. As an inquiry-based and relevant approach that expands and advances knowledge, interdisciplinary education facilitates creativity and flexibility,…

  11. Bridging the Gap.

    ERIC Educational Resources Information Center

    Kroto, Joseph J.

    1988-01-01

    Describes interdisciplinary activities with real-world applications ranging from science to mathematics to technology. Cites the study and construction of model bridges as a way for students to learn about engineering concepts and some of their relationships. States that the exercise enhanced teacher cooperation between the different fields. (RT)

  12. Building Migratory Bridges

    ERIC Educational Resources Information Center

    Roy, Michael; Doss, Laurie K.

    2007-01-01

    The Building Migratory Bridges (BOMB) program--a collaboration between the Marvel wood School and Audubon Sharon in Connecticut and Conservation Research Education Action (CR EA), a U.S. not-for-profit in Panama--uses nontropical migratory bird research in the United States and Panama to demonstrate how negative environmental impacts in one…

  13. Bridging the Gaps.

    ERIC Educational Resources Information Center

    Netzer, Greg

    1995-01-01

    Discusses a model water quality monitoring project, Project Bridge, established to train minority girls about to enter eighth grade in scientific procedures followed by hands-on experimentation. Students spent a week monitoring water in an urban stream and analyzing results. (LZ)

  14. Virtual Bridge Design

    ERIC Educational Resources Information Center

    Bisogno, Janet; JeanPierre, Bobby

    2008-01-01

    The West Point Bridge Design (WPBD) building project engages students in project-based learning by giving them a real-life problem to solve. By using technology, students are able to become involved in solving problems that they normally would not encounter. Involvement with interactive websites, such as WPBD, assists students in using…

  15. The Bridge to Somewhere

    ERIC Educational Resources Information Center

    Lum, Lydia

    2009-01-01

    Since its inception in 2000, Pan-Asian American Community House's (PAACH's) education mission has bridged Asian-American studies to student life. PAACH initiatives have helped spread Asian-American diaspora to thousands of students at the University of Pennsylvania. They have also helped students determine for themselves what it means to be a…

  16. Bridge condition assessment using D numbers.

    PubMed

    Deng, Xinyang; Hu, Yong; Deng, Yong

    2014-01-01

    Bridge condition assessment is a complex problem influenced by many factors. The uncertain environment increases more its complexity. Due to the uncertainty in the process of assessment, one of the key problems is the representation of assessment results. Though there exists many methods that can deal with uncertain information, however, they have more or less deficiencies. In this paper, a new representation of uncertain information, called D numbers, is presented. It extends the Dempster-Shafer theory. By using D numbers, a new method is developed for the bridge condition assessment. Compared to these existing methods, the proposed method is simpler and more effective. An illustrative case is given to show the effectiveness of the new method.

  17. Hydrogen versus fluorine: effects on molecular structure and intermolecular interactions in a platinum isocyanate complex.

    PubMed

    Raven, William; Joschko, Thomas; Kalf, Irmgard; Englert, Ulli

    2016-03-01

    At the molecular level, the enantiomerically pure square-planar organoplatinum complex (SP-4-4)-(R)-[2-(1-aminoethyl)-5-fluorophenyl-κ(2)C(1),N][(R)-1-(4-fluorophenyl)ethylamine-κN](isocyanato-κN)platinum(II), [Pt(C8H9FN)(NCO)(C8H10FN)], and its congener without fluorine substituents on the aryl rings adopt the same structure within error. The similarities between the compounds extend to the most relevant intermolecular interactions, i.e. N-H...O and N-H...N hydrogen bonds link neighbouring molecules into chains along the shortest lattice parameter in each structure. Differences between the crystal structures of the fluoro-substituted and parent complex become obvious with respect to secondary interactions perpendicular to the classical hydrogen bonds; the fluorinated compound features short C-H...F contacts with an F...H distance of ca 2.6 Å. The fluorine substitution is also reflected in reduced backbonding from the metal cation to the isocyanate ligand. PMID:26942427

  18. Hydrogen versus fluorine: effects on molecular structure and intermolecular interactions in a platinum isocyanate complex.

    PubMed

    Raven, William; Joschko, Thomas; Kalf, Irmgard; Englert, Ulli

    2016-03-01

    At the molecular level, the enantiomerically pure square-planar organoplatinum complex (SP-4-4)-(R)-[2-(1-aminoethyl)-5-fluorophenyl-κ(2)C(1),N][(R)-1-(4-fluorophenyl)ethylamine-κN](isocyanato-κN)platinum(II), [Pt(C8H9FN)(NCO)(C8H10FN)], and its congener without fluorine substituents on the aryl rings adopt the same structure within error. The similarities between the compounds extend to the most relevant intermolecular interactions, i.e. N-H...O and N-H...N hydrogen bonds link neighbouring molecules into chains along the shortest lattice parameter in each structure. Differences between the crystal structures of the fluoro-substituted and parent complex become obvious with respect to secondary interactions perpendicular to the classical hydrogen bonds; the fluorinated compound features short C-H...F contacts with an F...H distance of ca 2.6 Å. The fluorine substitution is also reflected in reduced backbonding from the metal cation to the isocyanate ligand.

  19. Bridged ferrocenes. 10. Structural phenomena

    SciTech Connect

    Hillman, M.; Fujita, E.; Dauplaise, H.; Kvick, A.; Kerber, R.C.

    1984-01-01

    The structures of 1,1',2,2'-bis(tetramethylene)ferrocene, I, 1,1',2,2',4,4'-tris(tetramethylene)ferrocene, II, and 1,1',2,2',4,4'-tris(pentamethylene)ferrocene, III, are given and are compared to the previously determined structure of 1,1',2,2',4,4'-tris(trimethylene)ferrocene, IV. The iron-to-ring distances are consistent with the reported Moessbauer spectra and redox potentials. The cyclopentadienyl rings are eclipsed in the compounds with trimethylene and pentamethylene bridges but are staggered by 12-14 in the compounds with tetramethylene bridges. In compounds with tetra- and pentamethylene bridges the presence of staggering or eclipsing is attributed to the need to avoid eclipsing of the protons in the bridges. In the compound with three trimethylene bridges, the shortness of the bridges is of primary importance. The staggered conformation observed in I and II may be the source of the apparent anomalies observed in the ring-proton region of the NMR spectra of bridged ferrocenes. The bridge-proton region of the NMR spectra at 360 MHz are given for I and other bridged ferrocenes. Disorder of the bridge carbons observed in the crystals are correlated with the flipping of the bridges observed in the NMR spectra. 30 references, 8 tables.

  20. Molecular engineering with bridged polysilsesquioxanes

    SciTech Connect

    LOY,DOUGLAS A.; SHEA,KENNETH J.

    2000-05-09

    Bridged polysilsesquioxanes are a class of hybrid organic-inorganic materials that permit molecular engineering of bulk properties including porosity. Prepared by sol-gel polymerization of monomers with two or more trialkoxysilyl groups, the materials are highly cross-linked amorphous polymers that are readily obtained as gels. The bridging configuration of the hydrocarbon group insures that network polymers are readily formed and that the organic functionality is homogeneously distributed throughout the polymeric scaffolding at the molecular level. This permits the bulk properties, including surface area, pore size, and dielectric constant to be engineered through the selection of the bridging organic group. Numerous bridging groups have been incorporated. This presentation will focus on the effects that the length, flexibility, and substitution geometry of the hydrocarbon bridging groups have on the properties of the resulting bridged polysilsesquioxanes. Details of the preparation, characterization, and some structure property relationships of these bridged polysilsesquioxanes will be given.

  1. Electrical Actuation Technology Bridging

    NASA Technical Reports Server (NTRS)

    Hammond, Monica (Compiler); Sharkey, John (Compiler)

    1993-01-01

    This document contains the proceedings of the NASA Electrical Actuation Technology Bridging (ELA-TB) Workshop held in Huntsville, Alabama, September 29-October 1, 1992. The workshop was sponsored by the NASA Office of Space Systems Development and Marshall Space Flight Center (MSFC). The workshop addressed key technologies bridging the entire field of electrical actuation including systems methodology, control electronics, power source systems, reliability, maintainability, and vehicle health management with special emphasis on thrust vector control (TVC) applications on NASA launch vehicles. Speakers were drawn primarily from industry with participation from universities and government. In addition, prototype hardware demonstrations were held at the MSFC Propulsion Laboratory each afternoon. Splinter sessions held on the final day afforded the opportunity to discuss key issues and to provide overall recommendations. Presentations are included in this document.

  2. Climbing techniques for bridge inspection

    NASA Astrophysics Data System (ADS)

    Kaslan, Erol C.

    1998-03-01

    California has about 24,000 publicly owned bridges that require routine structural evaluations to comply with National Bridge Inspection Standard (NBIS) mandates. Of these, about 800 are identified as possessing fatigue prone or fracture critical details requiring thorough tactile investigations. Gaining access to bridge elements to perform these investigations has become increasingly difficult and costly. The traditional uses of under bridge inspection trucks, lift equipment and rigging are economically and practically limited by bridge size, structure type, traffic demands and support costs. In some cases, bridges that have become damaged by earthquakes cannot safely support the loads of heavy personnel lift equipment. The California Department of Transportation (Caltrans)'s Office of Structural Materials and Office of Structure Maintenance and Investigations evaluated the use of rock climbing and mountaineering techniques as an alternative means of gaining access for bridge inspections. Under a small research grant, a bridge climbing training course was developed through a local University of California outdoor recreation group and 7 engineers and technicians were initially trained. A comprehensive Code of Safe Practices was created and standards of training, procedures and equipment required for bridge inspections were established. A successful climb investigation on a large, previously inaccessible arch bridge was completed at the end of the training that proved the techniques safe, economical and effective. Within one year, 20 bridge maintenance engineers were trained, and a formal program was established to organize, schedule, equip and certify engineers and technicians for bridge climbing. Several other offices within Caltrans as well as the California Department of Water Resources have since adopted these techniques for specialized structural inspection tasks. Climbing techniques are now used routinely in California as an alterative means of gaining access

  3. Basis of Design and Seismic Action for Long Suspension Bridges: the case of the Messina Strait Bridge

    SciTech Connect

    Bontempi, Franco

    2008-07-08

    The basis of design for complex structures like suspension bridges is reviewed. Specific attention is devoted to seismic action and to the performance required and to the connected structural analysis. Uncertainty is specially addressed by probabilistic and soft-computing techniques. The paper makes punctual reference to the work end the experience developed during the last years for the re-design of the Messina Strait Bridge.

  4. The structure of a dual-specificity tyrosine phosphorylation-regulated kinase 1A-PKC412 complex reveals disulfide-bridge formation with the anomalous catalytic loop HRD(HCD) cysteine.

    PubMed

    Alexeeva, Marina; Åberg, Espen; Engh, Richard A; Rothweiler, Ulli

    2015-05-01

    Dual-specificity tyrosine phosphorylation-regulated kinase 1A (DYRK1A) is a protein kinase associated with neuronal development and brain physiology. The DYRK kinases are very unusual with respect to the sequence of the catalytic loop, in which the otherwise highly conserved arginine of the HRD motif is replaced by a cysteine. This replacement, along with the proximity of a potential disulfide-bridge partner from the activation segment, implies a potential for redox control of DYRK family activities. Here, the crystal structure of DYRK1A bound to PKC412 is reported, showing the formation of the disulfide bridge and associated conformational changes of the activation loop. The DYRK kinases represent emerging drug targets for several neurological diseases as well as cancer. The observation of distinct activation states may impact strategies for drug targeting. In addition, the characterization of PKC412 binding offers new insights for DYRK inhibitor discovery. PMID:25945585

  5. Foundation Depth for Bridge Piers

    NASA Astrophysics Data System (ADS)

    Veerappadevaru, G.; Gangadharaiah, T.; Jagadeesh, T. R.

    2013-09-01

    The safety of bridge piers built in rivers having the bed is one of the prime aspects in the study of scouring process around bridge piers. The stability of bridge piers depends on the depth of foundation provided below maximum scour level. The stability analysis of bridge piers is carried based on moment of forces acting on the caisson pier when the pier slides and tilts slightly in downstream from its position. The experiments are conducted for three pier shapes on two sediment beds and for different flow conditions. The curves indicating the stability limits are compared with Lacey's recommendations which are used in present day practice in India. The analysis presented here indicates that the Lacey's recommendation for railway bridges is safe and for some cases of the road bridges depends on grip length, angle of tilt and weight of caisson.

  6. The active-bridge oscillator

    SciTech Connect

    Wessendorf, K.O.

