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Sample records for trans mixed ligand

  1. Synthesis, Photophysical and Electrochemical Properties of a Mixed Bipyridyl-Phenanthrolyl Ligand Ru(II Heteroleptic Complex Having trans-2-Methyl-2-butenoic Acid Functionalities

    Directory of Open Access Journals (Sweden)

    Adewale O. Adeloye

    2011-09-01

    Full Text Available In this work, two ligands: 4-(trans-2-Methyl-2-butenoic acid-2,2'-bipyridine (L1 and 5-(trans-2-methyl-2-butenoic acid-1,10-phenanthroline (L2, with the corresponding mixed-ligand heteroleptic Ru(II complex were synthesized and characterized by FT-IR, 1H-, 13C-NMR spectroscopy and elemental analysis. The influence of the mixed functionalized polypyridyl ruthenium(II complex on the photophysical and electrochemical properties were investigated and compared to individual single-ligand homoleptic complexes. Interestingly, the mixed-ligand complex formulated as [RuL1L2(NCS2] exhibits broad and intense metal-to-ligand charge transfer (MLCT absorption with a high molar extinction coefficient (λmax = 514 nm, ε = 69,700 M−1 cm−1, better than those of individual single-ligand complexes, [Ru(L12(NCS2] and [Ru(L22(NCS2], and a strong photoluminescence intensity ratio in the red region at λem = 686 nm. The electrochemical properties of the complex indicated that the redox processes are ligand-based.

  2. Trans-ligand-dependent arrangement (bent or linear) of Pt II-bound dialkylcyanamide ligands: Molecular structure of trans-dichloro(dimethylcyanamide)(dimethyl sulfoxide)platinum(II)

    Science.gov (United States)

    Anisimova, Tatyana B.; Bokach, Nadezhda A.; Fritsky, Igor O.; Haukka, Matti

    2011-11-01

    The title compound, trans-[PtCl 2(NCNMe 2)(Me 2SO)], is the first example of the structurally characterized Pt II species having the nitrile and the sulfoxide ligands in the trans-position to each other. The most significant feature of this structure is the non-linear arrangement of the Pt sbnd N1 sbnd C1 fragment providing the rare case of the bent form of the dialkylcyanamide ligand.

  3. Mixed-ligand binuclear copper(II)

    Indian Academy of Sciences (India)

    A new mixed-ligand binuclear copper(II) complex [Cu(MS)(bpy)]2.(ClO4)2, built of 5-methylsalicylaldehyde and 2,2'-bipyridyl has been synthesized and characterized by using elemental analysis, IR and UV-Vis spectroscopy. Crystal structure of the complex shows that copper(II) ion lies in a square pyramidal coordination ...

  4. Supramolecular coordination and antimicrobial activities of constructed mixed ligand complexes

    Science.gov (United States)

    El-Sonbati, A. Z.; Diab, M. A.; El-Bindary, A. A.; Abou-Dobara, M. I.; Seyam, H. A.

    2013-03-01

    A novel series of copper(II) and palladium(II) with 4-derivatives benzaldehyde pyrazolone (Ln) were synthesized. The mixed ligand complexes were prepared by using 1,10-phenanthroline (Phen) as second ligand. The structure of these complexes was identified and confirm by elemental analysis, molar conductivity, UV-Vis, IR and 1H NMR spectroscopy and magnetic moment measurements as well as thermal analysis. The ligand behaves as a neutral bidentate ligand through ON donor sites. ESR spectra show the simultaneous presence of a planar trans and a nearly planar cis isomers in the 1:2 ratio for all N,O complexes [Cu(Ln)2]Cl2ṡ2H2O. Schiff bases (Ln) were tested against bacterial species; namely two Gram positive bacteria (Staphylococcus aureus and Bacillus cereus) and two Gram negative bacteria (Escherichia coli and Klebsiella pneumoniae) and fungal species (Aspergillus niger, Fusarium oxysporium, Penicillium italicum and Alternaria alternata). The tested compounds have antibacterial activity against S. aureus, B. cereus and K. pneumoniae.

  5. Spectral studies on mixed ligand complexes of sodium dinitro-bis(acetylacetonato) cobaltate(iii) with imida-zole ligands

    Science.gov (United States)

    Roychaudhury, Goutam; Dash, Kailash C.

    1980-11-01

    A number of mixed ligand complexes, nitro(imidazole) bis(acetylacetonato) cobaltate(III), [Co(acac) 2 (NO 2 ) 2 (L)] (L = imidazole or substituted imidazole) have been synthesised and characterised on the basis of chemical analyses, IR, electronic, mass and nuclear ( 1H and 13C) magnetic resonance spectra as well as TGA and DTA data. All complexes are non-electrolytic and possess a trans octahedral structure. The NO 2- group is coordinated through the N atom. Though the 1H NMR data of fresh CDCl 3 solutions of complexes confirm the trans structure, slow isomerisation to the cis configuration is observed at room temperature.

  6. Synthesis and characterization of mixed ligand chiral nanoclusters

    KAUST Repository

    Guven, Zekiye P.

    2016-06-22

    Chiral mixed ligand silver nanoclusters were synthesized in the presence of a chiral and an achiral ligand. While the chiral ligand led mostly to the formation of nanoparticles, the presence of the achiral ligand drastically increased the yield of nanoclusters with enhanced chiral properties. © 2016 The Royal Society of Chemistry.

  7. Mixed-Ligand Complexes Of Nickel (II) With 2-Acetylpyridine ...

    African Journals Online (AJOL)

    The preparation and spectral properties of five nickel (II) mixed-ligands complexes (Ni [2-Actsc.Y]CI2), derived from 2-acetylpyridinethiosermicarbazones and some nitrogen/sulphur monodentate ligands such as thiophene, ammonia, picoline, pyridine and aniline are described. The complexes have been characterized on ...

  8. Mixed-ligand binuclear copper (II) complex of 5 ...

    Indian Academy of Sciences (India)

    A new mixed-ligand binuclear copper(II) complex [Cu(MS)(bpy)]2.(ClO4)2, built of 5-methylsalicylaldehyde and 2,2'-bipyridyl has been synthesized and characterized by using elemental analysis, IR and UV-Vis spectroscopy. Crystal structure of the complex shows that copper(II) ion lies in a square pyramidal coordination ...

  9. Synthesis and characterization of mixed ligand complexes of Zn (II ...

    Indian Academy of Sciences (India)

    Mixed ligand complexes of Zn(II) and Co(II) with cysteine, histidine, cysteinemethylester, and histidinemethylester have been synthesized and characterized by elemental analysis, conductivity, magnetic susceptibility measurements, and infrared, 1H NMR, TGA and FAB mass spectra. In these complexes, histidine, and ...

  10. Gas adsorption and gas mixture separations using mixed-ligand MOF material

    Science.gov (United States)

    Hupp, Joseph T [Northfield, IL; Mulfort, Karen L [Chicago, IL; Snurr, Randall Q [Evanston, IL; Bae, Youn-Sang [Evanston, IL

    2011-01-04

    A method of separating a mixture of carbon dioxiode and hydrocarbon gas using a mixed-ligand, metal-organic framework (MOF) material having metal ions coordinated to carboxylate ligands and pyridyl ligands.

  11. Characterization of Ligand Shell for Mixed-Ligand Coated Gold Nanoparticles.

    Science.gov (United States)

    Ong, Quy; Luo, Zhi; Stellacci, Francesco

    2017-08-15

    Gold nanoparticles owe a large number of their properties to their ligand shell. Indeed, many researchers routinely use mixtures of ligand molecules for their nanoparticles to impart complex property sets. It has been shown that the morphology of ligand shells (e.g., Janus, random, stripelike) leads to specific properties. Examples include wettability, solubility, protein nonspecific adsorption, cell penetration, catalysis, and cation-capturing abilities. Yet, it remains a great challenge to evaluate such morphologies in even the most fundamental terms such as dimension and shape. In this Account, we review recent progress in characterization techniques applicable to gold nanoparticles with ligand shells composed of mixed ligands. We divide the characterization into three major categories, namely, microscopy, spectroscopy, and simulation. In microscopy, we review progresses in scanning tunneling microscopy (STM), atomic force microscopy (AFM), and scanning/transmission electron microscopy. In spectroscopy, we mainly highlight recent achievements in nuclear magnetic resonance (NMR), mass spectrometry (MS), small angle neutron scattering (SANS), electron spin resonance (EPR), and adsorption based spectroscopies. In simulation, we point out the latest results in understanding thermodynamic stability of ligand shell morphology and emphasize the role of computer simulation for helping interpretation of experimental data. We conclude with a perspective of future development.

  12. Fringe proteins modulate Notch-ligand cis and trans interactions to specify signaling states.

    Science.gov (United States)

    LeBon, Lauren; Lee, Tom V; Sprinzak, David; Jafar-Nejad, Hamed; Elowitz, Michael B

    2014-09-25

    The Notch signaling pathway consists of multiple types of receptors and ligands, whose interactions can be tuned by Fringe glycosyltransferases. A major challenge is to determine how these components control the specificity and directionality of Notch signaling in developmental contexts. Here, we analyzed same-cell (cis) Notch-ligand interactions for Notch1, Dll1, and Jag1, and their dependence on Fringe protein expression in mammalian cells. We found that Dll1 and Jag1 can cis-inhibit Notch1, and Fringe proteins modulate these interactions in a way that parallels their effects on trans interactions. Fringe similarly modulated Notch-ligand cis interactions during Drosophila development. Based on these and previously identified interactions, we show how the design of the Notch signaling pathway leads to a restricted repertoire of signaling states that promote heterotypic signaling between distinct cell types, providing insight into the design principles of the Notch signaling system, and the specific developmental process of Drosophila dorsal-ventral boundary formation.

  13. Carbon monoxide and related π-acceptors are good ligands for trivalent metallocenes of uranium and the trans-uranium metals

    International Nuclear Information System (INIS)

    Andersen, R.A.