    1998-07-01

    This paper describes the Active-Bridge Oscillator (ABO), a new concept in high-stability oscillator design. The ABO is ab ridge-type oscillator design that is easly to design and overcomes many of the operational and design difficulties associated with standard bridge oscillator designs. The ABO will oscillate with a very stable output amplitude over a wide range of operating conditions without the use of an automatic-level-control (ALC). A standard bridge oscillator design requires an ALC to maintain the desired amplitude of oscillation. for this and other reasons, bridge oscilaltors are not used in mainstream designs. Bridge oscillators are generally relegated to relatively low-volume, high-performance applications. The Colpitts and Pierce designs are the most popular oscillators but are typically less stable than a bridge-type oscillator.

  7. The preparation of electrohydrodynamic bridges from polar dielectric liquids.

    PubMed

    Wexler, Adam D; López Sáenz, Mónica; Schreer, Oliver; Woisetschläger, Jakob; Fuchs, Elmar C

    2014-09-30

    Horizontal and vertical liquid bridges are simple and powerful tools for exploring the interaction of high intensity electric fields (8-20 kV/cm) and polar dielectric liquids. These bridges are unique from capillary bridges in that they exhibit extensibility beyond a few millimeters, have complex bi-directional mass transfer patterns, and emit non-Planck infrared radiation. A number of common solvents can form such bridges as well as low conductivity solutions and colloidal suspensions. The macroscopic behavior is governed by electrohydrodynamics and provides a means of studying fluid flow phenomena without the presence of rigid walls. Prior to the onset of a liquid bridge several important phenomena can be observed including advancing meniscus height (electrowetting), bulk fluid circulation (the Sumoto effect), and the ejection of charged droplets (electrospray). The interaction between surface, polarization, and displacement forces can be directly examined by varying applied voltage and bridge length. The electric field, assisted by gravity, stabilizes the liquid bridge against Rayleigh-Plateau instabilities. Construction of basic apparatus for both vertical and horizontal orientation along with operational examples, including thermographic images, for three liquids (e.g., water, DMSO, and glycerol) is presented.

  8. The preparation of electrohydrodynamic bridges from polar dielectric liquids.

    PubMed

    Wexler, Adam D; López Sáenz, Mónica; Schreer, Oliver; Woisetschläger, Jakob; Fuchs, Elmar C

    2014-01-01

    Horizontal and vertical liquid bridges are simple and powerful tools for exploring the interaction of high intensity electric fields (8-20 kV/cm) and polar dielectric liquids. These bridges are unique from capillary bridges in that they exhibit extensibility beyond a few millimeters, have complex bi-directional mass transfer patterns, and emit non-Planck infrared radiation. A number of common solvents can form such bridges as well as low conductivity solutions and colloidal suspensions. The macroscopic behavior is governed by electrohydrodynamics and provides a means of studying fluid flow phenomena without the presence of rigid walls. Prior to the onset of a liquid bridge several important phenomena can be observed including advancing meniscus height (electrowetting), bulk fluid circulation (the Sumoto effect), and the ejection of charged droplets (electrospray). The interaction between surface, polarization, and displacement forces can be directly examined by varying applied voltage and bridge length. The electric field, assisted by gravity, stabilizes the liquid bridge against Rayleigh-Plateau instabilities. Construction of basic apparatus for both vertical and horizontal orientation along with operational examples, including thermographic images, for three liquids (e.g., water, DMSO, and glycerol) is presented. PMID:25350319

  9. The Preparation of Electrohydrodynamic Bridges from Polar Dielectric Liquids

    PubMed Central

    Wexler, Adam D.; López Sáenz, Mónica; Schreer, Oliver; Woisetschläger, Jakob; Fuchs, Elmar C.

    2014-01-01

    Horizontal and vertical liquid bridges are simple and powerful tools for exploring the interaction of high intensity electric fields (8-20 kV/cm) and polar dielectric liquids. These bridges are unique from capillary bridges in that they exhibit extensibility beyond a few millimeters, have complex bi-directional mass transfer patterns, and emit non-Planck infrared radiation. A number of common solvents can form such bridges as well as low conductivity solutions and colloidal suspensions. The macroscopic behavior is governed by electrohydrodynamics and provides a means of studying fluid flow phenomena without the presence of rigid walls. Prior to the onset of a liquid bridge several important phenomena can be observed including advancing meniscus height (electrowetting), bulk fluid circulation (the Sumoto effect), and the ejection of charged droplets (electrospray). The interaction between surface, polarization, and displacement forces can be directly examined by varying applied voltage and bridge length. The electric field, assisted by gravity, stabilizes the liquid bridge against Rayleigh-Plateau instabilities. Construction of basic apparatus for both vertical and horizontal orientation along with operational examples, including thermographic images, for three liquids (e.g., water, DMSO, and glycerol) is presented. PMID:25350319

  10. Morphological aspects of myocardial bridges.

    PubMed

    Lujinović, Almira; Kulenović, Amela; Kapur, Eldan; Gojak, Refet

    2013-11-01

    Although some myocardial bridges can be asymptomatic, their presence often causes coronary disease either through direct compression of the "tunnel" segment or through stimulation and accelerated development of atherosclerosis in the segment proximally to the myocardial bridge. The studied material contained 30 human hearts received from the Department of Anatomy. The hearts were preserved 3 to 5 days in 10% formalin solution. Thereafter, the fatty tissue was removed and arterial blood vessels prepared by careful dissection with special reference to the presence of the myocardial bridges. Length and thickness of the bridges were measured by the precise electronic caliper. The angle between the myocardial bridge fibre axis and other axis of the crossed blood vessel was measured by a goniometer. The presence of the bridges was confirmed in 53.33% of the researched material, most frequently (43.33%) above the anterior interventricular branch. The mean length of the bridges was 14.64 ± 9.03 mm and the mean thickness was 1.23 ± 1.32 mm. Myocardial bridge fibres pass over the descending blood vessel at the angle of 10-90 degrees. The results obtained on a limited sample suggest that the muscular index of myocardial bridge is the highest for bridges located on RIA, but that the difference is not significant in relation to bridges located on other branches. The results obtained suggest that bridges located on other branches, not only those on RIA, could have a great contractive power and, consequently, a great compressive force, which would be exerted on the wall of a crossed blood vessel.

  11. Bridging the Gap.

    PubMed

    Webb, Michele

    2016-01-01

    The view from the top of Hoover Dam looking south over the Colorado River was breathtaking! My friend and I stood there in silence, taking it all in. I had visited Hoover Dam on many occasions, but this visit was the first time I had seen the arch bridge that carries US Route 93 over the river and joins Nevada and Arizona states. It was a beautiful day, the temperature was perfect, and there was a slight breeze coming from Lake Mead behind us as we took in the view. PMID:27556855

  12. Nasal Bridge Intramuscular Hemangioma

    PubMed Central

    Hamir Basah, Zulkifli; Ramza Ramli, Ramiza; Gayadh, Maha Khadum; Mutum, Samarendra Singh

    2015-01-01

    Intramuscular haemangioma (IMH) is a benign mesenchymal tumour. It appears as a deep, nontender mass within the soft tissue, particularly in the extremities. This tumour may not be obvious on clinical examination. Head and neck IMHs represent only 13.5% of the total IMHs. The most common site for a head and neck IMH is the masseter muscle, followed by trapezius, sternocleidomastoid, and very rarely temporalis muscle. We present a patient with left nasal bridge swelling which was excised and histologically confirmed as intramuscular hemangioma. PMID:25709848

  13. 33 CFR 115.40 - Bridge repairs.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 33 Navigation and Navigable Waters 1 2014-07-01 2014-07-01 false Bridge repairs. 115.40 Section 115.40 Navigation and Navigable Waters COAST GUARD, DEPARTMENT OF HOMELAND SECURITY BRIDGES BRIDGE LOCATIONS AND CLEARANCES; ADMINISTRATIVE PROCEDURES § 115.40 Bridge repairs. Repairs to a bridge which...

  14. 33 CFR 115.40 - Bridge repairs.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 33 Navigation and Navigable Waters 1 2010-07-01 2010-07-01 false Bridge repairs. 115.40 Section 115.40 Navigation and Navigable Waters COAST GUARD, DEPARTMENT OF HOMELAND SECURITY BRIDGES BRIDGE LOCATIONS AND CLEARANCES; ADMINISTRATIVE PROCEDURES § 115.40 Bridge repairs. Repairs to a bridge which...

  15. 33 CFR 115.40 - Bridge repairs.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 33 Navigation and Navigable Waters 1 2012-07-01 2012-07-01 false Bridge repairs. 115.40 Section 115.40 Navigation and Navigable Waters COAST GUARD, DEPARTMENT OF HOMELAND SECURITY BRIDGES BRIDGE LOCATIONS AND CLEARANCES; ADMINISTRATIVE PROCEDURES § 115.40 Bridge repairs. Repairs to a bridge which...

  16. 33 CFR 115.40 - Bridge repairs.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 33 Navigation and Navigable Waters 1 2013-07-01 2013-07-01 false Bridge repairs. 115.40 Section 115.40 Navigation and Navigable Waters COAST GUARD, DEPARTMENT OF HOMELAND SECURITY BRIDGES BRIDGE LOCATIONS AND CLEARANCES; ADMINISTRATIVE PROCEDURES § 115.40 Bridge repairs. Repairs to a bridge which...

  17. 33 CFR 115.40 - Bridge repairs.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 33 Navigation and Navigable Waters 1 2011-07-01 2011-07-01 false Bridge repairs. 115.40 Section 115.40 Navigation and Navigable Waters COAST GUARD, DEPARTMENT OF HOMELAND SECURITY BRIDGES BRIDGE LOCATIONS AND CLEARANCES; ADMINISTRATIVE PROCEDURES § 115.40 Bridge repairs. Repairs to a bridge which...

  18. PCNA tool belts and polymerase bridges form during translesion synthesis.

    PubMed

    Boehm, Elizabeth M; Spies, Maria; Washington, M Todd

    2016-09-30

    Large multi-protein complexes play important roles in many biological processes, including DNA replication and repair, transcription, and signal transduction. One of the challenges in studying such complexes is to understand their mechanisms of assembly and disassembly and their architectures. Using single-molecule total internal reflection (TIRF) microscopy, we have examined the assembly and disassembly of the multi-protein complex that carries out translesion synthesis, the error-prone replication of damaged DNA. We show that the ternary complexes containing proliferating cell nuclear antigen (PCNA) and two non-classical DNA polymerases, Rev1 and DNA polymerase η, have two architectures: PCNA tool belts and Rev1 bridges. Moreover, these complexes are dynamic and their architectures can interconvert without dissociation. The formation of PCNA tool belts and Rev1 bridges and the ability of these complexes to change architectures are likely means of facilitating selection of the appropriate non-classical polymerase and polymerase-switching events.

  19. 16. Little Hell Gate Bridge with Big Hell Gate Bridge ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    16. Little Hell Gate Bridge with Big Hell Gate Bridge in background. Wards Island, New York Co., NY. Sec. 4207, MP 8.02. - Northeast Railroad Corridor, Amtrak Route between New Jersey/New York & New York/Connecticut State Lines, New York County, NY

  20. 20. Bronx Kill Bridge with Hell Gate Bridge in background. ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    20. Bronx Kill Bridge with Hell Gate Bridge in background. Randalls Island, New York Co., NY. Sec. 4207, MP 8.54. - Northeast Railroad Corridor, Amtrak Route between New Jersey/New York & New York/Connecticut State Lines, New York County, NY

  1. 25. White Plains Road Bridge in foreground; Unionport Road Bridge ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    25. White Plains Road Bridge in foreground; Unionport Road Bridge in background. Van Nest, Bronx Co., NY. Sec. 4207, MP 12.75./78. - Northeast Railroad Corridor, Amtrak Route between New Jersey/New York & New York/Connecticut State Lines, New York County, NY

  2. Acquisition and Analysis of Dynamic Responses of a Historic Pedestrian Bridge using Video Image Processing

    NASA Astrophysics Data System (ADS)

    O'Byrne, Michael; Ghosh, Bidisha; Schoefs, Franck; O'Donnell, Deirdre; Wright, Robert; Pakrashi, Vikram

    2015-07-01

    Video based tracking is capable of analysing bridge vibrations that are characterised by large amplitudes and low frequencies. This paper presents the use of video images and associated image processing techniques to obtain the dynamic response of a pedestrian suspension bridge in Cork, Ireland. This historic structure is one of the four suspension bridges in Ireland and is notable for its dynamic nature. A video camera is mounted on the river-bank and the dynamic responses of the bridge have been measured from the video images. The dynamic response is assessed without the need of a reflector on the bridge and in the presence of various forms of luminous complexities in the video image scenes. Vertical deformations of the bridge were measured in this regard. The video image tracking for the measurement of dynamic responses of the bridge were based on correlating patches in time-lagged scenes in video images and utilisinga zero mean normalisedcross correlation (ZNCC) metric. The bridge was excited by designed pedestrian movement and by individual cyclists traversing the bridge. The time series data of dynamic displacement responses of the bridge were analysedto obtain the frequency domain response. Frequencies obtained from video analysis were checked against accelerometer data from the bridge obtained while carrying out the same set of experiments used for video image based recognition.

  3. Acquisition and Analysis of Dynamic Responses of a Historic Pedestrian Bridge using Video Image Processing

    NASA Astrophysics Data System (ADS)

    O'Byrne, Michael; Ghosh, Bidisha; Schoefs, Franck; O'Donnell, Deirdre; Wright, Robert; Pakrashi, Vikram

    2015-07-01

    Video based tracking is capable of analysing bridge vibrations that are characterised by large amplitudes and low frequencies. This paper presents the use of video images and associated image processing techniques to obtain the dynamic response of a pedestrian suspension bridge in Cork, Ireland. This historic structure is one of the four suspension bridges in Ireland and is notable for its dynamic nature. A video camera is mounted on the river-bank and the dynamic responses of the bridge have been measured from the video images. The dynamic response is assessed without the need of a reflector on the bridge and in the presence of various forms of luminous complexities in the video image scenes. Vertical deformations of the bridge were measured in this regard. The video image tracking for the measurement of dynamic responses of the bridge were based on correlating patches in time-lagged scenes in video images and utilisinga zero mean normalised cross correlation (ZNCC) metric. The bridge was excited by designed pedestrian movement and by individual cyclists traversing the bridge. The time series data of dynamic displacement responses of the bridge were analysedto obtain the frequency domain response. Frequencies obtained from video analysis were checked against accelerometer data from the bridge obtained while carrying out the same set of experiments used for video image based recognition.

  4. 47 CFR 80.1007 - Bridge-to-bridge radiotelephone installation.

    Code of Federal Regulations, 2014 CFR

    2014-10-01

    ... 47 Telecommunication 5 2014-10-01 2014-10-01 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...

  5. 47 CFR 80.163 - Operator requirements of the Bridge-to-Bridge Act.

    Code of Federal Regulations, 2012 CFR

    2012-10-01

    ... 47 Telecommunication 5 2012-10-01 2012-10-01 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...

  6. 47 CFR 80.163 - Operator requirements of the Bridge-to-Bridge Act.

    Code of Federal Regulations, 2014 CFR

    2014-10-01

    ... 47 Telecommunication 5 2014-10-01 2014-10-01 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...

  7. 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...

  8. 47 CFR 80.163 - Operator requirements of the Bridge-to-Bridge Act.

    Code of Federal Regulations, 2013 CFR

    2013-10-01

    ... 47 Telecommunication 5 2013-10-01 2013-10-01 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...

  9. 47 CFR 80.1007 - Bridge-to-bridge radiotelephone installation.

    Code of Federal Regulations, 2012 CFR

    2012-10-01

    ... 47 Telecommunication 5 2012-10-01 2012-10-01 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...

  10. 47 CFR 80.331 - Bridge-to-bridge communication procedure.

    Code of Federal Regulations, 2013 CFR

    2013-10-01

    ... 47 Telecommunication 5 2013-10-01 2013-10-01 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...

  11. 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...

  12. 47 CFR 80.331 - Bridge-to-bridge communication procedure.

    Code of Federal Regulations, 2012 CFR

    2012-10-01

    ... 47 Telecommunication 5 2012-10-01 2012-10-01 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...

  13. 47 CFR 80.331 - Bridge-to-bridge communication procedure.

    Code of Federal Regulations, 2014 CFR

    2014-10-01

    ... 47 Telecommunication 5 2014-10-01 2014-10-01 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...

  14. 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...

  15. 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...

  16. 47 CFR 80.1007 - Bridge-to-bridge radiotelephone installation.

    Code of Federal Regulations, 2013 CFR

    2013-10-01

    ... 47 Telecommunication 5 2013-10-01 2013-10-01 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...

  17. 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...

  18. 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...

  19. Saving the Kilgore Covered Bridge.

    ERIC Educational Resources Information Center

    Clark, Wilma

    1988-01-01

    Describes an American literature class project to save a covered bridge from collapse. Illustrates how student initiative in contacting government agencies and news media, learning the history of the bridge, and raising public awareness about the project led to a joint county agreement to preserve the historic span. (DHP)

  20. Mathematics in Use: Suspension Bridges.

    ERIC Educational Resources Information Center

    Ginther, John L.

    1992-01-01

    Reviews the mathematics utilized in the design and construction of suspension bridges, in general, then illustrates these mathematical concepts by examining data associated with the Mackinac Bridge, which connects the two peninsulas of Michigan. Emphasizes the strong interest factor these gigantic structures have for students by attaching a sense…

  1. Burning trees and bridges

    NASA Technical Reports Server (NTRS)

    Levine, Joel S.

    1990-01-01

    Most burning of biomass is the result of human activity, and on a global scale it is increasing. Tropospheric concentrations of CO2, CO, CH4, non-methane hydrocarbons, and ozone are all increasing with time; global biomass burning may make an important contribution to this increase and thus to potential global climate change. The nitrogen cycle also can have important climatic effects. Nitrous oxide put into the atmosphere by biomass burning is a greenhouse gas 250 times more powerful (molecule for molecule) than carbon dioxide. Nitric oxide, as well as being a photochemical precursor of ozone, a major pollutant in the troposphere, produces nitric acid, the fastest-growing component of acid rain. Hence, the new bridge in the nitrogen cycle is of more than mere technical interest.

  2. Cascaded resonant bridge converters

    NASA Technical Reports Server (NTRS)

    Stuart, Thomas A. (Inventor)

    1989-01-01

    A converter for converting a low voltage direct current power source to a higher voltage, high frequency alternating current output for use in an electrical system where it is desired to use low weight cables and other circuit elements. The converter has a first stage series resonant (Schwarz) converter which converts the direct current power source to an alternating current by means of switching elements that are operated by a variable frequency voltage regulator, a transformer to step up the voltage of the alternating current, and a rectifier bridge to convert the alternating current to a direct current first stage output. The converter further has a second stage series resonant (Schwarz) converter which is connected in series to the first stage converter to receive its direct current output and convert it to a second stage high frequency alternating current output by means of switching elements that are operated by a fixed frequency oscillator. The voltage of the second stage output is controlled at a relatively constant value by controlling the first stage output voltage, which is accomplished by controlling the frequency of the first stage variable frequency voltage controller in response to second stage voltage. Fault tolerance in the event of a load short circuit is provided by making the operation of the first stage variable frequency voltage controller responsive to first and second stage current limiting devices. The second stage output is connected to a rectifier bridge whose output is connected to the input of the second stage to provide good regulation of output voltage wave form at low system loads.

  3. Comparison of the One-electron Oxidations of CO-Bridged vs Unbridged Bimetallic Complexes: Electron-transfer Chemistry of Os2Cp2(CO)4 and Os2Cp*2(μ-CO)2(CO)2 (Cp = η5-C5H5, Cp* = η5-C5Me5)

    SciTech Connect

    Laws, Derek R.; Bullock, R. Morris; Lee, Richmond; Huang, Kuo-Wei; Geiger, William J.

    2014-09-22

    The one-electron oxidations of two dimers of half-sandwich osmium carbonyl complexes have been examined by electrochemistry, spectro-electrochemistry, and computational methods. The all-terminal carbonyl complex Os2Cp2(CO)4 (1, Cp = η5-C5H5) undergoes a reversible one-electron anodic reaction at E1/2 = 0.41 V vs ferrocene in CH2Cl2/0.05 M [NBu4][B(C6F5)4], giving a rare example of a metal-metal bonded radical cation unsupported by bridging ligands. The IR spectrum of 1+ is consistent with an approximately 1:1 mixture of anti and gauche structures for the 33 e- radical cation in which it has retained all-terminal bonding of the CO ligands. DFT calculations, including orbital-occupancy-perturbed Mayer bond-order analyses, show that the HOMOs of anti-1 and gauche-1 are metal-ligand delocalized. Removal of an electron from 1 has very little effect on the Os-Os bond order, accounting for the resistance of 1+ to heterolytic cleavage. The Os-Os bond distance is calculated to decrease by 0.10 Å and 0.06 Å as a consequence of one-electron oxidation of anti-1 and gauche-1, respectively. The CO-bridged complex Os2Cp*2(μ-CO)2(CO)2 (Cp* = η5-C5Me5), trans-2, undergoes a more facile oxidation, E1/2 = - 0.11 V, giving a persistent radical cation shown by solution IR analysis to preserve its bridged-carbonyl structure. However, ESR analysis of frozen solutions of 2+ is interpreted in terms of the presence of two isomers, most likely anti-2+ and trans-2+, at low temperature. Calculations show that the HOMO of trans-2 is highly delocalized over the metal-ligand framework, with the bridging carbonyls accounting for about half of the orbital makeup. The Os-Os bond order again changes very little with removal of an electron, and the Os-Os bond length actually undergoes minor shortening. Calculations suggest that the second isomer of 2+ has both the trans CO-bridged and the anti all-terminal CO structures. DRL and WEG acknowledge the support of the National Science Foundation under

  4. Incorporation of nondestructive evaluation in Pontis Bridge Management System

    NASA Astrophysics Data System (ADS)

    Hadavi, Ahmad

    1998-03-01

    The highway system in the United States includes nearly 577,000 bridges, the majority of which were built during two major bridge building periods -- just before World War II (1930s) and in the first two decades of the Cold War (1950s and 1960s). Given the age and increased usage of these bridges over the years, many now require substantial maintenance to satisfy their desired level of service. The complex task of allocating scarce funds for the repair, maintenance, and rehabilitation of this large number of bridges led to the development of several optimization studies and two major bridge management system, namely BRIDGIT and Pontis. Pontis has emerged as the system of choice for all states in the Nation. At this time over 40 highway agencies continue to license, evaluate and implement the current AASHTOWARE Program, Pontis V. 3.2. However, all data currently required by Pontis to assess the structural stability and resulting suggestions for repair and maintenance of bridges are based on visual inspection and judgement. Consequently, all suggestions are based on that visual inspection. This paper discusses development of a plan for how non-destructive evaluation (NDE) data can be used to provide more information than visual inspection.

  5. Law, Ethics, and Social Justice: Commentary from the Bridge

    ERIC Educational Resources Information Center

    Stefkovich, Jacqueline A.

    2012-01-01

    Providing commentary on this "Journal of School Leadership's" special issue, "Constructing a Bridge Between Law and Social Justice: An Ethical Journey," has been not only a daunting task because of the complex nature of this topic but also a humbling experience because of the superior quality of these articles. At the same time, it is most…

  6. 3. General view from Richmond Branch Reading RR bridge over ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    3. General view from Richmond Branch Reading RR bridge over Ridge Avenue, looking down Ridge Avenue showing Building 7, entrance to complex, Building 8 and finally Building 10. Building 11, tallest building in center, predominates. View looking NNW. - John & James Dobson Carpet Mill (West Parcel), 4041-4055 Ridge Avenue, Philadelphia, Philadelphia County, PA

  7. 9. DETAIL VIEW OF BRIDGE CRANE ON WEST SIDE OF ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    9. DETAIL VIEW OF BRIDGE CRANE ON WEST SIDE OF BUILDING. CAMERA FACING NORTHEAST. CONTAMINATED AIR FILTERS LOADED IN TRANSPORT CASKS WERE TRANSFERRED TO VEHICLES AND SENT TO RADIOACTIVE WASTE MANAGEMENT COMPLEX FOR STORAGE. INEEL PROOF NUMBER HD-17-1. - Idaho National Engineering Laboratory, Old Waste Calcining Facility, Scoville, Butte County, ID

  8. 61. SIDE VIEW OF SUPPORT CARRIAGE ASSEMBLY WITH VAL BRIDGE ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    61. SIDE VIEW OF SUPPORT CARRIAGE ASSEMBLY WITH VAL BRIDGE STRUCTURE IN BACKGROUND AT ISLIP CANYON, Date unknown, circa February 1948. (Original photograph in possession of Dave Willis, San Diego, California.) - Variable Angle Launcher Complex, Variable Angle Launcher, CA State Highway 39 at Morris Reservior, Azusa, Los Angeles County, CA

  9. 56. ASSEMBLY OF THE VAL BRIDGE STRUCTURE AT ISLIP CANYON, ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    56. ASSEMBLY OF THE VAL BRIDGE STRUCTURE AT ISLIP CANYON, July 31, 1947. (Original photograph in possession of Dave Willis, San Diego, California.) - Variable Angle Launcher Complex, Variable Angle Launcher, CA State Highway 39 at Morris Reservior, Azusa, Los Angeles County, CA

  10. 66. VAL BRIDGE AND BARGES FLOATING FROM ISLIP CANYON TO ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    66. VAL BRIDGE AND BARGES FLOATING FROM ISLIP CANYON TO THE VAL SITE, April 12, 1948. (Original photograph in possession of Dave Willis, San Diego, California.) - Variable Angle Launcher Complex, Variable Angle Launcher, CA State Highway 39 at Morris Reservior, Azusa, Los Angeles County, CA