    1990-01-01

    The evolution of the concept that tertiary phosphines are good ligands towards the tetravalent uranium halides and that phosphines, carbon monoxide, and related π-acceptor ligands are good ligands towards the trivalent uranium metallocenes will be described. Solid state X-ray, crystallographic and solution state equilibrium quotient studies show the ligand displacement series: (RO) 3 P > R 3 P > R 3 N; RNC > RCN. These concepts will be extended to the trans-uranium element neptunium and plutonium

  14. CODE MIXING FOUND IN BUKAN EMPAT MATA PROGRAM ON TRANS 7 TELEVISION CHANNEL

    Directory of Open Access Journals (Sweden)

    Fitria Nur Hamidah

    2015-05-01

    Full Text Available This study is aimed to find the kinds of code mixing and to know which kinds of code mixing are dominantly used in Bukan Empat Mata Program on TRANS 7 Television channel. Descriptive qualitative method is used in this study. The data were collected through watching, recording, transferring, playing, selecting and transcribing the data from the conversations between the presenters and the guest stars. The collected data were then analyzed through identifying the data, selecting the data related to the code mixing, listing and classifying the data based on the kinds of code mixing and finally drawing conclusion. It was found that there are two kinds of code mixing used by prersenters and guest stars in Bukan Empat Mata program, namely situational and conversational code mixing. Between two kinds of code mixing, conversational code mixing is dominantly used both by presenters and the guest stars in which they sometimes change the pronunciation from English into Indonesian in the conversation.

  15. Trans labilization of am(m)ine ligands from platinum(II) complexes by cancer cell extracts.

    Science.gov (United States)

    Kasherman, Yonit; Sturup, Stefan; Gibson, Dan

    2009-03-01

    Cisplatin, cis-[Pt(NH(3))(2)Cl(2)], is an effective anticancer agent in wide clinical use whose efficacy is affected by cellular interactions with sulfur-containing nucleophiles. These interactions can potentially enhance the efficacy of the drug by mediating its delivery to nuclear DNA or inactivate the drug by binding to it irreversibly or by labilizing the NH(3) ligands. Despite the potential importance of trans-labilization reactions in the mechanism of action of the drug, few detailed studies on trans labilization of the ammines have been conducted. We used 2D NMR to show that some trans labilization occurs in proliferating cells and that aqueous extracts of cancer cells labilized 20% of the amine ligands of cis-[PtCl(2)((13)CH(3)NH(2))(2)] after a 12-h incubation. Both low molecular mass nucleophiles (less than 3 kDa) and high molecular mass nucleophiles (more than 3 kDa) labilize the amines with similar efficiency. Studies with model compounds show that thiols and thioethers bind to platinum(II) at similar rates, but thioethers are significantly more efficient at labilizing the am(m)ine at lower pH. N-Acetylcysteine is a more efficient trans-labilizer than glutathione, suggesting that the displacement of the amine proceeds through an associative mechanism. The lag time, the time that elapses from the formation of the Pt-S bond till the release of the amine trans to the sulfur, depends on the pH (for thiols), increasing at lower pH. Quantification of the platinum adducts obtained from incubation of cisplatin with cell extracts indicates that two thirds of the platinum is bound to cellular components with molecular mass greater than 3 kDa.

  16. Rigid nonproteinogenic cyclic amino acids as ligands for glutamate receptors: trans-tris(homoglutamic) acids

    DEFF Research Database (Denmark)

    Meyer, Udo; Bisel, Philippe; Bräuner-Osborne, Hans

    2005-01-01

    of the trans-1S,2R-configured secondary alpha-amino amido-ester. In receptor binding assays and functional tests, trans-1S,2R-1-amino-2-carboxymethylcyclopentanecarboxylic acid hydrochloride was found to behave as a selective mGluR(2)-antagonist without relevant binding properties at iGluRs.......The second-generation asymmetric synthesis of the trans-tris(homoglutamic) acids reported herein proceeds via Strecker reaction of chiral ketimines, obtained from condensation of racemic 2-ethoxycarbonylmethylcyclopentanone and commercially available (S)- and (R)-1-phenylethylamine, respectively......) yielded diastereomeric mixtures of secondary alpha-amino amido-esters, which after separation were hydrogenolyzed and hydrolyzed each to the enantiomeric trans-1-amino-2-carboxymethylcyclopentanecarboxylic acids. Their configuration was completely established by NMR methods, CD spectra, and X-ray analysis...

  17. Semiexperimental equilibrium structures for cis,cis- and trans,trans-1,4-difluorobutadiene by the mixed estimation method and definitive relative energies of the isomers.

    Science.gov (United States)

    Demaison, Jean; Császár, Attila G; Groner, Peter; Rudolph, Heinz Dieter; Craig, Norman C

    2013-12-12

    Equilibrium molecular structures accurate to 0.001 Å and 0.2° have been determined for cis,cis- and trans,trans-1,4-difluorobutadiene by the semiexperimental mixed estimation method. In this method, structures are fitted concurrently to equilibrium rotational constants and bond parameters obtained from an intermediate level of electronic structure theory. The effect of fluorine substitution on the carbon backbone of butadiene is surprisingly small. Definitive energy differences for the ground states were computed, employing the focal-point analysis (FPA) technique, between the trans,trans and cis,cis isomers (ΔH°0 = 5.6(3) kJ mol(-1)) and the cis,trans and cis,cis isomers (ΔH°0 = 3.2(2) kJ mol(-1)) of 1,4-difluorobutadiene. These differences confirm the exceptional relationship that the trans,trans isomer has the highest energy and the cis,cis isomer the lowest energy, endorsing what was reported earlier on the basis of experimental observations in benzene solution.

  18. Preparation, Spectroscopic Investigation and Biological Activity of New Mixed Ligand Chelates

    International Nuclear Information System (INIS)

    Alassbaly, F.S.; Ajaily, M.M.E.

    2014-01-01

    Preparation and investigation of new Co(II), Ni(II), Zn(II) and Cr(III) chelates with mixed ligands including Schiff base (L1) formed from the condensation of 4-dimethylaminobenzaldehyde with 2-aminophenol and anthranilic acid (L2) were studied. The obtained Schiff base and mixed ligand chelates were subjected to several physiochemical techniques, in terms of CHN elemental analyses, molar conductivity, magnetic moment measurements, infrared, proton nuclear magnetic resonance, electronic and mass spectra. The analytical data showed the formation of the Schiff base compound and the ratio of metal to ligands of the chelates are 1:1:1(M:L1:L2). The infrared spectral data exhibited that the used ligands behaving as bidentate ligands towards the metal ions. The proton nuclear magnetic resonance spectral data showed the signals of the active groups in the ligands which entered in chelation with Zn(II) metal ion. The electronic spectral results showed the existence of pie (phenyl ring) and n = pie (C=N) of the ligands and suggested the geometrical structures of the chelates. Meanwhile, the mass spectral data revealed the fragmentations of the Schiff base, anthranilic acid and their Ni(II) mixed ligand chelate has been preformed the only chelate conducted for justification. All the prepared mixed chelates were non-electrolyte in nature. The antibacterial activity of the Schiff base, anthranilic acid, metal salts and mixed ligand chelates were studied and found to be that mixed ligand chelates have the most biological activity in comparison to the free ligands and salts. (author)

  19. Synthesis and characterization of fac-[M(CO)3(P)(OO)] and cis-trans-[M(CO)2(P)2(OO)] complexes (M = Re, (99m)Tc) with acetylacetone and curcumin as OO donor bidentate ligands.

    Science.gov (United States)

    Triantis, Charalampos; Tsotakos, Theodoros; Tsoukalas, Charalampos; Sagnou, Marina; Raptopoulou, Catherine; Terzis, Aris; Psycharis, Vassilis; Pelecanou, Maria; Pirmettis, Ioannis; Papadopoulos, Minas

    2013-11-18

    The synthesis and characterization of neutral mixed ligand complexes fac-[M(CO)3(P)(OO)] and cis-trans-[M(CO)2(P)2(OO)] (M = Re, (99m)Tc), with deprotonated acetylacetone or curcumin as the OO donor bidentate ligands and a phosphine (triphenylphosphine or methyldiphenylphosphine) as the monodentate P ligand, is described. The complexes were synthesized through the corresponding fac-[M(CO)3(H2O)(OO)] (M = Re, (99m)Tc) intermediate aqua complex. In the presence of phosphine, replacement of the H2O molecule of the intermediate complex at room temperature generates the neutral tricarbonyl monophosphine fac-[Re(CO)3(P)(OO)] complex, while under reflux conditions further replacement of the trans to the phosphine carbonyl generates the new stable dicarbonyl bisphosphine complex cis-trans-[Re(CO)2(P)2(OO)]. The Re complexes were fully characterized by elemental analysis, spectroscopic methods, and X-ray crystallography showing a distorted octahedral geometry around Re. Both the monophosphine and the bisphosphine complexes of curcumin show selective binding to β-amyloid plaques of Alzheimer's disease. At the (99m)Tc tracer level, the same type of complexes, fac-[(99m)Tc(CO)3(P)(OO)] and cis-trans-[(99m)Tc(CO)2(P)2(OO)], are formed introducing new donor combinations for (99m)Tc(I). Overall, β-diketonate and phosphine constitute a versatile ligand combination for Re(I) and (99m)Tc(I), and the successful employment of the multipotent curcumin as β-diketone provides a solid example of the pharmacological potential of this system.

  20. Mixed-ligand complexes of zirconium (IV) and uranium with salicylaldehyde and some heterocyclic azopyrazolones

    International Nuclear Information System (INIS)

    Amrallahi, A.H.

    1994-01-01

    Mixed-ligand complexes of Zr(IV) and U(IV) with salicylaldehyde (SA) and some heterocyclic azopyrazolenes have been studied spectrophotometrically. All formed chelates have ratio 1:1:1. The stoichiometry and stability of the binary mixed chelates been evaluated. Elemental analysis, molar conductance and IR spectra have been used for identification of solid mixed complexes. (author)

  1. Copper(II) mixed ligands complexes of hydroxamic acids with glycine, histamine and histidine

    OpenAIRE

    Fernandes, Maria Celina M.M.; Paniago, Eucler B.; Carvalho, Sandra

    1997-01-01

    A potentiometric and spectrophotometric study of physiologically interesting CuII mixed ligand complexes has been performed involving hydroxamic acids as primary ligands (A) and secondary ligands (B) represented either by histamine or the aminoacids glycine and histidine. All are potentially able to form chelate complexes with either five or six membered rings. The formation constant and the visible absorption spectrum were calculated for each one of the identified species, both binary and mi...