  11. 74. DETAIL VIEW OF INSIDE THE LAUNCHING BRIDGE LOOKING SOUTHWEST ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    74. DETAIL VIEW OF INSIDE THE LAUNCHING BRIDGE LOOKING SOUTHWEST SHOWING ADJUSTABLE STAIRS ON THE LEFT AND LAUNCHING TUBE ON THE RIGHT, Date unknown, circa 1948. - Variable Angle Launcher Complex, Variable Angle Launcher, CA State Highway 39 at Morris Reservior, Azusa, Los Angeles County, CA

  12. 65. AERIAL VIEW OF VAL BRIDGE AND BARGES AT ISLIP ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    65. AERIAL VIEW OF VAL BRIDGE AND BARGES AT ISLIP CANYON, December 9, 1947. (Original photograph in possession of Dave Willis, San Diego, California.) - Variable Angle Launcher Complex, Variable Angle Launcher, CA State Highway 39 at Morris Reservior, Azusa, Los Angeles County, CA

  13. 57. INTERIOR VIEW OF VAL BRIDGE STRUCTURE SHOWING LAUNCHING TUBE, ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    57. INTERIOR VIEW OF VAL BRIDGE STRUCTURE SHOWING LAUNCHING TUBE, STAIRS AND PORTION OF LAUNCHING DECK. NOTE SUPPORT CARRIAGE ASSEMBLY IN DISTANCE. Date unknown, circa March 1948. (Original photograph in possession of Dave Willis, San Diego, California.) - Variable Angle Launcher Complex, Variable Angle Launcher, CA State Highway 39 at Morris Reservior, Azusa, Los Angeles County, CA

  14. 4. VAL PARTIAL ELEVATION SHOWING LAUNCHER BRIDGE ON SUPPORTS, LAUNCHER ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    4. VAL PARTIAL ELEVATION SHOWING LAUNCHER BRIDGE ON SUPPORTS, LAUNCHER SLAB, SUPPORT CARRIAGE, CONCRETE 'A' FRAME STRUCTURE AND CAMERA TOWER LOOKING SOUTHEAST. - Variable Angle Launcher Complex, Variable Angle Launcher, CA State Highway 39 at Morris Reservior, Azusa, Los Angeles County, CA

  15. 9. COMPLETED ROLLING CAMERA CAR ON RAILROAD TRACK AND BRIDGE ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    9. COMPLETED ROLLING CAMERA CAR ON RAILROAD TRACK AND BRIDGE LOOKING WEST, APRIL 26, 1948. (ORIGINAL PHOTOGRAPH IN POSSESSION OF DAVE WILLIS, SAN DIEGO, CALIFORNIA.) - Variable Angle Launcher Complex, Camera Car & Track, CA State Highway 39 at Morris Reservior, Azusa, Los Angeles County, CA

  16. Seafloor off Natural Bridges State Beach, Santa Cruz, California

    USGS Publications Warehouse

    Storlazzi, Curt D.; Golden, Nadine E.; Gibbons, Helen

    2013-01-01

    The seafloor off Natural Bridges State Beach, Santa Cruz, California, is extremely varied, with sandy flats, boulder fields, faults, and complex bedrock ridges. These ridges support rich marine ecosystems; some of them form the "reefs" that produce world-class surf breaks. Colors indicate seafloor depth, from red-orange (about 2 meters or 7 feet) to magenta (25 meters or 82 feet).

  17. Can HN[double bond, length as m-dash]NH, FN[double bond, length as m-dash]NH, or HN[double bond, length as m-dash]CHOH bridge the σ-hole and the lone pair at P in binary complexes with H2XP, for X = F, Cl, NC, OH, CN, CCH, CH3, and H?

    PubMed

    Del Bene, Janet E; Alkorta, Ibon; Elguero, José

    2015-11-11

    Ab initio MP2/aug'-cc-pVTZ calculations have been carried out to investigate the properties of complexes formed between H2XP, for X = F, Cl, NC, OH, CN, CCH, CH3, and H, and the possible bridging molecules HN[double bond, length as m-dash]NH, FN[double bond, length as m-dash]NH, and HN[double bond, length as m-dash]CHOH. H2XP:HNNH and H2XP:FNNH complexes are stabilized by PN pnicogen bonds, except for H2(CH3)P:FNNH and H3P:FNNH which are stabilized by N-HP hydrogen bonds. H2XP:HNCHOH complexes are stabilized by PN pnicogen bonds and nonlinear O-HP hydrogen bonds. For a fixed H2XP molecule, binding energies decrease in the order HNCHOH > HNNH > FNNH, except for the binding energies of H2(CH3)P and H3P with HNNH and FNNH. Binding energies of complexes with HNCHOH and HNNH increase as the P-N1 distance decreases, but binding energies of complexes with FNNH show little dependence on this distance. The large binding energies of H2XP:HNCHOH complexes arise from a cooperative effect involving electron-pair acceptance by P to form a pnicogen bond, and electron-pair donation by P to form a hydrogen bond. The dominant charge-transfer interaction in these complexes involves electron-pair donation by N across the pnicogen bond, except for complexes in which X is one of the more electropositive substituents, CCH, CH3, and H. For these, lone-pair donation by P across the hydrogen bond dominates. AIM and NBO data for these complexes are consistent with their bonding characteristics, showing molecular graphs with bond critical points and charge-transfer interactions associated with hydrogen and pnicogen bonds. EOM-CCSD spin-spin coupling constants (1p)J(P-N) across the pnicogen bond for each series of complexes correlate with the P-N distance. In contrast, (2h)J(O-P) values for complexes H2XP:HNCHOH do not correlate with the O-P distance, a consequence of the nonlinearity of these hydrogen bonds.

  18. Isocyanato- and methacryloxysilanes promote Bis-GMA adhesion to titanium.

    PubMed

    Matinlinna, J P; Lassila, L V J; Kangasniemi, I; Vallittu, P K

    2005-04-01

    In dentistry, adhesion promotion with 3-methacryloyloxypropyltrimethoxysilane is usually sufficient, but its hydrolytic stability is a continuous concern. The hydrolytic stability of an alternative, 3-isocyanatopropyltriethoxysilane, was compared with that of conventional 3-methacryloyloxypropyltrimethoxysilane. Two silanes, both in 0.1 and 1.0 vol-% in ethanol-water, were evaluated in the attachment of an experimental bis-phenol-A-diglycidyldimethacrylate (Bis-GMA) resin to grit-blasted (with two different systems) titanium. Silane hydrolysis was monitored by FTIR spectrometry. Bis-GMA resin was applied and photo-polymerized on titanium. The specimens were thermocycled (6000 cycles, 5-55 degrees C). Surface analysis was carried out with scanning electron microscopy. Statistical analysis (ANOVA) showed that the highest shear bond was achieved with 0.1% 3-isocyanatopropyltriethoxysilane (12.5 MPa) with silica-coating, and the lowest with 1.0% 3-methacryloyloxypropyltrimethoxysilane (3.4 MPa) with alumina-coating. The silane, its concentration, and the grit-blasting method significantly affected the shear bond strength (p < 0.05). SEM images indicated cohesive failure of bonding, and, in conclusion, 3-isocyanatopropyltriethoxysilane is a potential coupling agent. PMID:15790744

  19. Binuclear complexes of technetium. Evidence for bis(terdentate)bidentate coordination by the bridging ligand 2,3,5,6-tetrakis(2-pyridyl)pyrazine to technetium(V)

    SciTech Connect

    Du Preez, J.G.H.; Gerber, T.I.A.; Gibson, M.L.; Geyser, R. )

    1990-01-01

    The authors have used the potentially bis(terdentate) nitrogen aromatic heterocyclic ligand 2,3,5,6-tetrakis(2-pyridyl)pyrazine (tppz) to prepare mono- and bimetallic technetium(V) complexes bound to tppz. The stimulus for the development of the coordination chemistry of the man-made element technetium is provided by the use of complexes of this element as anatomical imaging agents in nuclear medicine. Although the chemistry of technetium(V) with nitrogen donor ligands is well understood, no complexes have been prepared using potentially terdentate neutral nitrogen donor ligands of this metal in the +5 oxidation state.

  20. 77 FR 16784 - General Bridge Regulation; Amendment

    Federal Register 2010, 2011, 2012, 2013, 2014

    2012-03-22

    ... SECURITY Coast Guard 33 CFR Part 114, 116, 118 RIN 1625-AB36 General Bridge Regulation; Amendment AGENCY... rulemaking concerning amendments to the general bridge regulations. The rulemaking was initiated to clarify the statutory responsibilities of bridge owners to remove their bridges from navigable waterways...

  1. Bridge diagnosis at 55 mph

    SciTech Connect

    Azevedo, S

    1998-10-01

    The Federal Highway Administration (FHWA) has helped sponsor a research project at Lawrence Livermore that produced a beneficial new tool as well as an R&D 100 Award. The HERMES Bridge Inspector will provide an invaluable capability to diagnose the problems of deteriorating bridge decks and do it accurately, efficiently, nondestructively, and, perhaps most important to motorists, without closing bridges. Almost 30% of 600,000 large highway bridges in the U.S. are classified "deficient" by the FHWA, and HERMES can make a significant contribution toward solving the problem of infrastructure assessment and repair. With further development, HERMES holds promise for other concrete inspection problems, such as railroads, tunnels, and runways. HERMES, or High-performance Electromagnetic Roadway Mapping and Evaluation System, is a radar-based sensing system mounted in a trailer. It can be pulled by a vehicle at traffic speeds over a bridge deck to collect information about the roadway subsurface -- its sensors gathering data 30 centimeters or more into concrete. An onboard computer system processes the data into three-dimensional images that pinpoint problems in the roadway concrete and give engineers quantitative information about deterioration in the bridge deck. Engineers can then better assess what repairs or reconstruction is necessary and avoid the cost overruns and delays that result from inexact problem diagnoses.

  2. Sacrificial bridges for MEMS fabrication

    NASA Astrophysics Data System (ADS)

    Chang, Chao-Min; Chen, Yang-Che; Fong, Chien-Fu; Guu, Yunn-Horng; Chen, Rongshun; Yeh, J. Andrew; Hou, Max T.

    2011-09-01

    This study discusses sacrificial bridges that are used to release MEMS devices. Before being released, sacrificial bridges connect all the component structures into an integral structure. Solder bump bonding is used to mount the MEMS chip on another chip or a printed circuit board (PCB) and to maintain the alignment among all component structures after removal of the sacrificial bridges. Two types of sacrificial bridges were designed, analyzed and fabricated. The fabrication process—which used low resistivity single crystal silicon (SCS) wafers as the device material—was developed to implement the sacrificial bridges. Novel SCS through silicon vias (TSVs), which interconnect stacked chips, was made using the same process. An electrostatic comb drive actuator was fabricated and mounted onto a PCB. The fabricated actuator was tested to demonstrate the feasibility of the fabrication process, sacrificial bridges and SCS TSVs. The results show that the actuator worked well. Its maximum displacement and resonant frequency were 69.9 µm and 406 Hz, respectively. This method is promising for the delivery of a novel 3D system in package for MEMS devices.

  3. OVERVIEW OF BRIDGES WITH WAIKELE CANAL BRIDGE IN CENTER, OR&L ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    OVERVIEW OF BRIDGES WITH WAIKELE CANAL BRIDGE IN CENTER, OR&L BRIDGE IN BACKGROUND. SHOWING THE EARTHEN INCLINE THAT RAISES FARRINGTON HIGHWAY OVER THE FORMER OR&L TRACKS. NOTE THE 1963 WESTBOUND BRIDGE IN THE FOREGROUND. VIEW FACING EAST. - Waikele Canal Bridge and Highway Overpass, Farrington Highway and Waikele Stream, Waipahu, Honolulu County, HI

  4. Development of inspection robots for bridge cables.

    PubMed

    Yun, Hae-Bum; Kim, Se-Hoon; Wu, Liuliu; Lee, Jong-Jae

    2013-01-01

    This paper presents the bridge cable inspection robot developed in Korea. Two types of the cable inspection robots were developed for cable-suspension bridges and cable-stayed bridge. The design of the robot system and performance of the NDT techniques associated with the cable inspection robot are discussed. A review on recent advances in emerging robot-based inspection technologies for bridge cables and current bridge cable inspection methods is also presented.

  5. Development of inspection robots for bridge cables.

    PubMed

    Yun, Hae-Bum; Kim, Se-Hoon; Wu, Liuliu; Lee, Jong-Jae

    2013-01-01

    This paper presents the bridge cable inspection robot developed in Korea. Two types of the cable inspection robots were developed for cable-suspension bridges and cable-stayed bridge. The design of the robot system and performance of the NDT techniques associated with the cable inspection robot are discussed. A review on recent advances in emerging robot-based inspection technologies for bridge cables and current bridge cable inspection methods is also presented. PMID:24459453

  6. Development of Inspection Robots for Bridge Cables

    PubMed Central

    Kim, Se-Hoon; Lee, Jong-Jae

    2013-01-01

    This paper presents the bridge cable inspection robot developed in Korea. Two types of the cable inspection robots were developed for cable-suspension bridges and cable-stayed bridge. The design of the robot system and performance of the NDT techniques associated with the cable inspection robot are discussed. A review on recent advances in emerging robot-based inspection technologies for bridge cables and current bridge cable inspection methods is also presented. PMID:24459453

  7. Synthesis and spectroscopic studies of homo-binuclear, alkoxo bridged homo- and hetero-tetranuclear metal complexes of a bis-N 2O 4 Schiff base ligand derived from ethanolamine and macroacyclic tetranaphthaldehyde

    NASA Astrophysics Data System (ADS)

    Karaoğlu, Kaan; Baran, Talat; Değirmencioğlu, İsmail; Serbest, Kerim

    2011-09-01

    Three new homo-binuclear Ni(II), Cu(II), Zn(II) complexes ( 2-4), homo-tetranuclear Cu(II) complex ( 5), and hetero-tetranuclear Cu(II)-Ni(II) complex ( 6) of a macroacyclic potentially bis-hexadentate N 2O 4 Schiff base have been synthesized. The imino-alcohol ligand, H 4L was obtained by the condensation of ethanolamine with 2,2'-[2,3-bis(1-formyl-2-naphthyloxymethyl)-but-2-ene-1,4-diyldioxy]bis(naphthalene-1-carbaldehyde). The structures of both the Schiff base and its complexes have been proposed by elemental analyses, spectroscopic data i.e. IR, 1H and 13C NMR, UV-vis, electrospray ionisation mass spectra, molar conductivities and magnetic susceptibility measurements. The ligand has two similar compartments to bind first primary two metal ions, and acts bi- or tetra-negative, bis-tetradentate forming five membered chelate ring. However, secondary two metal ions (either Cu 2+ or Ni 2+) are ligated with dianionic oxygen atoms of the alcohol groups and are linked to the 1,10-phenanthroline-nitrogen atoms in the tetranuclear complexes ( 5 and 6).

  8. 26. NEW STEEL BRIDGE COMPLETED ASSEMBLED. OLD BRIDGE BELOW. U.S.G.S. ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    26. NEW STEEL BRIDGE COMPLETED ASSEMBLED. OLD BRIDGE BELOW. U.S.G.S. GAGING STATION IN RIGHT BACKGROUND. VIEW LOOKING NORTHEAST - Kaibab Trail Suspension Bridge, Spanning Colorado River, Grand Canyon, Coconino County, AZ

  9. 49 CFR 237.101 - Scheduling of bridge inspections.

    Code of Federal Regulations, 2014 CFR

    2014-10-01

    ... bridge, and the weight and frequency of traffic carried on the bridge. (c) Each bridge management program... bridge inspections. (a) Each bridge management program shall include a provision for scheduling an... for in the bridge management program when a railroad bridge engineer determines that such...

  10. 49 CFR 237.101 - Scheduling of bridge inspections.

    Code of Federal Regulations, 2013 CFR

    2013-10-01

    ... bridge, and the weight and frequency of traffic carried on the bridge. (c) Each bridge management program... bridge inspections. (a) Each bridge management program shall include a provision for scheduling an... for in the bridge management program when a railroad bridge engineer determines that such...

  11. 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...

  12. 47 CFR 80.309 - Watch required by the Bridge-to-Bridge Act.

    Code of Federal Regulations, 2014 CFR

    2014-10-01

    ... 47 Telecommunication 5 2014-10-01 2014-10-01 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...

  13. 47 CFR 80.309 - Watch required by the Bridge-to-Bridge Act.

    Code of Federal Regulations, 2012 CFR

    2012-10-01

    ... 47 Telecommunication 5 2012-10-01 2012-10-01 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...

  14. 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...

  15. 47 CFR 80.309 - Watch required by the Bridge-to-Bridge Act.

    Code of Federal Regulations, 2013 CFR

    2013-10-01

    ... 47 Telecommunication 5 2013-10-01 2013-10-01 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...

  16. Polynuclear complexes with bridging pyrophosphate ligands: synthesis and characterisation of {[(bipy)Cu(H2O)(mu-P2O7)Na2(H2O)6] x 4H2O}, {[(bipy)Zn-(H2O)(mu-P2O7)Zn(bipy)]2 x 14H2O} and {[(bipy)(VO)2]2(mu-P2O7)] x 5H2O}.

    PubMed

    Doyle, Robert P; Nieuwenhuyzen, Mark; Kruger, Paul E

    2005-12-01

    The reaction in water of M(II) ions (M = Cu, 1; Zn, 2; VO, 3) with 2,2'-bipyridine (bipy) followed by Na4P2O7 leads to the formation of three new complexes which feature the pyrophosphate anion, P2O7(4-), as a bridging ligand. Single crystal X-ray diffraction revealed 1 to be {[(bipy)Cu(H2O)(micro-P2O7)Na2(H2O)6] x 4H2O}, and 2 as a tetranuclear Zn(II) complex, {[(bipy)Zn(H2O)(micro-P2O7)Zn(bipy)]2 x 14H2O}. The structure of 1 consists of a mononuclear [(bipy)Cu(H2O)(P2O7)]2- unit that links via a pyrophosphate bridge to two Na atoms. The hydrated six-coordinate Na atoms themselves join together through bridging water molecules to generate a 2D Na-water sheet. The structure of 2 consists of a tetranuclear Zn(II) cluster (dimer-of-dimers) with two pyrophosphate ligands bridging between four metal centres. Adjacent clusters interact through face-to-face pi-pi interactions via the bipy ligands to yield a 2D sheet. Adjacent sheets pack in register to create channels, which are filled by the water molecules of crystallisation. An intricate 2D H-bonded water network separates adjacent sheets and encapsulates the tetranuclear clusters. Aspects of the pyrophosphate coordination modes in 1 and 2 are of structural relevance to those found within the inorganic pyrophosphatases. Compound 3, {[(bipy)(VO)2]2(micro-P2O7)] x 5H2O}, was isolated as an insoluble lime-green powder. Its dinuclear structure was elucidated from elemental and thermal analysis, magnetic susceptibility measurement and IR spectroscopy. The latter displayed characteristic bridging pyrophosphate and signature V=O stretches, which were corroborated by contrast to the IR spectra of 1 and 2 and through comparison with those found in the structurally characterised dinuclear complex, {[(bipy)Cu(H2O)]2(micro-P2O7) x 7H2O}, 4. PMID:16471055

  17. Floating liquid bridge charge dynamics

    NASA Astrophysics Data System (ADS)

    Teschke, Omar; Soares, David Mendez; Gomes, Whyllerson Evaristo; Valente Filho, Juracyr Ferraz

    2016-01-01

    The interaction of liquid with electric fields is investigated in a configuration where up to 13 kV are applied between electrodes resulting in a 106 V/m electric field in the capillaries and where there is the formation of a free-standing fluid bridge in the interelectrode gap. The Mott-Gurney equation was fitted to the measured ionization current vs applied voltage curve which indicates that the ionization rate at the high-voltage anode electrode dimethylsulfoxide (DMSO) interface and space charging in the interelectrode gap determine the floating liquid bridge current for a given cathode-to-anode voltage. Space charge effects were measured in the cathode becker and also at the liquid bridge since the ionized charges at the anode migrate to the bridge outer surface and decrease the interfacial tension from 43 mJ/m2 to 29 mJ/m2. Two distinct structural regions then form the bridge, a charged plastic (bulk modulus ˜100 MPa) conducting outer layer with a surface conductivity of ˜10-9 Ω-1, which shapes and supports the floating fluid structure, and an inner liquid cylinder, where DMSO molecules flow.

  18. Summary and Comparison of Multiphase Streambed Scour Analysis at Selected Bridge Sites in Alaska

    USGS Publications Warehouse

    Conaway, Jeffrey S.

    2004-01-01

    The U.S. Geological Survey and the Alaska Department of Transportation and Public Facilities undertook a cooperative multiphase study of streambed scour at selected bridges in Alaska beginning in 1994. Of the 325 bridges analyzed for susceptibility to scour in the preliminary phase, 54 bridges were selected for a more intensive analysis that included site investigations. Cross-section geometry and hydraulic properties for each site in this study were determined from field surveys and bridge plans. Water-surface profiles were calculated for the 100- and 500-year floods using the Hydrologic Engineering Center?s River Analysis System and scour depths were calculated using methods recommended by the Federal Highway Administration. Computed contraction-scour depths for the 100- and 500-year recurrence-interval discharges exceeded 5 feet at six bridges, and pier-scour depths exceeded 10 feet at 24 bridges. Complex pier-scour computations were made at 10 locations where the computed contraction-scour depths would expose pier footings. Pressure scour was evaluated at three bridges where the modeled flood water-surface elevations intersected the bridge structure. Site investigation at the 54 scour-critical bridges was used to evaluate the effectiveness of the preliminary scour analysis. Values for channel-flow angle of attack and approach-channel width were estimated from bridge survey plans for the preliminary study and were measured during a site investigation for this study. These two variables account for changes in scour depths between the preliminary analysis and subsequent reanalysis for most sites. Site investigation is needed for best estimates of scour at bridges with survey plans that indicate a channel-flow angle of attack and for locations where survey plans did not include sufficient channel geometry upstream of the bridge.

  19. Rhenium complexes with weakly coordinating solvent ligands, cis[Re(PR{sub 3})(CO){sub 4}(L)][BAr{sub F}], L = CH{sub 2}Cl{sub 2}, Et{sub 2}O, NC{sub 5}F{sub 5}: Decomposition to chloride-bridged dimers in CH{sub 2}Cl{sub 2} solution

    SciTech Connect

    Huhmann-Vincent, J.; Scott, B.L.; Kubas, G.J.

    1999-01-11

    The solvent-coordinated complexes [cis-Re(CO){sub 4}(PR{sub 3})(S)][BAr{sub F}] (R = Ph, {sup i}Pr, Cy, BAr{sub F} = [B(3,5-(CF{sub 3}){sub 2}C{sub 6}H{sub 3}){sub 4}]{sup {minus}}) for S = Et{sub 2}O, CH{sub 2}Cl{sub 2}, and NC{sub 5}F{sub 5} have been prepared from reaction of the neutral methyl precursors, cis-Re-(CO){sub 4}(PR{sub 3})(Me), with either [H(OEt{sub 2}){sub 2}][BAr{sub F}] or [Ph{sub 3}C][BAr{sub F}] in the appropriate solvent. A crystal structure of the complex [cis-Re(CO){sub 4}(P{sup i}Pr{sub 3})(ClCH{sub 2}Cl)][BAr{sub F}] shows that the dichloromethane ligand is coordinated through one chlorine, with an Re-Cl distance of 2.554(2) {angstrom}. The first example of a structurally characterized pentafluoropyridine complex of rhenium was also determined, [cis-Re(CO){sub 4}(P{sup i}Pr{sub 3})(NC{sub 5}F{sub 5})][BAr{sub F}], with an Re-N distance of 2.319(5) {angstrom}. Activation of C-Cl bonds in the dichloromethane complexes result in the formation of the chloride-bridged dimers, {l_brace}[cis-Re(CO){sub 4}(PR{sub 3})]{sub 2}({mu}-Cl){r_brace}{l_brace}BAr{sub f}{r_brace}, and the X-ray structures of the Ph and Cy derivatives were determined.

  20. Structural models of the bimetallic subunit at the A-cluster of acetyl coenzyme a synthase/CO dehydrogenase: binuclear sulfur-bridged Ni-Cu and Ni-Ni complexes and their reactions with CO.

    PubMed

    Harrop, Todd C; Olmstead, Marilyn M; Mascharak, Pradip K

    2004-11-17

    The Ni(II)-dicarboxamido-dithiolato complexes (Et4N)2[Ni(NpPepS)] (1) and (Et4N)2[Ni(PhPepS)] (2) were used as Nid metallosynthons in the construction of higher nuclearity dinuclear Ni-Cu and Ni-Ni species to model the bimetallic Mp-Nid site of the A-cluster of acetyl coenzyme A synthase/CO dehydrogenase (ACS/CODH). Reaction of 1 with [Cu(neo)Cl] and [Ni(terpy)Cl2] in MeCN affords the dinuclear complexes (Et4N)[Cu(neo)Ni(NpPepS)] (3) and [Ni(terpy)Ni(NpPepS)] (4), respectively. Reaction of 2 with [Ni(dppe)Cl2] in MeCN yields [Ni(dppe)Ni(PhPepS)] (6). The Ni-Cu complex 3 exhibits no redox chemistry at the Nid site and no reaction with CO. In contrast, the Nip sites in 4 and 6 are readily reduced (characterized by their Ni(I) EPR spectra) and bind CO, exhibiting nuco bands at 2044 and 1997 cm-1, respectively, indicating terminal CO binding. The present Ni-Ni systems replicate the structural and chemical properties of the A-cluster site in ACS/CODH and support the presence of Ni at Mp in the catalytically active enzyme.