  2. Assembly of Zn(II) and Cd(II) coordination polymers based on a flexible multicarboxylate ligand and nitrogen-containing auxiliary ligands through a mixed-ligand synthetic strategy: syntheses, structures and fluorescence properties.

    Science.gov (United States)

    Lu, Ji Tao; Meng, Dan Dan; Meng, Qing-Guo

    2016-02-01

    The structures of coordination polymers are strongly influenced by the organic ligands and metal ions used for their construction, so it is important to choose suitable ligands and metal ions and appropriate synthetic processes. Two novel d(10) coordination polymers, namely poly[[diaquabis(2,2'-bipyridine)[μ4-4,4'-(1,4-phenylenedioxy)bis(benzene-1,2-dicarboxylato)]dizinc(II)] dihydrate], {[Zn2(C22H10O10)(C10H8N2)2(H2O)2]·2H2O}n, (1), and poly[[diaquabis(1,10-phenanthroline)[μ4-4,4'-(1,4-phenylenedioxy)bis(benzene-1,2-dicarboxylato)]dicadmium(II)] dimethylformamide disolvate], {[Cd2(C22H10O10)(C12H8N2)2(H2O)2]·2C3H7NO}n, (2), have been synthesized from 4,4'-(1,4-phenylenedioxy)bis(benzene-1,2-dicarboxylic acid) (H4L) and two different N-containing auxiliary ligands through a mixed-ligand synthetic strategy under a solvothermal environment. The structures were characterized by single-crystal X-ray diffraction, powder X-ray diffraction, elemental analysis and IR spectroscopy. Compounds (1) and (2) both present one-dimensional chain structures and two-dimensional supramolecular layer structures constructed by weak hydrogen bonds. It is interesting to note that the carboxylate ligands reveal stable trans configurations in both compounds. The fluorescence properties of (1) and (2) in the solid state were also investigated.

  3. Mixed-ligand binuclear copper(II) complex of 5 ...

    Indian Academy of Sciences (India)

    ligand binuclear copper(II) complex of 5-methylsalicylaldehyde and 2,2 -bipyridyl: Synthesis, crystal structure, DNA binding and nuclease activity. PERUMAL GURUMOORTHYa, JAYARAM RAVICHANDRANa,b and AZIZ KALILUR RAHIMANa,∗.

  4. Mixed-ligand complexes of ruthenium(II) incorporating a diazo ...

    Indian Academy of Sciences (India)

    Unknown

    Dedicated to the memory of the late Professor Bhaskar G Maiya. *For correspondence. Mixed-ligand complexes of ruthenium(II) incorporating a diazo ligand: Synthesis .... water (1 : 1) for 5 h to give a dark red solution. The solution was cooled to room temperature. After eva- poration of the solvent, the solid was collected,.

  5. Mixed-ligand complex formation equilibria of Cu with biguanide in ...

    Indian Academy of Sciences (India)

    Unknown

    Indian Academy of Sciences. 411. *For correspondence. Mixed-ligand complex formation equilibria of Cu. II with biguanide in presence of glycine as the auxiliary ligand. TANNISTHA ROY BARMAN and G N MUKHERJEE*. Department of Chemistry, University College of Science, University of Calcutta, 92, Acharya Prafulla.

  6. Hexacoordinated mixed-ligand complexes of vanadium(IV) and copper(II)

    International Nuclear Information System (INIS)

    Islam, M.S.; Motahera Begum; Roy, H.N.; Haroon, S.A.Q.M.

    1996-01-01

    The literature reports simple complexes of metal ions with Schiff bases derived from amino acids. But their mixed-ligand complexes are very rare. Keeping this fact in mind, some new mixed ligand complexes of V IV and Cu II with tridentate Schiff bases derived from glycine, salicylaldehyde and amino bases, e.g. quinoline (Q), isoquinoline (IQ), 2-picoline (2-pic), 4-picoline (4-pic) and pyridine (Py) were prepared and studied. 6 refs., 1 tab

  7. Equilibrium studies on mixed ligand complexes of some tripositive rare earth ions

    International Nuclear Information System (INIS)

    Vimal, Rashmi; Singh, Mamta; Ram Nayan

    1996-01-01

    Interaction of the rare earth ions, La 3+ , Ce 3+ , Pr 3+ , Nd 3+ , Sm 3+ and Eu 3+ with the pair of ligands 1-amino-2-naphthol-4-sulphonic acid (an, H 2 A) and o-aminophenol (ap, HB) have been studied in aqueous solution at 25 degC (μ=0.1 M KNO 3 /NaCl). Equilibrium constants of the reactions involving the formations of the mixed ligand species MAB, MA 2 B 2- , MB 2 A - (M = metal ion) and the binary complexes containing up to three ligand molecules have been evaluated from the pH-metric data, and coordinating behaviour of the ligands in the formation of the mixed ligand complexes has been discussed. (author). 10 refs., 1 tab., 1 fig

  8. synthesis and spectra characterization of mixed- ligand complexes

    African Journals Online (AJOL)

    BARTH EKWUEME

    bipyridine(bpy) has been announced to be “the most used ligand in coordination chemistry” (Humphries, et al., 2005), 2,2':6',2''-terpyridine (tpy) also has a rich chemistry. Almost 70 years ago, Burstall and Morgan reported the first synthesis of 2, 2':6', 2''-terpyridine. (Bermejo, et al., 1999). The kinetics and mechanism of ...

  9. Mixed-ligand binuclear copper(II) complex of 5 ...

    Indian Academy of Sciences (India)

    carbon, saturated Ag/AgCl and platinum wire are used as the working, reference and auxiliary electrodes, ... was mounted on a glass fibre for diffraction experiment. X-ray single crystal data were collected on a Kappa ..... with the covalent nature of the metal–ligand bond. 3.4 DNA binding studies. 3.4a Absorption spectral ...

  10. Further Insight into the Lability of MeCN Ligands of Cytotoxic Cycloruthenated Compounds: Evidence for the Antisymbiotic Effect Trans to the Carbon Atom at the Ru Center.

    Science.gov (United States)

    Barbosa, Ana Soraya Lima; Werlé, Christophe; Colunga, Claudia Olivia Oliva; Rodríguez, Cecilia Franco; Toscano, Ruben Alfredo; Le Lagadec, Ronan; Pfeffer, Michel

    2015-08-03

    The two MeCN ligands in [Ru(2-C6H4-2'-Py-κC,N)(Phen, trans-C)(MeCN)2]PF6 (1), both trans to a sp(2) hybridized N atom, cannot be substituted by any other ligand. In contrast, the isomerized derivative [Ru(2-C6H4-2'-Py-κC,N)(Phen, cis-C)(MeCN)2]PF6 (2), in which one MeCN ligand is now trans to the C atom of the phenyl ring orthometalated to Ru, leads to fast and quantitative substitution reactions with several monodentate ligands. With PPh3, 2 affords [Ru(2-C6H4-2'-Py-κC,N)(Phen, cis-C)(PPh3)(MeCN)]PF6 (3), in which PPh3 is trans to the C σ bound to Ru. Compound 3 is not kinetically stable, because, under thermodynamic control, it leads to 4, in which the PPh3 is trans to a N atom of the Phen ligand. Dimethylsulfoxide (DMSO) can also substitute a MeCN ligand in 2, leading to 5, in which DMSO is coordinated to Ru via its S atom trans to the N atom of the Phen ligand, the isomer under thermodynamic control being the only compound observed. We also found evidence for the fast to very fast substitution of MeCN in 2 by water or a chloride anion by studying the electronic spectra of 2 in the presence of water or NBu4Cl, respectively. An isomerization related to that observed between 3 and 4 is also found for the known monophosphine derivative [Ru(2-C6H4-2'-Py-κC,N)(PPh3, trans-C)(MeCN)3]PF6 (10), in which the PPh3 is located trans to the C of the cyclometalated 2-phenylpyridine, since, upon treatment by refluxing MeCN, it leads to its isomer 11, [Ru(2-C6H4-2'-Py-κC,N)(PPh3, cis-C)(MeCN)3]PF6. Further substitutions are also observed on 11, whereby N^N chelates (N^N = 2,2'-bipyridine and phenanthroline) substitute two MeCN ligands, affording [Ru(2-C6H4-2'-Py-κC,N)(PPh3, cis-C)(N^N)(MeCN)]PF6 (12a and 12b). Altogether, the behavior of the obtained complexes by ligand substitution reactions can be rationalized by an antisymbiotic effect on the Ru center, trans to the C atom of the cyclometalated unit, leading to compounds having the least nucleophilic ligand trans to C

  11. The autoxidation activity of new mixed-ligand manganese and iron complexes with tripodal ligands

    NARCIS (Netherlands)

    van Gorkum, R.; Berding, J.; Tooke, D.M.; Spek, A.L.|info:eu-repo/dai/nl/156517566; Reedijk, J.; Bouwman, E.

    2007-01-01

    The activity of new manganese and iron complexes of dianionic tripodal ligands in the autoxidation of ethyl linoleate (EL) is reported. EL consumption rates were monitored using time-resolved FTIR and the degree of oligomerisation was determined by SEC. Almost all complexes showed the same trend in

  12. Activation of trans geometry in bifunctional mononuclear platinum complexes by a non-bulky methylamine ligand

    Czech Academy of Sciences Publication Activity Database

    Frýbortová, M.; Nováková, Olga; Štěpánková, Jana; Novohradský, Vojtěch; Gibson, D.; Kašpárková, Jana; Brabec, Viktor

    2013-01-01

    Roč. 126, SEP2013 (2013), s. 46-54 ISSN 0162-0134 R&D Projects: GA ČR(CZ) GAP301/10/0598; GA ČR(CZ) GA13-08273S Institutional research plan: CEZ:AV0Z50040702 Institutional support: RVO:68081707 Keywords : HETEROCYCLIC AMINE LIGAND * INTERSTRAND CROSS-LINKS * DNA-BINDING MODE Subject RIV: BO - Biophysics Impact factor: 3.274, year: 2013

  13. Synthesis of novel '4+1' Tc(III)/Re(III) mixed-ligand complexes with dendritically modified ligands

    International Nuclear Information System (INIS)

    Gniazdowska, E.; Kuenstler, J.U.; Stephan, H.; Pietzsch, H.J.