  1. Chickamauga National Military Park Tour Roads, Gordon's Slough Bridge, At ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    Chickamauga National Military Park Tour Roads, Gordon's Slough Bridge, At the confluence of Alexander's Bridge Road and Gordon's Slough, southeast of Alexander's Bridge, Fort Oglethorpe, Catoosa County, GA

  2. 27. VIEW SHOWING SOUTH ELEVATION OF NOTRE DAM BRIDGE, LOOKING ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    27. VIEW SHOWING SOUTH ELEVATION OF NOTRE DAM BRIDGE, LOOKING NORTHEAST Ernest Gould, photographer, 1987 - Notre Dame Bridge, Spanning Merrimack River on Bridge Street, Manchester, Hillsborough County, NH

  3. 2. Elkmont, deck view of corrugated arched bridge. Great ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    2. Elkmont, deck view of corrugated arched bridge. - Great Smoky Mountains National Park Roads & Bridges, Elkmont Vehicle Bridge, Spanning Little River at Elkmont Campground, Gatlinburg, Sevier County, TN

  4. 3. Elkmont, underside detail of corrugated arched bridge. Great ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    3. Elkmont, underside detail of corrugated arched bridge. - Great Smoky Mountains National Park Roads & Bridges, Elkmont Vehicle Bridge, Spanning Little River at Elkmont Campground, Gatlinburg, Sevier County, TN

  5. Excitation Methods for Bridge Structures

    SciTech Connect

    Farrar, C.R.; Duffy, T.A.; Cornwell, P.J.; Doebling, S.W.

    1999-02-08

    This paper summarizes the various methods that have been used to excited bridge structures during dynamic testing. The excitation methods fall into the general categories of ambient excitation methods and measured-input excitation methods. During ambient excitation the input to the bridge is not directly measured. In contrast, as the category label implies, measured-input excitations are usually applied at a single location where the force input to the structure can be monitored. Issues associated with using these various types of measurements are discussed along with a general description of the various excitation methods.

  6. Balanced bridge feedback control system

    NASA Technical Reports Server (NTRS)

    Lurie, Boris J. (Inventor)

    1990-01-01

    In a system having a driver, a motor, and a mechanical plant, a multiloop feedback control apparatus for controlling the movement and/or positioning of a mechanical plant, the control apparatus has a first local bridge feedback loop for feeding back a signal representative of a selected ratio of voltage and current at the output driver, and a second bridge feedback loop for feeding back a signal representative of a selected ratio of force and velocity at the output of the motor. The control apparatus may further include an outer loop for feeding back a signal representing the angular velocity and/or position of the mechanical plant.

  7. A rational design for imidazolate-bridged linear trinuclear compounds from mononuclear copper(II) complexes with 2-[((imidazol-2-ylmethylidene)amino)ethyl]pyridine (HL): syntheses, structures, and magnetic properties of [Cu(L)(hfac)M(hfac)2Cu(hfac)(L)] (M = ZnII, CuII, MnII).

    PubMed

    Colacio, E; Ghazi, M; Kivekäs, R; Klinga, M; Lloret, F; Moreno, J M

    2000-06-26

    Two mononuclear copper(II) complexes with the unsymmetrical tridentate ligand 2-[((imidazol-2-ylmethylidene)amino)ethyl]pyridine (HL), [Cu(HL)(H2O)](ClO4)2.2H2O (1) and [Cu(HL)Cl2] (2), have been prepared and characterized. The X-ray analysis of 2 revealed that the copper(II) ion assumes a pentacoordinated square pyramidal geometry with an N3Cl2 donor set. When 1 and 2 are treated with an equimolecular amount of potassium hydroxide, the deprotonation of the imidazole moiety promotes a self-assembled process, by coordination of the imidazolate nitrogen atom to a Cu(II) center of an adjacent unit, leading to the polynuclear complexes [[Cu(L)(H2O)](ClO4)]n (3) and [[Cu(L)Cl].2H2O]n (4). Variable-temperature magnetic data are well reproduced for one-dimensional infinite regular chain systems with J = -60.3 cm(-1) and g = 2.02 for 3 and J = -69.5 cm(-1) and g = 2.06, for 4. When 1 is used as a "ligand complex" for [M(hfac)2] (M = Cu(II), Ni(II), Mn(II), Zn(II)) in a basic medium, only the imidazolate-bridged trinuclear complexes [Cu(L)(hfac)M(hfac)2Cu(hfac)(L)] (M = Zn(II), Cu(II)) (5, 6) can be isolated. Nevertheless, the analogous complex containing Mn(II) as the central metal (7) can be prepared from the precursor [Cu(HL)Cl2] (2). All the trinuclear complexes are isostructural. The structures of 5 and 6 have been solved by X-ray crystallographic methods and consist of well-isolated molecules with Ci symmetry, the center of symmetry being located at the central metal. Thus, the copper(II) fragments are in trans positions, leading to a linear conformation. The magnetic susceptibility data (2-300 K), which reveal the occurrence of antiferromagnetic interactions between copper(II) ions and the central metal, were quantitatively analyzed for symmetrical three-spin systems to give the coupling parameters JCuCu = -37.2 and JCuMn = -3.7 cm(-1) with D = +/-0.4 cm(-1) for 6 and 7, respectively. These magnetic behaviors are compared with those for analogous systems and

  8. Substructure Main Bridge, River Piers A & V ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    Substructure - Main Bridge, River Piers A & V - Huey P. Long Bridge, Spanning Mississippi River approximately midway between nine & twelve mile points upstream from & west of New Orleans, Jefferson, Jefferson Parish, LA

  9. NASA Now: Operation IceBridge

    NASA Video Gallery

    During this NASA Now program, you'€™ll meet Michael Studinger, Project Scientist for Operation IceBridge. He'€™ll describe the purpose of the IceBridge campaign and how the campaign objectives will...

  10. The Bridge School: A Profile.

    ERIC Educational Resources Information Center

    Sementelli, Catherine

    2001-01-01

    At the Bridge School (Hillsborough, California), children with severe speech and physical disabilities are trained in the use of augmentative and alternative communication technologies, transitioned back to their home school districts, and given continuing support. Outreach and research endeavors keep the broader community informed and educated…

  11. A Bridge to the Future

    ERIC Educational Resources Information Center

    Anderson, Richard

    2008-01-01

    Career and technical education (CTE) has a promising future at Darlington (WI) High School. In this article, the author describes how a class bridge project became a real-world, project-based learning opportunity involving higher-level thinking skills that are at the core of CTE at his school. It began when a local citizen approached him at the…

  12. Bridging Cultures with Classroom Strategies.

    ERIC Educational Resources Information Center

    Rothstein-Fisch, Carrie; Greenfield, Patricia M.; Trumbull, Elise

    1999-01-01

    Collectivism, stressing family members' interdependence, is common to Latino cultures. In contrast, schools foster independence and individual achievement. To help teachers understand assumptions underlying these different values, the authors developed the "Bridging Cultures Project" as a research-based professional-development program. Science…

  13. Over the Ramp: Building Bridges

    ERIC Educational Resources Information Center

    Sutton, Mary

    2007-01-01

    TheatreWorks is the third largest theatre in the San Francisco bay area. Through the usual educational programs that $6 million companies tend to offer, it has reached over 100,000 students of all ages in the past 8 years. The TheatreWorks Bridges Projects, however, are special. They are intricate and expansive, work with multiple community…

  14. Evaluation of Summer Bridge Programs

    ERIC Educational Resources Information Center

    Garcia, Lisa D.; Paz, Chiara C.

    2009-01-01

    Many colleges and universities in the United States offer summer programs for their incoming students. While programs are structured and administered in a variety of ways and target various student populations, the most common type of summer bridge program aims to serve historically underrepresented students and students of low socioeconomic…

  15. Mixed 3d/4f polynuclear complexes with 2,2‧-oxydiacetate as bridging ligand: Synthesis, structure and chemical speciation of La M compounds (M = bivalent cation)

    NASA Astrophysics Data System (ADS)

    Domínguez, Sixto; Torres, Julia; Peluffo, Florencia; Mederos, Alfredo; González-Platas, Javier; Castiglioni, Jorge; Kremer, Carlos

    2007-03-01

    Heterometallic compounds containing La(III), bivalent cations M (M = Co, Ni, Ca), and 2,2‧-oxydiacetate (oda) as connecting ligand have been prepared and characterized. The complexes can be formulated as [La2M3(oda)6(H2O)6] · 12H2O. The structure of [La2Co3(oda)6(H2O)6] shows the presence of the La(III) coordinated by six carboxy and three ether oxygen atoms, and the Co(II) cation bonded to four carboxy oxygens and two molecules of water. An open 3D framework is observed, containing large hexagonal channels. The chemical systems were also investigated in solution (25.0 °C, I = 0.5 M Me4NCl) by potentiometry. The same kind of polynuclear species have been found in aqueous solution.

  16. 21. View of Clark Fork Vehicle Bridge facing west. Looking ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    21. View of Clark Fork Vehicle Bridge facing west. Looking at bridge deck, guard rail, juncture of two bridge spans. - Clark Fork Vehicle Bridge, Spanning Clark Fork River, serves Highway 200, Clark Fork, Bonner County, ID

  17. 28. Under ninth bridge, view to concrete dam and eighth ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    28. Under ninth bridge, view to concrete dam and eighth bridge in background during heavy rain, view to the SW. - Vicksburg National Military Park Roads & Bridges, Melan Arch Bridges, Spanning various tributaries at Confederate Avenue, Vicksburg, Warren County, MS

  18. North & South Elevations and Bridge Plan Chickamauga National ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    North & South Elevations and Bridge Plan - Chickamauga National Military Park Tour Roads, Gordon's Slough Bridge, At the confluence of Alexander's Bridge Road and Gordon's Slough, southeast of Alexander's Bridge, Fort Oglethorpe, Catoosa County, GA

  19. 26. Ninth Melan Bridge on tour route, in southern area ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    26. Ninth Melan Bridge on tour route, in southern area of park, looking to the SW back to eighth bridge. - Vicksburg National Military Park Roads & Bridges, Melan Arch Bridges, Spanning various tributaries at Confederate Avenue, Vicksburg, Warren County, MS

  20. Bridging nitrate groups in [Mn(4)O(3)(NO(3))(O(2)CMe)(3)(R(2)dbm)(3)] (R = H, Et) and [Mn(4)O(2)(NO(3))(O(2)CEt)(6)(bpy)(2)](ClO(4)): acidolysis routes to tetranuclear manganese carboxylate complexes.

    PubMed

    Aromí, Guillem; Bhaduri, Sumit; Artús, Pau; Folting, Kirsten; Christou, George

    2002-02-25

    New synthesis procedures are described to tetranuclear manganese carboxylate complexes containing the [Mn(4)O(2)](8+) or [Mn(4)O(3)X](6+) (X(-) = MeCO(2)(-), F(-), Cl(-), Br(-), NO(3)(-)) core. These involve acidolysis reactions of [Mn(4)O(3)(O(2)CMe)(4)(dbm)(3)] (1; dbm is the anion of dibenzoylmethane) or [Mn(4)O(2)(O(2)CEt)(6)(dbm)(2)] (8) with HX (X(-) = F(-), Cl(-), Br(-), NO(3)(-)); high-yield routes to 1 and 8 are also described. The X(-) = NO(3)(-) complexes [Mn(4)O(3)(NO(3))(O(2)CR)(3)(R'(2)dbm)(3)] (R = Me, R' = H (6); R = Me, R' = Et (7); R = Et, R' = H (12)) represent the first synthesis of the [Mn(4)O(3)(NO(3))](6+) core, which contains an unusual eta(1):mu(3)-NO(3)(-) group. Treatment of known [Mn(4)O(2)(O(2)CEt)(7)(bpy)(2)](ClO(4)) with HNO(3) gives [Mn(4)O(2)(NO(3))(O(2)CEt)(6)(bpy)(2)](ClO(4)) (15) containing a eta(1):eta(1):mu-NO(3)(-) group bridging the two body Mn(III) ions of the [Mn(4)O(2)](8+) butterfly core. Complex 7 x 4CH(2)Cl(2) crystallizes in space group P2(1)2(1)2(1) with (at -168 degrees C) a = 21.110(3) A, b = 22.183(3) A, c = 15.958(2) A, Z = 4, and V = 7472.4(3) A(3). Complex 15 x (3)/(2)CH(2)Cl(2) crystallizes in space group P2(1)/c with (at -165 degrees C) a = 26.025(4) A, b = 13.488(2) A, c = 32.102(6) A, beta = 97.27(1) degrees, Z = 8, and V = 11178(5) A(3). Complex 7 contains a [Mn(4)(mu(3)-O)(3)(mu(3)-NO(3))](6+) core (3Mn(III), Mn(IV)) as seen for previous [Mn(4)O(3)X](6+) complexes. Complex 15 contains a butterfly [Mn(4)(mu(3)-O)(2)](8+) core. (1)H NMR spectra have been recorded for all complexes reported in this work and the various resonances assigned. All complexes retain their structural integrity on dissolution in chloroform and dichloromethane. Magnetic susceptibility (chi(M)) data were collected on 12 in the 5-300 K range in a 10.0 kG (1 T) field. Fitting of the data to the theoretical chi(M) vs T expression appropriate for a [Mn(4)O(3)X](6+) complex of C(3)(v)() symmetry gave J(34) = -23.9 cm(-)(1), J(33) = 4.9 cm

  1. Bridge Programs in Illinois: Results of the 2010 Illinois Bridge Status Survey

    ERIC Educational Resources Information Center

    Taylor, J. L.; Harmon, T.

    2010-01-01

    This report provides a summary of major results of the Illinois Bridge Status Survey, administered online between April and June 2010. The purpose of the survey was to understand the extent to which bridge programs are being implemented in Illinois, as well as to build an online directory of bridge programs. Bridge programs are an emerging…

  2. 77 FR 53251 - Annual Materials Report on New Bridge Construction and Bridge Rehabilitation

    Federal Register 2010, 2011, 2012, 2013, 2014

    2012-08-31

    ... Rehabilitation AGENCY: Federal Highway Administration (FHWA), DOT. ACTION: Notice. SUMMARY: Section 1114 of the... used in new Federal-aid bridge construction and bridge rehabilitation projects. As part of the SAFETEA... bridge construction and bridge rehabilitation projects. Data on Federal-aid and non-Federal-aid...

  3. OVERVIEW OF BRIDGES WITH OR&L BRIDGE IN CENTER, WAIKELE CANAL ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    OVERVIEW OF BRIDGES WITH OR&L BRIDGE IN CENTER, WAIKELE CANAL BRIDGE IN BACKGROUND. SHOWING THE EARTHEN INCLINE THAT RAISES FARRINGTON HIGHWAY OVER THE FORMER OR&L TRACKS. VIEW FACING SOUTHWEST. - Waikele Canal Bridge and Highway Overpass, Farrington Highway and Waikele Stream, Waipahu, Honolulu County, HI

  4. Structural Bridges through Fold Space

    PubMed Central

    Edwards, Hannah; Deane, Charlotte M.

    2015-01-01

    Several protein structure classification schemes exist that partition the protein universe into structural units called folds. Yet these schemes do not discuss how these units sit relative to each other in a global structure space. In this paper we construct networks that describe such global relationships between folds in the form of structural bridges. We generate these networks using four different structural alignment methods across multiple score thresholds. The networks constructed using the different methods remain a similar distance apart regardless of the probability threshold defining a structural bridge. This suggests that at least some structural bridges are method specific and that any attempt to build a picture of structural space should not be reliant on a single structural superposition method. Despite these differences all representations agree on an organisation of fold space into five principal community structures: all-α, all-β sandwiches, all-β barrels, α/β and α + β. We project estimated fold ages onto the networks and find that not only are the pairings of unconnected folds associated with higher age differences than bridged folds, but this difference increases with the number of networks displaying an edge. We also examine different centrality measures for folds within the networks and how these relate to fold age. While these measures interpret the central core of fold space in varied ways they all identify the disposition of ancestral folds to fall within this core and that of the more recently evolved structures to provide the peripheral landscape. These findings suggest that evolutionary information is encoded along these structural bridges. Finally, we identify four highly central pivotal folds representing dominant topological features which act as key attractors within our landscapes. PMID:26372166

  5. Structural Bridges through Fold Space.

    PubMed

    Edwards, Hannah; Deane, Charlotte M

    2015-09-01

    Several protein structure classification schemes exist that partition the protein universe into structural units called folds. Yet these schemes do not discuss how these units sit relative to each other in a global structure space. In this paper we construct networks that describe such global relationships between folds in the form of structural bridges. We generate these networks using four different structural alignment methods across multiple score thresholds. The networks constructed using the different methods remain a similar distance apart regardless of the probability threshold defining a structural bridge. This suggests that at least some structural bridges are method specific and that any attempt to build a picture of structural space should not be reliant on a single structural superposition method. Despite these differences all representations agree on an organisation of fold space into five principal community structures: all-α, all-β sandwiches, all-β barrels, α/β and α + β. We project estimated fold ages onto the networks and find that not only are the pairings of unconnected folds associated with higher age differences than bridged folds, but this difference increases with the number of networks displaying an edge. We also examine different centrality measures for folds within the networks and how these relate to fold age. While these measures interpret the central core of fold space in varied ways they all identify the disposition of ancestral folds to fall within this core and that of the more recently evolved structures to provide the peripheral landscape. These findings suggest that evolutionary information is encoded along these structural bridges. Finally, we identify four highly central pivotal folds representing dominant topological features which act as key attractors within our landscapes.

  6. 49 CFR 236.713 - Bridge, movable.

    Code of Federal Regulations, 2010 CFR

    2010-10-01

    ... 49 Transportation 4 2010-10-01 2010-10-01 false Bridge, movable. 236.713 Section 236.713 Transportation Other Regulations Relating to Transportation (Continued) FEDERAL RAILROAD ADMINISTRATION... Bridge, movable. That section of a structure bridging a navigable waterway so designed that it may...

  7. Building Bridges One Line at a Time

    ERIC Educational Resources Information Center

    Grigsby, Cathy Murray

    2012-01-01

    In this article, first-grade students were taught the different kinds of lines that were part of the construction of various bridges--the curved lines of the arches of stone bridges, straight lines connecting the cables of a suspension bridge, vertical lines, horizontal lines, and so on. They gained practice in drawing structures and in fine brush…

  8. 49 CFR 236.713 - Bridge, movable.

    Code of Federal Regulations, 2013 CFR

    2013-10-01

    ... 49 Transportation 4 2013-10-01 2013-10-01 false Bridge, movable. 236.713 Section 236.713 Transportation Other Regulations Relating to Transportation (Continued) FEDERAL RAILROAD ADMINISTRATION... Bridge, movable. That section of a structure bridging a navigable waterway so designed that it may...

  9. 49 CFR 236.713 - Bridge, movable.

    Code of Federal Regulations, 2014 CFR

    2014-10-01

    ... 49 Transportation 4 2014-10-01 2014-10-01 false Bridge, movable. 236.713 Section 236.713 Transportation Other Regulations Relating to Transportation (Continued) FEDERAL RAILROAD ADMINISTRATION... Bridge, movable. That section of a structure bridging a navigable waterway so designed that it may...

  10. 49 CFR 236.713 - Bridge, movable.

    Code of Federal Regulations, 2011 CFR

    2011-10-01

    ... 49 Transportation 4 2011-10-01 2011-10-01 false Bridge, movable. 236.713 Section 236.713 Transportation Other Regulations Relating to Transportation (Continued) FEDERAL RAILROAD ADMINISTRATION... Bridge, movable. That section of a structure bridging a navigable waterway so designed that it may...

  11. 49 CFR 236.713 - Bridge, movable.

    Code of Federal Regulations, 2012 CFR

    2012-10-01

    ... 49 Transportation 4 2012-10-01 2012-10-01 false Bridge, movable. 236.713 Section 236.713 Transportation Other Regulations Relating to Transportation (Continued) FEDERAL RAILROAD ADMINISTRATION... Bridge, movable. That section of a structure bridging a navigable waterway so designed that it may...

  12. Remediation: Higher Education's Bridge to Nowhere

    ERIC Educational Resources Information Center

    Complete College America, 2012

    2012-01-01

    The intentions were noble. It was hoped that remediation programs would be an academic bridge from poor high school preparation to college readiness. Sadly, remediation has become instead higher education's "Bridge to Nowhere." This broken remedial bridge is travelled by some 1.7 million beginning students each year, most of whom will…

  13. Removal of failed crown and bridge

    PubMed Central

    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

  14. Removal of failed crown and bridge.

    PubMed

    Sharma, Ashu; Rahul, G R; Poduval, Soorya T; Shetty, Karunakar

    2012-07-01

    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

  15. Comparison between Modern Violin Bridge and Baroque Violin Bridge by Photoelastic Observation and Frequency Analysis

    NASA Astrophysics Data System (ADS)

    Matsutani, Akihiro

    2004-05-01

    A comparison between the modern bridge and the baroque bridge of the violin by photoelastic observation was carried out. The relationship between the stress part and the hole is symmetric in the modern and baroque bridges. The measured spectral envelopes of baroque bridges are similar to those of modern bridges in D- or G-strings, and have peaks at a frequency higher than those of modern bridges in E-string. The visualization method as used in this study may provide hints for the design of violin bridges.

  16. Bridging the gap

    PubMed Central

    Mahler, Stephen M; Huang, Edwin P; Chin, David Y; Gray, Peter P

    2011-01-01

    Therapeutic monoclonal antibodies (mAbs) currently dominate the biologics marketplace. Development of a new therapeutic mAb candidate is a complex, multistep process and early stages of development typically begin in an academic research environment. Recently, a number of facilities and initiatives have been launched to aid researchers along this difficult path and facilitate progression of the next mAb blockbuster. Complementing this, there has been a renewed interest from the pharmaceutical industry to reconnect with academia in order to boost dwindling pipelines and encourage innovation. In this review, we examine the steps required to take a therapeutic mAb from discovery through early stage preclinical development and toward becoming a feasible clinical candidate. Discussion of the technologies used for mAb discovery, production in mammalian cells and innovations in single-use bioprocessing is included. We also examine regulatory requirements for product quality and characterization that should be considered at the earliest stages of mAb development. We provide details on the facilities available to help researchers and small-biotech build value into early stage product development, and include examples from within our own facility of how technologies are utilized and an analysis of our client base. PMID:21822050

  17. L-edge X-ray Absorption Spectroscopy and DFT Calculations on Cu2O2 Species: Direct Electrophilic Aromatic Attack by Side-on Peroxo Bridged Dicopper(II) Complexes

    PubMed Central

    Qayyum, Munzarin F.; Sarangi, Ritimukta; Fujisawa, Kiyoshi; Stack, T. Daniel P.; Karlin, Kenneth D.; Hodgson, Keith O.; Hedman, Britt; Solomon, Edward I.

    2013-01-01

    The hydroxylation of aromatic substrates catalyzed by coupled binuclear copper enzymes has been observed with side-on-peroxo-dicopper(II) (P) and bis-μ-oxo-dicopper(III) (O) model complexes. The substrate-bound-O intermediate in [Cu(II)2(DBED)2(O)2]2+ (DBED=N,N′-di-tert-butyl-ethylenediamine) was shown to perform aromatic hydroxylation. For the [Cu(II)2(NO2-XYL)(O2)]2+ complex, only a P species was spectroscopically observed. However, it was not clear whether this O-O bond cleaves to proceed through an O-type structure along the reaction coordinate for hydroxylation of the aromatic xylyl linker. Accurate evaluation of these reaction coordinates requires reasonable quantitative descriptions of the electronic structures of the P and O species. We have performed Cu L-edge XAS on two well-characterized P and O species to experimentally quantify the Cu 3d character in their ground state wavefunctions. The lower per-hole Cu character (40±6%) corresponding to higher covalency in the O species compared to the P species (52±4%) reflects a stronger bonding interaction of the bis-μ-oxo core with the Cu(III) centers. DFT calculations show that 10-20% Hartree-Fock (HF) mixing for P and ~38% for O species are required to reproduce the Cu-O bonding; for the P species this HF mixing is also required for an antiferromagnetically coupled description of the two Cu(II) centers. B3LYP (with 20% HF) was, therefore, used to calculate the hydroxylation reaction coordinate of P in [Cu(II)2(NO2-XYL)(O2)]2+. These experimentally calibrated calculations indicate that the electrophilic attack on the aromatic ring does not involve formation of a Cu(III)2(O2−)2 species. Rather, there is direct electron donation from the aromatic ring into the peroxo σ* orbital of the Cu(II)2(O22−) species, leading to concerted C-O bond formation with O-O bond cleavage. Thus, species P is capable of direct hydroxylation of aromatic substrates without the intermediacy of an O-type species. PMID:24102191

  18. 33 CFR 118.100 - Retroreflective panels on bridge piers.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 33 Navigation and Navigable Waters 1 2013-07-01 2013-07-01 false Retroreflective panels on bridge... SECURITY BRIDGES BRIDGE LIGHTING AND OTHER SIGNALS § 118.100 Retroreflective panels on bridge piers. The... 12 inches square. (c) To mark bridge piers or channel sides on bridges not required to have...

  19. 49 CFR 237.111 - Review of bridge inspection reports.

    Code of Federal Regulations, 2013 CFR

    2013-10-01

    ... 49 Transportation 4 2013-10-01 2013-10-01 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...