    2006-01-01

    Coordination chemistry of technetium and rhenium attracts a considerable interest due to the nuclear medicine applications of their radionuclides. Inert, so-called '3+1' or '4+1' technetium/rhenium mixed-ligand complexes open a new way to application of 99 mTc/ 188 Re labeled compounds in tumor diagnosis and therapy. In the presented paper, authors describe the synthesis and study of novel 99 mTc/ 188 Re complexes with dendritically functionalized tetradentate (tripodal chelator 2,2',2''-nitrilotris(ethanethiol), NS 3 and carboxyl group-bearing ligand, NS 3 (COOH) 3 ) and monodentate (dendritically modified isocyanide, CN-R(COOMe) 3 and isocyanide-modified peptide, CN-GGY) ligands. To verify the identity of the prepared n.c.a. complexes, non-radioactive analogous '4+1' Re compounds were synthesized. The experimental data show that a dendritic modification of the tetradentate/monodentate ligands changes the complex lipophilicity and does not influence its stability

  14. The autoxidation activity of new mixed-ligand manganese and iron complexes with tripodal ligands

    OpenAIRE

    van Gorkum, R.; Berding, J.; Tooke, D.M.; Spek, A.L.; Reedijk, J.; Bouwman, E.

    2007-01-01

    The activity of new manganese and iron complexes of dianionic tripodal ligands in the autoxidation of ethyl linoleate (EL) is reported. EL consumption rates were monitored using time-resolved FTIR and the degree of oligomerisation was determined by SEC. Almost all complexes showed the same trend in the autoxidation of EL. After a short induction time, the reaction started at a relatively high constant rate; later, this rate changes to a lower rate, which was again constant and on average was ...

  15. Potentiometric studies on mixed-ligand chelates of uranyl ion with carboxylic acid phenolic acids

    International Nuclear Information System (INIS)

    Bandiwadekar, S.P.; Chavar, A.M.

    1988-01-01

    Mixed ligand complexes of UO 2 2+ with bidentate carboxylic and phenolic acids have been studied potentiometrically at 30 ± 0.1degC and μ=0.2M (NaClO 4 ). 1:1 and 1:2 complexes of UO 2 2+ with phthalic acid (PTHA), maleic acid (MAE), malonic acid (MAL), quinolinic acid (QA), 5-sulphosalicylic acid (5-SSA), salicylic acid (SA), and only 1:1 complexes in the case of mandelic acid (MAD) have been detected. The formation of 1:1:1 mixed ligand complexes has been inferred from simultaneous equilibria in the present study. The values of ΔlogK, Ksub(DAL), Ksub(2LA) or Ksub(2AL) for the ternary complexes have been calculated. The stabilities of mixed ligand complexes depend on the size of the chelate ring and the stabilities of the binary complexes. (author). 15 refs

  16. One ligand capable of in situ reaction in a mixed-ligand system with two new different frameworks

    KAUST Repository

    Wang, Xiaofang

    2017-12-24

    The in situ ligand 2,3-pyrazinedicarboxylic acid (2,3-H2pzdc) mixed with 1,1′-(1,4-butanediyl)bis(benzimidazole) (bbbi) is used to form two coordination polymers ([Cd(2,3-pzdc)(bbbi)] (1) and [Cd2Cl3(2-pzc)(bbbi)2] (2)) under hydrothermal conditions. Complex 1 was obtained in the absence of in situ reaction and 2 was synthesized with 2,3-H2pzdc in situ generating 2-pyrazinecarboxylate (2-pzc−). The structural details reveal that 1 has a 3D framework with dia topology, and 2 is a 2D layer structure and develops a 3D supramolecular structure via strong π⋯π stacking interactions. The ligand effects were compared for the two frameworks. In addition, fluorescence properties and thermal stabilities of 1 and 2 in the solid were studied.

  17. Formation of mixed ligand complexes of UO22+ involving some nitrogen and oxygen donor ligands

    International Nuclear Information System (INIS)

    Singh, Mamta; Ram Nayan

    1996-01-01

    The complexation reactions of UO 2 2+ ion with nitrogen and oxygen donor ligands, 1-amino-2-naphthol-4-sulphonic acid, o-aminophenol (ap), 2-hydroxybenzoic acid (sa), 3-carboxy-4-hydroxybenzenesulphonic acid (ss) and 1,2-dihydroxybenzene (ca) have been investigated in aqueous solution employing the pH-titration technique. Analysis of the experimental data recorded at 25 degC and at an ionic strength of 0.10 M KNO 3 indicates formation of binary, hydroxo and ternary complexes of uranium. Formation constant values of the existing species have been evaluated and the results have been discussed. (author). 21 refs., 2 figs., 2 tabs

  18. Trans and cis effects of axial fluoroalkyl ligands in vitamin B12 analogues: relationship between alkyl- and fluoroalkyl-cobalamins.

    Science.gov (United States)

    Randaccio, Lucio; Brancatelli, Giovanna; Demitri, Nicola; Dreos, Renata; Hickey, Neal; Siega, Patrizia; Geremia, Silvano

    2013-12-02

    CF2HCbl, CF3Cbl , and CF3CH2Cbl have been synthesized and characterized in solution by (1)H NMR and UV-vis spectroscopy, and their X-ray crystal structures have been determined using synchrotron radiation. The structure of CF3CH2Cbl is reported for the first time, whereas those of CF2HCbl and CF3Cbl are re-examined to obtain more precise structural data. Comparison of the structural data obtained with the alkylcobalamin analogues, MeCbl and EtCbl, indicates that the Co-C and Co-NB3 bond lengths are shorter in the fluoroalkylcobalamins. The structural data of the fluoroalkylcobalamins previously reported in the literature had been conflicting in this regard. Thus, a much less dramatic shortening of the two axial bonds was found for CF3Cbl, whereas in the case of CF2HCbl, the Co-NB3 bond length is shorter than in MeCbl. Direct comparison of the structures of CF3CH2Cbl and EtCbl indicates a large distortion of the axial fragment in the former case that can be attributed to steric effects. A number of previously reported correlations of the effect of the β-ligand on the structure and properties of cobalamins are re-examined in light of the present results. Particular emphasis is placed on the axial fragment. This analysis substantially confirms and, with the new data reported here, adjusts and expands the data set for correlations between trans and cis influences of the β-ligand of cobalamins and their structure (Co-X and Co-NB3 distances and corrin fold angle) and properties (UV-vis spectra, NMR spectra, and pK(base-off)).

  19. Studies on mixed ligand complexes of lanthanide (III) ions

    International Nuclear Information System (INIS)

    Rajendran, G.; Usha Devi, K.G.

    2002-01-01

    As part of our research programme, we have prepared and characterized a few nitrato, thiocyanato and perchlorato complexes of lanthanide(III) ions with ligands, viz., a Schiff base derived from p-anisidine and vanillin and diphenyl sulphoxide. The complexes were characterized by the measurement of electrical conductances and magnetic susceptibilities, molecular mass and metal percentage and spectral analysis. The thermal decompositions were studied by TG and DTG techniques. The thiocyanato complexes were prepared by substitution method from nitrato complexes. p-Anisidine-vanillin (HDDA) and diphenyl sulphoxide (DPSO) are coordinated to the metal ion in unidentate fashion. All the anions were involved in coordination in these complexes. Thus they were found to have non- electrolytic behaviour with composition [Ln(HDDA) 2 (DPSO)X 3 ] where X = NO 3 ) or SCN perchlorato complexes were prepared from metal perchlorate as done in the case of nitrato complexes. They were found to have electrical conductance which corresponds to 1 : 1 electrolyte. Hence one of the perchlorate ions is outside the coordination sphere. The composition of this complex is found to be [Ln(HDDA) 3 (DPSO)(ClO 4 ) 2 ]ClO 4 . (author)

  20. Plutonium decorporation by mixed ligand chelates. Final report, June 2, 1976--April 15, 1977

    International Nuclear Information System (INIS)

    Schubert, J.

    1977-04-01

    The effects of mixed ligand chelates on the removal of 239 Pu and 234 Th from the tissues of mice were investigated. The primary ligands, L 1 , used were mainly EDTA and DTPA, while the secondary ligands, L 2 , were of the bidentate type, as, for example, catechol, salicylic acid, and benzohydroxamic acid. A suitably chosen mixed ligand system binds Pu or Th at physiological pH's about 10 11 to 10 15 times greater than EDTA or DTPA. An ultrafiltration screening procedure was employed in which soluble Pu or Th salts were injected into mice, the livers were removed several days later and homogenized in the presence of different concentrations of the single and mixed chelants. Similarly, in vivo studies were carried out in which mice were treated 4 hours post Pu (monomeric) injection (I.P.) with a single injection (I.P.) of the chelant systems. Results to date show that the mixed chelant systems are roughly 10 times more effective than EDTA or DTPA alone. Thus, under conditions where DTPA alone (5 x 10 -5 M) removed 1.1 percent of Pu or Th, DTPA + equimolar catechol removed 13.5 percent and 15 percent respectively. Catechol alone had no significant effect. In an in vivo decorporation experiment, a single injection of DTPA plus catechol reduced the liver burden from 45 percent to 2.3 percent and the skeleton from 22 percent to 5.5 percent

  1. Polar self-assembly: steric effects leading to polar mixed-ligand coordination cages.

    Science.gov (United States)

    Zhang, Jianyong; Miller, Philip W; Nieuwenhuyzen, Mark; James, Stuart L

    2006-03-08

    We present a highly unusual example of self-assembly, specifically a polar, mixed-ligand cage which forms in preference to symmetrical homo-ligand products, and which suggests that steric effects can be exploited to obtain novel non-uniform polyhedral cages. In particular, reaction between the bulky tripodal triphosphine 2,4,6-tris(diphenylphosphino)triazine, L1, the non-bulky tripodal trinitrile 2,4,6-tris(cyanomethyl)trimethylbenzene, L2 and silver hexafluoroantimonate, AgSbF6, in a 3:1:4 ratio gives the mixed-ligand aggregate [Ag4(L1)3(L2)(SbF6)]3+, 1-SbF6, instantly as the only product in quantitative yield. The X-ray crystal structure of complex 1-SbF6 is consistent with the suspected solution-state structure. The cage derives from trigonal-pyramidal geometry, the basal vertices of which are defined by three bulky triphosphines, L1, and the apical vertex by the non-bulky trinitrile, L2. There is apical elongation amounting to 19% in comparison to the ideal uniform tetrahedron. The cage also encapsulates an SbF6 anion. 19F NMR spectra in solution for the analogous PF6 complex [Ag4(L1)3(L2)(PF6)]3+, 1-PF6, confirm that one anion is also encapsulated in solution. The synthesis of the analogous CF3SO3(-) complex, [Ag4(L1)3(L2)(OTf)]3+, 1-OTf, in solution is also described, although 1-PF6 and 1-OTf could not be isolated due to slow decomposition in solution. The selective formation of these mixed-ligand cages is discussed in terms of ligand-ligand and ligand-included anion steric repulsions, which we propose prevent the formation of the competing hypothetical homo-ligand tetrahedral structure [Ag4(L1)4(SbF6)]3+, and thus favour the mixed ligand cage. "Cage cone angles" for L1 and L2 are estimated at 115 degrees and 101 degrees, respectively. Variable-temperature 31P NMR spectroscopy shows that complex 1-SbF6 and the related previously reported partial tetrahedral complex [Ag4(L1)3(anion)]3+ undergo dynamic twisting processes in solution between enantiomeric C3

  2. Screening the efficient biological prospects of triazole allied mixed ligand metal complexes

    Science.gov (United States)

    Utthra, Ponnukalai Ponya; Kumaravel, Ganesan; Raman, Natarajan

    2017-12-01

    Triazole appended mixed ligand complexes (1-8) of the general formula [ML (bpy/phen)2]Cl2, where M = Cu(II), Co(II), Ni(II) and Zn(II), L = triazole appended Schiff base (E)sbnd N-(4-nitrobenzylidene)-1H-1,2,4-triazol-3-amine and bpy/phen = 2,2‧-bipyridine/1,10-phenanthroline, have been synthesized. The design and synthesis of this elaborate ligand has been performed with the aim of increasing stability and conjugation of 1,2,4 triazole, whose Schiff base derivatives are known as biologically active compounds thereby exploring their DNA binding affinity and other biological applications. The compounds have been comprehensively characterized by elemental analysis, spectroscopic methods (IR, UV-Vis, EPR, 1H and 13C NMR spectroscopy), ESI mass spectrometry and magnetic susceptibility measurements. The complexes were found to exhibit octahedral geometry. The complexes 1-8 were subjected to DNA binding techniques evaluated using UV-Vis absorption, CV, CD, Fluorescence spectroscopy and hydrodynamic measurements. Complex 5 showed a Kb value of 3.9 × 105 M-1. The DNA damaging efficacy for the complexes was observed to be high compared to the ligand. The antimicrobial screening of the compounds against bacterial and fungal strains indicates that the complexes possess excellent antimicrobial activity than the ligand. The overall biological activity of the complexes with phen as a co-ligand possessed superior potential than the ligand.

  3. Mixed-component sulfone-sulfoxide tagged zinc IRMOFs:In situ ligand oxidation, carbon dioxide, and water sorption studies

    OpenAIRE

    Bryant, Macguire R; Burrows, Andrew D; Kepert, Cameron J; Southon, Peter D; Qazvini, Omid T; Telfer, Shane G; Richardson, Christopher

    2017-01-01

    Reported here are the syntheses and adsorption properties of a series of single- and mixed-component zinc IRMOFs derived from controlled ratios of sulfide and sulfone functionalized linear biphenyldicarboxylate (bpdc) ligands. During MOF synthesis the sulfide moieties undergo in situ oxidation, giving rise to sulfoxide functionalized ligands, which are incorporated to give mixed-component sulfoxide–sulfone functionalized MOFs. The single- and mixed-component systems all share the IRMOF-9 stru...

  4. Synthesis, spectral, thermal and biological studies of mixed ligand complexes with newly prepared Schiff base and 1,10-phenanthroline ligands

    Science.gov (United States)

    Abd El-Halim, Hanan F.; Mohamed, Gehad G.; Khalil, Eman A. M.

    2017-10-01

    A series of mixed ligand complexes were prepared from the Schiff base (L1) as a primary ligand, prepared by condensation of oxamide and furan-2-carbaldehyde, and 1,10-phenanthroline (1,10-phen) as a secondary ligand. The Schiff base ligand and its mixed ligand chelates were characterized based on elemental analysis, IR, 1H NMR, thermal analysis, UV-Visible, mass, molar conductance, magnetic moment. X-ray diffraction, solid reflectance and ESR also have been studied. The mixed ligand complexes were found to have the formulae of [M(L1) (1,10-phen)]Clm.nH2O (M = Cr(III) and Fe(III) (m = 3) (n = 0); M = Mn(II), Cu(II) and Cd(II) (m = 2) (n = 0); and M = Co(II) (m = 2) (n = 1), Ni(II) (m = 2) (n = 2) and Zn(II) (m = 2) (n = 3)) and that the geometrical structure of the complexes were octahedral. The parameters of thermodynamic using Coats-Redfern and Horowitz-Metzger equations were calculated. The synthesized Schiff base ligand, 1,10-phenanthroline ligand and Their mixed ligand complexes were also investigated for their antibacterial and antifungal activity against bacterial species (Gram-Ve bacteria: Pseudomonas aeruginosa and Escherichia coli) and (Gram + Ve bacteria: Bacillus subtilis and Streptococcus pneumonia) and fungi (Aspergillus fumigates and Candida albicans). The anticancer activity of the new compounds had been tested against breast (MFC7) and colon (HCT-116) cell lines. The results showed high activity for the synthesized compounds.

  5. Synthesis, crystal structure and photoluminescence property of Eu/Tb MOFs with mixed polycarboxylate ligands

    Energy Technology Data Exchange (ETDEWEB)

    Yang, Lu; Zhang, Sheng; Qu, Xiaoni; Yang, Qi [Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of Ministry of Education, College of Chemistry and Materials Science, Northwest University, Xi’an 710127 (China); Liu, Xiangyu [Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of Ministry of Education, College of Chemistry and Materials Science, Northwest University, Xi’an 710127 (China); School of Chemistry and Chemical Engineering, Ningxia University, Yinchuan 750021 (China); Wei, Qing; Xie, Gang [Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of Ministry of Education, College of Chemistry and Materials Science, Northwest University, Xi’an 710127 (China); Chen, Sanping, E-mail: sanpingchen@126.com [Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of Ministry of Education, College of Chemistry and Materials Science, Northwest University, Xi’an 710127 (China)

    2015-11-15

    Lanthanide MOFs, [Eu(TCA)(NDC)·H{sub 2}O]{sub n} (1) and [Tb(TCA)(NDC)·H{sub 2}O]{sub n} (2), have been prepared with the mixed aromatic carboxylate ligands, namely, 4,4′,4″-tricarboxytriphenylamine (H{sub 3}TCA) and 1,4-naphthalenedicarboxylate (H{sub 2}NDC). Single-crystal X-ray diffraction analysis reveals that isomorphic 1 and 2 present pillar-layered 3D framework that Eu/Tb(III) bond with carboxylate in various coordination fashions. Optical investigation indicates that the as-prepared compounds feature characteristic luminescence emission bands of Eu/Tb ions in the visible regions at room temperature. Moreover, compound 2 shows a relatively longer luminescence lifetime (τ=0.342 ms) and significantly enhanced quantum yield (Φ{sub overall}=11%) comparing with those of 1 (τ=0.335 ms, Φ{sub overall}=0.06%). - Graphical abstract: Synoptic: Two Ln-MOFs (Ln=Eu{sup III}, Tb{sup III}) with mixed polycarboxylate ligands present different luminescent properties. - Highlights: • Two Eu/Tb-MOFs with H{sub 3}TCA and H{sub 2}NDC ligands have been obtained. • The ancillary ligand is employed to decrease water molecule coordinate numbers. • 2displays superior quantum yield and lifetime than those of 1.

  6. Solvent extraction studies on the mixed ligand complexes of lanthanides with antipyrine and perchlorate

    International Nuclear Information System (INIS)

    Murthy, M.V.K.; Satyanarayana, D.

    1981-01-01

    Lanthanide ions are found to form colourless mixed-ligand complexes with antipyrine in presence of perchlorate at pH 4.0, and these are quantitatively extractable into nitrobenzene. The composition of the extracted species is shown to be metal:antipyrine:perchlorate = 1:6:3. The variation of the extraction constants with atomic number of the lanthanides is attributed to the 'tetrad effect'. (author)

  7. Ligand Exchange and 1H NMR Quantification of Single- and Mixed-Moiety Thiolated Ligand Shells on Gold Nanoparticles.

    Science.gov (United States)

    Smith, Ashley M; Millstone, Jill E

    2017-01-01

    The use of nanoparticles in biomedicine critically depends on their surface chemistry. For metal nanoparticles, a common way to tune this surface chemistry is through mass action ligand exchange, where ligand exchange can be used to expand the functionality of the resulting nanoparticle conjugates. Specifically, the quantity, identity, and arrangement of the molecules in the resulting ligand shell each can be tuned significantly. Here, we describe methods to exchange and quantify thiolated and non-thiolated ligands on gold nanoparticle surfaces. Importantly, these strategies allow the quantification of multiple ligand types within a single ligand shell, simultaneously providing ligand composition and ligand density information. These results are crucial for both designing and assigning structure-function relationships in bio-functionalized nanoparticles, and these methods can be applied to a broad range of nanoparticle cores and ligand types including peptides, small molecule drugs, and oligonucleotides.