  20. 49 CFR 237.109 - Bridge inspection records.

    Code of Federal Regulations, 2013 CFR

    2013-10-01

    ... 49 Transportation 4 2013-10-01 2013-10-01 false Bridge inspection records. 237.109 Section 237.109..., DEPARTMENT OF TRANSPORTATION BRIDGE SAFETY STANDARDS Bridge Inspection § 237.109 Bridge inspection records... performed on those bridges under this part. (b) Each record of an inspection under the bridge...

  1. 49 CFR 237.111 - Review of bridge inspection reports.

    Code of Federal Regulations, 2012 CFR

    2012-10-01

    ... 49 Transportation 4 2012-10-01 2012-10-01 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...

  2. 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...

  3. 49 CFR 237.109 - Bridge inspection records.

    Code of Federal Regulations, 2010 CFR

    2010-10-01

    ... 49 Transportation 4 2010-10-01 2010-10-01 false Bridge inspection records. 237.109 Section 237.109..., DEPARTMENT OF TRANSPORTATION BRIDGE SAFETY STANDARDS Bridge Inspection § 237.109 Bridge inspection records... performed on those bridges under this part. (b) Each record of an inspection under the bridge...

  4. 49 CFR 237.111 - Review of bridge inspection reports.

    Code of Federal Regulations, 2014 CFR

    2014-10-01

    ... 49 Transportation 4 2014-10-01 2014-10-01 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...

  5. 33 CFR 118.100 - Retroreflective panels on bridge piers.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 33 Navigation and Navigable Waters 1 2014-07-01 2014-07-01 false Retroreflective panels on bridge... SECURITY BRIDGES BRIDGE LIGHTING AND OTHER SIGNALS § 118.100 Retroreflective panels on bridge piers. The... 12 inches square. (c) To mark bridge piers or channel sides on bridges not required to have...

  6. 49 CFR 237.109 - Bridge inspection records.

    Code of Federal Regulations, 2012 CFR

    2012-10-01

    ... 49 Transportation 4 2012-10-01 2012-10-01 false Bridge inspection records. 237.109 Section 237.109..., DEPARTMENT OF TRANSPORTATION BRIDGE SAFETY STANDARDS Bridge Inspection § 237.109 Bridge inspection records... performed on those bridges under this part. (b) Each record of an inspection under the bridge...

  7. 33 CFR 118.100 - Retroreflective panels on bridge piers.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 33 Navigation and Navigable Waters 1 2010-07-01 2010-07-01 false Retroreflective panels on bridge... SECURITY BRIDGES BRIDGE LIGHTING AND OTHER SIGNALS § 118.100 Retroreflective panels on bridge piers. The... 12 inches square. (c) To mark bridge piers or channel sides on bridges not required to have...

  8. 33 CFR 118.100 - Retroreflective panels on bridge piers.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 33 Navigation and Navigable Waters 1 2012-07-01 2012-07-01 false Retroreflective panels on bridge... SECURITY BRIDGES BRIDGE LIGHTING AND OTHER SIGNALS § 118.100 Retroreflective panels on bridge piers. The... 12 inches square. (c) To mark bridge piers or channel sides on bridges not required to have...

  9. 49 CFR 237.109 - Bridge inspection records.

    Code of Federal Regulations, 2014 CFR

    2014-10-01

    ... 49 Transportation 4 2014-10-01 2014-10-01 false Bridge inspection records. 237.109 Section 237.109..., DEPARTMENT OF TRANSPORTATION BRIDGE SAFETY STANDARDS Bridge Inspection § 237.109 Bridge inspection records... performed on those bridges under this part. (b) Each record of an inspection under the bridge...

  10. 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...

  11. 49 CFR 237.109 - Bridge inspection records.

    Code of Federal Regulations, 2011 CFR

    2011-10-01

    ... 49 Transportation 4 2011-10-01 2011-10-01 false Bridge inspection records. 237.109 Section 237.109..., DEPARTMENT OF TRANSPORTATION BRIDGE SAFETY STANDARDS Bridge Inspection § 237.109 Bridge inspection records... performed on those bridges under this part. (b) Each record of an inspection under the bridge...

  12. Diode-quad bridge circuit means

    NASA Technical Reports Server (NTRS)

    Harrison, D. R.; Dimeff, J. (Inventor)

    1975-01-01

    Diode-quad bridge circuit means is described for use as a transducer circuit or as a discriminator circuit. It includes: (1) a diode bridge having first, second, third, and fourth bridge terminals consecutively coupled together by four diodes polarized in circulating relationship; (2) a first impedance connected between the second bridge terminal and a circuit ground; (3) a second impedance connected between the fourth bridge terminal and the circuit ground; (4) a signal source having a first source terminal capacitively coupled to the first and third bridge terminals, and a second source terminal connected to the circuit ground; and (5) an output terminal coupled to the first bridge terminal and at which an output signal may be taken.

  13. 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

  14. New oxa-bridged macrocycles.

    PubMed

    Panten, Johannes; Surburg, Horst; Hölscher, Bernd

    2008-06-01

    In creating new aroma molecules, the fragrance chemist can make use of several tools: receptor or combinatorial research as well as lead structure optimization of existing chemicals or substances from the natural pool. Sometimes, it is also possible to discover new structures via another way: the careful analysis of existing products and their production processes. In analyzing the production process of 1-oxacyclohexadecan-2-one (6), we identified at least two new oxa-bridged macrocyclic molecules. In continuation, these results inspired us to synthesize and evaluate more representatives with similar structures. In this contribution, presented at the RSC/SCI conference 'flavours & fragrances 2007' in London, September 24-26, 2007, the synthesis and olfactory properties of several new oxa-bridged macrocycles will be introduced and discussed.

  15. Full-bridge capacitive extensometer

    NASA Astrophysics Data System (ADS)

    Peters, Randall D.

    1993-08-01

    Capacitive transducers have proven to be very effective sensors of small displacements, because of inherent stability and noninvasive high resolution. The most versatile ones have been those of a differential type, in which two elements are altered in opposite directions in response to change of the system parameter being monitored. Oftentimes, this differential pair has been incorporated into a bridge circuit, which is a useful means for employing synchronous detection to improve signal to noise ratios. Unlike previous differential capacitive dilatometers which used only two active capacitors, the present sensor is a full-bridge type, which is well suited to measuring low-level thermal expansions. This analog sensor is capable of 0.1 μm resolution anywhere within a range of several centimeters, with a linearity of 0.1%. Its user friendly output can be put on a strip chart recorder or directed to a computer for sophisticated data analysis.

  16. Synthesis, structure, luminescent, and magnetic properties of carbonato-bridged Zn(II)2Ln(III)2 complexes [(μ4-CO3)2{Zn(II)L(n)Ln(III)(NO3)}2] (Ln(III) = Gd(III), Tb(III), Dy(III); L(1) = N,N'-bis(3-methoxy-2-oxybenzylidene)-1,3-propanediaminato, L(2) = N,N'-bis(3-ethoxy-2-oxybenzylidene)-1,3-propanediaminato).

    PubMed

    Ehama, Kiyomi; Ohmichi, Yusuke; Sakamoto, Soichiro; Fujinami, Takeshi; Matsumoto, Naohide; Mochida, Naotaka; Ishida, Takayuki; Sunatsuki, Yukinari; Tsuchimoto, Masanobu; Re, Nazzareno

    2013-11-01

    Carbonato-bridged Zn(II)2Ln(III)2 complexes [(μ4-CO3)2{Zn(II)L(n)Ln(III)(NO3)}2]·solvent were synthesized through atmospheric CO2 fixation reaction of [Zn(II)L(n)(H2O)2]·xH2O, Ln(III)(NO3)3·6H2O, and triethylamine, where Ln(III) = Gd(III), Tb(III), Dy(III); L(1) = N,N'-bis(3-methoxy-2-oxybenzylidene)-1,3-propanediaminato, L(2) = N,N'-bis(3-ethoxy-2-oxybenzylidene)-1,3-propanediaminato. Each Zn(II)2Ln(III)2 structure possessing an inversion center can be described as two di-μ-phenoxo-bridged {Zn(II)L(n)Ln(III)(NO3)} binuclear units bridged by two carbonato CO3(2-) ions. The Zn(II) ion has square pyramidal coordination geometry with N2O2 donor atoms of L(n) and one oxygen atom of a bridging carbonato ion at the axial site. Ln(III) ion is coordinated by nine oxygen atoms consisting of four from the deprotonated Schiff-base L(n), two from a chelating nitrate, and three from two carbonate groups. The temperature-dependent magnetic susceptibilities in the range 1.9-300 K, field-dependent magnetization from 0 to 5 T at 1.9 K, and alternating current magnetic susceptibilities under the direct current bias fields of 0 and 1000 Oe were measured. The magnetic properties of the Zn(II)2Ln(III)2 complexes are analyzed on the basis of the dicarbonato-bridged binuclear Ln(III)-Ln(III) structure, as the Zn(II) ion with d(10) electronic configuration is diamagnetic. ZnGd1 (L(1)) and ZnGd2 (L(2)) show a ferromagnetic Gd(III)-Gd(III) interaction with J(Gd-Gd) = +0.042 and +0.028 cm(-1), respectively, on the basis of the Hamiltonian H = -2J(Gd-Gd)ŜGd1·ŜGd2. The magnetic data of the Zn(II)2Ln(III)2 complexes (Ln(III) = Tb(III), Dy(III)) were analyzed by a spin Hamiltonian including the crystal field effect on the Ln(III) ions and the Ln(III)-Ln(III) magnetic interaction. The Stark splitting of the ground state was so evaluated, and the energy pattern indicates a strong easy axis (Ising type) anisotropy. Luminescence spectra of Zn(II)2Tb(III)2 complexes were observed, while those

  17. Parabolic metamaterials and Dirac bridges

    NASA Astrophysics Data System (ADS)

    Colquitt, D. J.; Movchan, N. V.; Movchan, A. B.

    2016-10-01

    A new class of multi-scale structures, referred to as `parabolic metamaterials' is introduced and studied in this paper. For an elastic two-dimensional triangular lattice, we identify dynamic regimes, which corresponds to so-called `Dirac Bridges' on the dispersion surfaces. Such regimes lead to a highly localised and focussed unidirectional beam when the lattice is excited. We also show that the flexural rigidities of elastic ligaments are essential in establishing the `parabolic metamaterial' regimes.

  18. Cross-Quint-Bridge Resistor

    NASA Technical Reports Server (NTRS)

    Hannaman, David J.; Lieneweg, Udo; Buehler, Martin G.; Mantalas, Linda

    1991-01-01

    Integrated-circuit conductive test pattern intended to provide data on effects of design widths and design spacings upon actual widths of conductive lines. Provides for electrical measurements both on lines of unknown width and on features having known dimensions. Data from measurements on five bridges used to determine four parameters of mathematical model describing system. In principle, pattern determines effects of width and spacing and interaction between them.

  19. Halliburton Composite Bridge Plug Assembly

    SciTech Connect

    Starbuck, J.M.; Luttrell, C.R.; Aramayo, G.

    2005-01-15

    The overall objectives of this CRADA were to assist Halliburton in analyzing a composite bridge plug and to determine why their original design was failing in the field. In Phase 1, finite element analyses were done on the original composite slip design and several alternative designs. The composite slip was the component in the bridge plug that was failing. The finite element code ABAQUS was used for these calculations and I-DEAS was used as the pre- and post-processor in the analyses. Several different designs and materials were analyzed and recommendations were made towards improving the design. In Phase 2, the objective was to develop finite element models that would accurately represent the deformations in the entire all-composite 4-1/2' diameter bridge plug assembly. The finite element code LS-DYNA was used and the results from this effort were intended to expand Halliburton's composite design and analysis capabilities with regard to developing future composite components for downhole tools. In addition to the finite element modeling, this effort involved the utilization of micromechanics to determine the necessary composite material properties that were needed as input for finite element codes.

  20. Bim from Laser SCANS… not Just for Buildings: Nurbs-Based Parametric Modeling of a Medieval Bridge

    NASA Astrophysics Data System (ADS)

    Barazzetti, L.; Banfi, F.; Brumana, R.; Previtali, M.; Roncoroni, F.

    2016-06-01

    Building Information Modelling is not limited to buildings. BIM technology includes civil infrastructures such as roads, dams, bridges, communications networks, water and wastewater networks and tunnels. This paper describes a novel methodology for the generation of a detailed BIM of a complex medieval bridge. The use of laser scans and images coupled with the development of algorithms able to handle irregular shapes allowed the creation of advanced parametric objects, which were assembled to obtain an accurate BIM. The lack of existing object libraries required the development of specific families for the different structural elements of the bridge. Finally, some applications aimed at assessing the stability and safety of the bridge are illustrated and discussed. The BIM of the bridge can incorporate this information towards a new "BIMonitoring" concept to preserve the geometric complexity provided by point clouds, obtaining a detailed BIM with object relationships and attributes.