  8. Ionophoretic method in the study of mixed ligand ternary chelates of UO2(II), Ni(II) and Zn(II) involving nitrilotriacetate and cytosine as ligands

    International Nuclear Information System (INIS)

    Mishra, A.P.; Mishra, S.K.; Yadava, K.L.

    1987-01-01

    A novel electrophoretic technique is described for the assessment of the equilibria in mixed-ligand complex system in solution. It is based on the movement of spot of the metal ion under an electric field with the complexants added in the background electrolyte at fixed pH. The concentration of primary ligand nitrilotriacetate was constant while that of secondary ligand (cytosine) was varied. The plot of log (cytosine) against mobility was used to obtain information on the formation of the mixed complexes and to calculate its stability constants. Experimentally obtained logK values are as 5.62, 4.55 and 4.42 for mixed complexes of UO 2 (II), Ni(II) and Zn(II) respectively at μ=0.1 and temp.=35 +- 01.degC. (author). 10 refs

  9. The infrared-driven cis-trans isomerization of nitrous acid HONO III: A mixed quantum-classical simulation

    International Nuclear Information System (INIS)

    Hamm, Peter

    2008-01-01

    A mixed quantum-classical simulation of the IR-driven cis-trans isomerization of HONO in a Kr matrix at 30 K is presented, treating the hydrogen atom as quantum particle and the Kr matrix as well as intermolecular degrees of freedom of the ONO-body as classical. A new method is presented to time-propagate the coupled set of equations in a DVR basis in internal spherical coordinates, rather than in laboratory frame fixed cartesian coordinates. In spherical coordinates, a much more precise computation of the weak vibrational couplings is possible using a still manageable basis size. Good qualitative agreement between simulation and experiment is obtained, underestimating relaxation and isomerization rates by a modest factor ∼5. Upon matrix fluctuations, frequent curve crossings occur between the initially excited OH-stretch vibration and a closely lying combination mode of torsional and bending coordinate that lead to a transfer of population. The subsequent pathway of energy flow is deduced and discussed within a tier model, where trans-states, that belong to the second tier, are populated through a first tier of states that is composed of combinations of bending and torsional excitations. No specific energy pathway is revealed that would funnel the hydrogen atom directly towards the trans-side, hence the experimentally observed high cis → trans quantum yield of close to one probably has to be explained in a statistical scenario on a timescale much longer than that of the present simulation

  10. Photochemistry of fac-[Re(CO)3(dcbH2)( trans-stpy)]+: New Insights on the Isomerization Mechanism of Coordinated Stilbene-like Ligands.

    Science.gov (United States)

    Faustino, Leandro A; Hora Machado, Antonio Eduardo; Patrocinio, Antonio Otavio T

    2018-03-05

    In this work, a novel complex fac-[Re(CO) 3 (dcbH 2 )( trans-stpy)] + , (dcbH 2 = 4,4'-dicarboxylic acid-2,2'-bipyridine; trans-stpy = trans-4-styrylpyridine) was synthesized and characterized toward its spectroscopic, photochemical, and photophysical properties. The experimental data provide new insights on the mechanism of photochemical trans-to- cis isomerization of the stilbene-like ligand coordinated to Re(I) polypyridyl complexes. The new complex exhibits an unusual and strong dependence of the isomerization quantum yield (Φ t →c ) on the irradiation wavelength. Φ t →c was 0.81 ± 0.08 for irradiation at 365 nm and continuously decreased as the irradiation wavelength is shifted to the visible. At 405 nm irradiation Φ t →c is almost 2 orders of magnitude lower (0.010 ± 0.005) than that observed at 365 nm excitation. This behavior can be explained by the low-lying triplet metal-to-ligand charge-transfer excited state ( 3 MLCT) that hinders the triplet photoreaction mechanism under visible light absorption. Under UV irradiation, direct population of styrylpyridine-centered excited state ( 1 IL) leads to the occurrence of the photoisomerization via a singlet mechanism. Further experiments were performed with the complex immobilized on the surface of TiO 2 and Al 2 O 3 films. The nonoccurrence of isomerization at the oxide surfaces even under UV excitation evidences the role of energy gap between the 1 IL/ 1 MLCT states on the photochemical/photophysical processes. The results establish important relationships between the molecular structure and the photoelectrochemical behavior, which can further contribute to the development of solid-state molecular switches based on Re(I) polypyridyl complexes.

  11. Enthused research on DNA-binding and DNA-cleavage aptitude of mixed ligand metal complexes

    Science.gov (United States)

    Mahalakshmi, Rajkumar; Raman, Natarajan

    2013-08-01

    Five new Mn(II), Co(II), Ni(II), Cu(II) and Zn(II) mixed ligand complexes have been synthesized using a Schiff base precursor (obtained by the condensation of N-(4-aminophenyl)acetamide and 4-chlorobenzaldehyde) as main ligand and 1,10-phenanthroline as co-ligand. They have been characterized by microanalytical data, IR, UV-Vis, magnetic moment values, conductivity and electrochemical measurements. The spectral data reveal that all the complexes exhibit octahedral geometry. The high electrical conductance of the complexes supports their electrolytic nature. The monomeric nature of the complexes has been assessed from their magnetic susceptibility values. These complexes are better antimicrobial active agents than the free ligands. DNA (CT) binding properties of these complexes have been explored by UV-Vis., viscosity measurements, cyclic voltammetry, and differential pulse voltammetry measurements. The oxidative cleavage activity of the complexes has been studied using supercoiled pUC19 DNA by gel electrophoresis. The experimental results show that the complexes are good intercalators.

  12. Studies on some mixed ligand complexes of UO2(VI) in solution

    International Nuclear Information System (INIS)

    Katkar, V.S.; Munshi, K.N.

    1987-01-01

    Potentiometric studies on some mixed ligand complexes of UO 2 (VI) with ethylenediamine N,N' diacetic acid as primary ligand and succinic acid, malic acid, maleic acid, fumaric acid, malonic acid, adipic acid, itaconic acid, phthalic acid and mandelic acid as secondary ligands have been carried out employing modified form of Irving-Rossotti's pH titration technique. The study was carried out at three different temperatures, viz. 5deg, 25deg and 45degC and at fixed ionic strength of 0.2M KNO 3 . Thermodynamic parameters, e.g. ΔG, ΔH and ΔS have been evaluated and further ΔG and ΔH values have been separated into their electrostatic components, ΔGe and ΔHe and cratic components, ΔGsub(c) and ΔHsub(c). The effect of change in dielectric constant and change in ionic strength of the medium have also been investigated. The sequence of stability constants has been correlated with the properties of secondary ligands. (author). 21 refs., 5 tabs

  13. Studies on mixed ligand complexes of adenine and xanthine with some rare earth ions

    International Nuclear Information System (INIS)

    Rastogi, P.R.; Singh, Mamta; Nayan, Ram

    1993-01-01

    Interactions of 6-aminopurine (adenine, HA) and 2,6-dihydroxypurine (xanthine, HB) with trivalent rare earth ions Y, Tb, Dy, Ho, Er and Tm, have been studied by pH-titration methods in aqueous solution at 20 o (μ = 0.1 M KNO 3 ). The ligands in their mixtures with tripositive rare earth ions (M 3+ ) form a number of mixed ligand complexes, M 3+ -adenine-xanthine, M 3+ -(adenine) 2 -xanthine, M 3+ -adenine-(xanthine) 2 in addition to the binary complexes, M 3+ -(adenine), M 3+ -(adenine) 2 , M 3+ -(adenine) 3 , M 3+ -(xanthine), M 3+ -(xanthine) 2 and M 3+ -(xanthine) 3 . The stability constants of these complexes have been evaluated and the results discussed. (author). 13 refs., 1 fig., 1 tab

  14. cis-dioxovanadium(V) and mixed-valence divanadium(IV, V) complexes containing β-diketonate and heterocyclic nitrogen-base ligands

    International Nuclear Information System (INIS)

    Taguchi, Hiroshi; Isobe, Kiyoshi; Nakamura, Yukio; Kawaguchi, Shinichi

    1978-01-01

    Diamagnetic dioxovanadium(V) complexes, VO 2 (β-dik)(phen or bpy), were prepared by the direct reactions of VO(β-dik) 2 with 1,10-phenanthroline and 2,2'-bipyridine in dichloromethane under aerobic conditions as well as by two other methods. These compounds were concluded to have a cis configuration on the basis of the IR and Raman data. These complexes are solvolyzed to afford the di-μ-methoxo- or di-μ-hydroxo-divanadium(V) species, and are reduced by hydrogen bromide to the oxovanadium(IV) species in dichloromethane. In methanol instead of dichloromethane, VO(acac) 2 reacted with 2,2'-bipyridine to produce a novel mixed-valence divanadium(IV, V) complex, V 2 O 3 (acac) 3 (bpy), which was revealed by the magnetic, spectral, and polarographic data to be a trans adduct of VO(acac) 2 with VO 2 (acac)(bpy) via an oxide ligand. (auth.)

  15. Synthesis, characterization and electrochemical investigations of mixed-ligand copper(II)-organic supramolecular frameworks

    Science.gov (United States)

    Singh, Sandeep K.; Srivastava, Ashish Kumar; Srivastava, Krishna; Banerjee, Rahul; Prasad, Jagdish

    2017-11-01

    Two mixed-ligand copper(II)-organic coordination compounds with 5,5‧-dimethyl-2,2‧-bipyridine (5,5‧-Me2bpy) as a primary ligand while aliphatic malonate (Hmal) and aromatic 2-hydroxynicotinate (2-OHNA) as secondary ligands, were synthesized. These complexes are formulated as: [Cu(Hmal)(5,5‧-Me2bpy)(H2O)](ClO4) 1 and [Cu2(2-OHNA)2(5,5‧-Me2bpy)2(NO3)](NO3) 2. These two complexes were structurally characterized by single crystal X-ray diffraction analysis. Characterization was further supported by powder X-ray diffraction analysis, elemental analyses, FT-IR, FAB-MASS and TGA, DSC studies. Cyclic voltammetric and UV-visible spectral studies of these two complexes have also been done. The electrochemical studies of complex 1 in DMSO and DMF have shown that this complex undergoes quasi-reversible diffusion-controlled one-electron transfer reaction without any chemical complication while complex 2 in DMSO undergoes quasi-reversible diffusion-controlled one electron transfer reaction, following EC mechanism. The electrochemical behaviour of complex 2 in DMF is complicated probably due to presence of more than one species in solution phase.

  16. Stability Constants of Mixed Ligand Complexes of Transition Metal(II Ions with Salicylidene-4-methoxyaniline as Primary Ligand and 5-Bromosalicylidene-4-nitroaniline as Secondary Ligand

    Directory of Open Access Journals (Sweden)

    N. G. Nadkarni

    2011-01-01

    Full Text Available Binary and ternary complexes of the type M-Y and M-X-Y [M = Mn(II, Ni(II, Cu(II and Zn(II; X = salicylidene-4-methoxyaniline and Y=5-bromosalicylidene-4-nitroaniline] have been examined pH-metrically at 27±0.5 °C and at constant ionic strength, μ= 0.1 M (KCl in 75 : 25(v/v 1,4-dioxne-water medium. The stability constants for binary (M-Y and ternary (M-X-Y systems were calculated. The relative stability (Δ log KT values of the ternary complexes with corresponding binary complexes for all the metal(II ions in the present study found to be negative indicating that ternary 1:1:1 (M-X-Y complexes are less stable than binary 1:1 (M-Y complexes. In the ternary system studied, the order of stability constants of mixed ligand complexes with respect to the metal ions was found to be Cu(II > NI(II > Mn(II > Zn(II; which is same as in the corresponding binary (M-Y systems.

  17. Stability constants of mixed ligand complexes of dioxouranium(II) and thorium(IV) with complexones and isomeric alanines

    International Nuclear Information System (INIS)

    Singh, R.K.; Saxena, M.C.

    1992-01-01

    The present work reports on the stability sequence between UO 2 II and Th IV ions for their mixed ligands complexes with the two isomeric alanines, α-alanine (α-ala) and β-alanine (β-ala) containing a complexone as primary ligand. The complexones used are iminodiacetate (IMDA), nitrilotricetate (NTA), 2-hydroxyethylenediaminetriacetate (HEDTA), ethylenediaminetetraacetate (EDTA), 1,2-diaminocyclohexanetraacetate (CDTA) and diethylenetriminepentaacetate (DTPA). (author). 9 refs., 1 tab

  18. Syntheses, structures and chemical sensing properties of three complexes with mixed ligands of carboxylate and bipyridine.

    Science.gov (United States)

    Jiao, Chengli; Li, Fen; Zhang, Jian; Li, Zhangpeng; Wang, Shuang; Wang, Zhonggang; Yu, Hao; Li, Zhibao; Liu, Shuang; Wang, Ziqiang; Jiang, Xia; Sun, Lixian; Xu, Fen

    2013-02-07

    Three mixed-ligand coordination polymers, [Cu(oda)(2,2'-bipy)](2) (1), Ni(2)(oda)(2)(4,4'-bipy)·DMF (2), and [{Ni(oda)(H(2)O)(2)}(2)(μ-4,4'-bipy)]·2H(2)O (3) were synthesized and characterized. Complex 1 features a 1D chain via intermolecular π-π interactions. Complex 2 is a novel 3D microporous coordination polymer with 1D polarized channels. Complex 3 forms a 3D network via extensive hydrogen bonding interactions. Thermogravimetric analyses have been studied. The chemical sensing properties have been investigated in situ by quartz crystal microbalance (QCM). Complex 1 has a good sensitivity to toluene, complexes 2 and 3 have exceptionally high selectivity and sensitivity to water over organic solvents.

  19. Carbon dioxide selective adsorption within a highly stable mixed-ligand Zeolitic Imidazolate Framework

    KAUST Repository

    Huang, Lin

    2014-08-01

    A new mixed-ligand Zeolitic Imidazolate Framework Zn4(2-mbIm) 3(bIm)5·4H2O (named JUC-160, 2-mbIm = 2-methylbenzimidazole, bIm = benzimidazole and JUC = Jilin University China) was synthesized with a solvothermal reaction of Zn(NO3) 2·6H2O, bIm and 2-mbIm in DMF solution at 180 °C. Topological analysis indicated that JUC-160 has a zeolite GIS (gismondine) topology. Study of the gas adsorption and thermal and chemical stability of JUC-160 demonstrated its selective adsorption property for carbon dioxide, high thermal stability, and remarkable chemical resistance to boiling alkaline water and organic solvent for up to one week. © 2014 Elsevier B.V.

  20. Polarographic study of simple and mixed ligand complexes of Eu(III) with imidazole and succinate

    International Nuclear Information System (INIS)

    Shivhare, Madhu; Singh, Mukhtar

    1982-01-01

    The formation of simple and mixed ligand complexes of Eu(III) with imidazole (Im) and succinate (Succ 2- ) has been studied polarographically at 25deg C+-0.1deg C, μ=1.0 (NaClO 4 ) and pH=6. The reduction of the complexes at d.m.e. is quasi-reversible and diffusion-controlled. Eu(III) forms six successive complexes with Im, viz. [Eu(Im)] 3+ , [Eu(Im) 2 ] 3+ , [Eu(Im) 2 ] 3+ , [Eu(Im) 3 ] 3+ , [Eu(Im) 4 ] 3+ , [Eu(Im) 5 ] 3+ , and[Eu(Im) 6 ] 3+ . Their stability constant values are: logβ 10 =3.6, logβ 20 =4.6, logβ 30 =6.5, logβ 40 =7.8, logβ 50 =8.4 and logβ 60 =9.6 respectively. With succ 2- , Eu(III) forms four successive complexes; [Eu(Succ)] + , [Eu(Succ) 2 ] - , [Eu(Succ) 3 ] 3- and [Eu(Succ) 4 ] 5- with the stability constants, logβ 01 =3.8, logβ 02 =4.6, logβ 03 =5.3 and logβ 04 =6.9 respectively. Eu(III) forms five mixed ligand complexes; [Eu(Im)(Succ) 2 ] - , Eu(Im) 2 (Succ) 2 ] - , [Eu(Im) 3 (Succ) 2 ], [Eu(Im) 4 (Succ) 2 ] and [Eu(Im) 5 (Succ)] + with stability constants, logβ 12 =6.1, logβ 22 =8.0, logβ 32 =9.5, logβ 42 =10.9 and logβ 51 =10.2 respectively. (author)

  1. Mixed-ligand complexes of copper (II with ditiolfenols and heterocyclic diamines

    Directory of Open Access Journals (Sweden)

    K. A. Kuliev

    2017-01-01

    Full Text Available By the methods spectrophotometric methods was investigated complex formation of copper with 2,6-ditiolphenol and its derivatives (2,6-ditiol-4-methylphenol, 2,6-ditiol-4-ethylphenol and 2,6-ditiol-4-tert-buthylphenol in the presence of heterocyclic diamines. As heterocyclic diamines phenantroline (Fen, batophenantroline and dipyridile were used. It was established, that mixedligand complex were formed in weak acidic medium (pHop=6,0-8,5. Maximum of light absorption observed at (=522–550 nm. Molar coefficient of light absorption was ( = (3.08–4.92?104. The stoichiometry of complexes had been discovered using shift the equilibrium and relative yield methods. During the extraction of copper(II complexes with ditiol-phenols with the presence of heterocyclic diamines there was discovered that there is no chlorophorm molecules in the composition of the extracted complexes. IR spectra shows that hydroxyl group is involved to the formation of a bond with the metal and that phenantroline is included in the composition of the copper complex. In the organic phase mixed-ligand complexes have the monomeric form and can’t polymerize; that fact can be proved by calculations. By dint of spectrophotometric, IR-spectroscopic, thermogravimetric experiments and some published data we were able to determine the structural formula of complexes. Also had been determined main spectrophotometric characteristics of copper(II mixed-ligand complexes: pH of the beginning of the deposition, optimal pH, detection limit and sensivity. For separation and finding copper, we studied the effect of interfering foreign ions: alkali, alkaline earth and rare earth elements, as well as acid anions selected masking reagents. On the base of the results was offered photometric method for determination of copper in steel different trade-marks and in food. This method characterized by good reproduction (relatively standard deviation no more 0.05 and low limit of discovery.

  2. The synthesis, structures and characterisation of new mixed-ligand manganese and iron complexes with tripodal, tetradentate ligands

    NARCIS (Netherlands)

    van Gorkum, R.; Berding, J.; Mills, A.M.; Kooijman, H.; Tooke, D.M.; Spek, A.L.; Mutikainen, I.; Turpeinen, U.; Reedijk, J.; Bouwman, E.

    2008-01-01

    The preparation of new manganese and iron complexes with the general formula [M(tripod)(anion)] is described, where M = FeIII or MnIII, “tripod” is a dianionic tetradentate tripodal ligand and the anion is a chelating β-diketonate, 8-oxyquinoline or acetate. The synthesis of this type of complexes

  3. IR luminescence of mixed-ligand complexes of Nd(III), Yb(III), and Er(III) with dibenzoylmethane and 1,2,4-triazoles

    Science.gov (United States)

    Meshkova, S. B.; Kiriyak, A. V.; Gusev, A. N.; Nischimenko, G. A.; Shul'gin, V. F.

    2012-11-01

    The synthesis and photoluminescence spectra of mixed-ligand complexes of Nd(III), Yb(III), and Er(III) with dibenzoylmethanate anion as the principal ligand and functionalized 1,2,4-triazoles and spacer bis-triazoles as ancillary ligands were described.

  4. Stability constants of mixed ligand complexes of lanthanide(III) and yttrium(III) with complexone and substituted salicylic acids

    International Nuclear Information System (INIS)

    Kolhe, Vishnu; Dwivedi, K.

    1996-01-01

    Salicylic acid and substituted salicylic acids are potential antimicrobial agents. Binary complexes of salicylic acid and its substituted derivatives with lanthanide(III) and yttrium(III) metal ions have been reported. There are reports on the ternary metal complexing equilibria with some lanthanide(III) and yttrium(III) metal ions involving aminopolycarboxylic acid as one ligand and salicylic acid (SA) and other related compounds as the second ligands. Ethylene glycol bis(2-aminoethylether)- N, N, N', N'-tetraacetic acid (EGTA) is an important member of aminopolycarboxylic acid and finds many applications in medicine and biology. Recently, few ternary complexes have been reported using EGTA as ligand. In view of biological importance of simple and mixed ligand complexes EGTA, SA and DNSA (3,5-dinitrosalicylic acid), a systematic study has been undertaken for the determination of stability constant and the results are reported. (author). 6 refs., 1 fig., 2 tabs

  5. Solution stabilities of some mixed ligand complexes of UO22+ and Th4+ with complexones and salicylic acids

    International Nuclear Information System (INIS)

    Singh, R.K.; Saxena, M.C.

    1991-01-01

    Formation constants (log Ksub(MAL)sup(MA)) of mixed ligands complexes (MAL), where M = UO 2 2+ or Th 4+ , A = IMDA, NTA, HEDTA, EDTA, CDTA or DTPA, L = salicylic acid (SA) or 5-sulphosalicylic acid (SSA), have been determined by pH titrations using Irving-Rossotti approach at 25 o C and at I =0.2 (mol dm -3 , KNO 3 ). The solution stabilities exhibit the sequence (i) Th 4+ >UO 2 2+ , (ii) IMDA>NTA>HEDTA>EDTA>CDTA>DTPA, and (iii) SA>SSA with respect to metal ions, primary ligands and secondary ligands, respectively. The formation constants log Ksub(ML)sup(M) and log Ksub(ML 2 )sup(ML) have also been determined. The Δlog K values have been found to be negative-increasing numerically with the negative charge on the deprotonated primary ligand (A n- ). (author). 17 refs., 1 tab

  6. Complexes of biuret with Cr(III), Ag(II), Cu(III) mixed ligand and UO2(II)

    International Nuclear Information System (INIS)

    Sanyal, R.M.; Ansari, B.J.; Srivastava, P.C.; Banerjee, B.K.; Chakraburtty

    1979-01-01

    The methods of preparation of some new complexes of Cr(III), Ag(III), Cu(II) mixed ligand and UO 2 (II) and their characterisation from their electronic, infrared and ESR spectra as well as from their magnetic susceptibility values are described. Crystal field parameters of some of the complexes have been calculated. (auth.)

  7. Potential role of nuclear receptor ligand all-trans retinoic acids in the treatment of fungal keratitis

    Directory of Open Access Journals (Sweden)

    Hong-Yan Zhou

    2015-08-01

    Full Text Available Fungal keratitis (FK is a worldwide visual impairment disease. This infectious fungus initiates the primary innate immune response and, later the adaptive immune response. The inflammatory process is related to a variety of immune cells, including macrophages, helper T cells, neutrophils, dendritic cells, and Treg cells, and is associated with proinflammatory, chemotactic and regulatory cytokines. All-trans retinoic acids (ATRA have diverse immunomodulatory actions in a number of inflammatory and autoimmune conditions. These retinoids regulate the transcriptional levels of target genes through the activation of nuclear receptors. Retinoic acid receptor α (RAR α, retinoic acid receptor γ (RAR γ, and retinoid X receptor α (RXR α are expressed in the cornea and immune cells. This paper summarizes new findings regarding ATRA in immune and inflammatory diseases and analyzes the perspective application of ATRA in FK.

  8. Synthesis and Optical Characterization of Mixed Ligands Beryllium Complexes for Display Device Applications

    Directory of Open Access Journals (Sweden)

    Vandna Nishal

    2015-01-01

    Full Text Available Synthesis and photoluminescent behaviour of mixed ligand based beryllium complexes with 2-(2-hydroxyphenylbenzoxazole (HPB and 5-chloro-8-hydroxyquinoline (Clq or 5,7-dichloro-8-hydroxyquinoline (Cl2q or 2-methyl-8-hydroxyquinoline (Meq or 8-hydroxyquinoline (q are reported in this work. These complexes, that is, [BeHPB(Clq], [BeHPB(Cl2q], [BeHPB(Meq], and [BeHPB(q], were prepared and their structures were confirmed by elemental analysis, Fourier transform infrared spectroscopy, nuclear magnetic resonance spectroscopy, and thermal analysis. The beryllium complexes exhibited good thermal stability up to ~300°C temperature. The photophysical properties of beryllium complexes were studied using ultraviolet-visible absorption and photoluminescence emission spectroscopy. The complexes showed absorption peaks due to π-π∗ and n-π∗ electronic transitions. The complexes emitted greenish blue light with peak wavelength at 496 nm, 510 nm, 490 nm, and 505 nm, respectively, consisting of high intensity. Color tuning was observed with changing the substituents in quinoline ring ligand in metal complexes. The emitted light had Commission Internationale d’Eclairage color coordinates values at x=0.15 and y=0.43 for [BeHPB(Clq], x=0.21 and y=0.56 for [BeHPB(Cl2q], x=0.14 and y=0.38 for [BeHPB(Meq], x=0.17 and y=0.41 for [BeHPB(q]. Theoretical calculations using DFT/B3LYP/6-31G(d,p method were performed to reveal the three-dimensional geometries and the frontier molecular orbital energy levels of these synthesized metal complexes.

  9. Expanding the family of uranium(III) alkyls. Synthesis and characterization of mixed-ligand derivatives

    Energy Technology Data Exchange (ETDEWEB)

    Matson, Ellen M.; Kiernicki, John J.; Fanwick, Phillip E.; Bart, Suzanne C. [Department of Chemistry, Purdue University, West Lafayette, IN (United States)

    2016-06-15

    The generation of uranium(III) alkyls supported by hydrotris(pyrazolyl)borate (Tp) and pentamethylcyclopentadienyl (Cp*) ligands is reported. Mixed ancillary ligand frameworks were synthesized by treating TpUI{sub 2}(THF){sub 3} (1) and Cp*UI{sub 2}(THF){sub 3} with potassium hydrotris(pyrazolyl)borate salts. Addition of one equivalent of potassium hydrotris(3,5-dimethylpyrazolyl)borate (Tp*) generated TpTp*UI (2), while treatment of Cp*UI{sub 2}(THF){sub 3} with either KTp or KTp* resulted in the respective formation of Cp*TpUI(THF) (3) or Cp*Tp*UI(THF) (4). Alkylation of 2 with KCH{sub 2}Ph or NaCH{sub 2}SiMe{sub 3} furnished TpTp*UCH{sub 2}Ph (2-CH{sub 2}Ph) or TpTp*UCH{sub 2}SiMe{sub 3} (2-CH{sub 2}SiMe{sub 3}). Similarly, treatment of 3 with NaCH{sub 2}SiMe{sub 3} formed Cp*TpUCH{sub 2}SiMe{sub 3} (3-CH{sub 2}SiMe{sub 3}), whereas treatment of 4 with KCH{sub 2}Ph generated Cp*Tp*UCH{sub 2}Ph (4-CH{sub 2}Ph). All compounds were characterized by multinuclear NMR, IR, and electronic absorption spectroscopy. Compounds 2-CH{sub 2}Ph, 3, and 3-CH{sub 2}SiMe{sub 3} were structurally characterized using X-ray crystallography as well. (copyright 2016 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  10. Optoelectronic Properties of Color-Tunable Mixed Ligand-Based Light-Emitting Zinc Complexes

    Science.gov (United States)

    Singh, Devender; Bhagwan, Shri; Saini, Raman Kumar; Tanwar, Vijeta; Nishal, Vandna

    2016-10-01

    A series of mixed ligand-based zinc complexes (Zn1-Zn5); [(8-hydroxyquinolinato)(2-(2-hydroxyphenyl)benzimidazolato)zinc(II)] (Zn1), [(5-chloro-8-hydroxyquinolinato)(2-(2-hydroxyphenyl)benzimidazolato)zinc(II)] (Zn2), [(5,7-dichloro-8-hydroxyquinolinato)(2-(2-hydroxyphenyl)benzimidazolato)zinc(II)] (Zn3), [(2-methyl-8-hydroxyquinolinato)(2-(2-hydroxyphenyl)benzimidazolato)zinc(II)] (Zn4) and [(5,7-dimethyl-8-hydroxyquinolinato)(2-(2-hydroxyphenyl)benzimidazolato)zinc(II)] (Zn5) were synthesized and characterized. The photophysical properties of zinc complexes were examined by ultraviolet-visible absorption and photoluminescence emission spectroscopy. All prepared metal complexes produced intense luminescence on excitation with a UV light source. In this study, the color-tunable characteristics of metal complexes were investigated by introducing the electron-donating and electron-withdrawing groups on the 8-hydroxyquinoline ligand. The emission spectra of metal complexes showed emission wavelength at 500 nm for [ZnHBI(q)], 509 nm for [ZnHBI(Clq)], 504 nm for [Zn(HBI)(Cl2q)], 496 nm for [ZnHBI (Meq)] and 573 nm for [ZnHBI(Me2Q)] materials. A temperature-dependent PL spectrum was used to study the emission profile of zinc complex and observed that variation in the temperature altered the position and the intensity of emission peak. The synthesized metal complex also exhibited good thermal stability (>300°C). Photophysical characteristics of color-tunable light-emitting zinc complexes suggested that these materials could be efficiently used for emissive display device applications.

  11. Deviation from the trans -Effect in Ligand-Exchange Reactions of Zeise’s Ions PtCl3(C2H4)- with Heavier Halides (Br, I- )

    Energy Technology Data Exchange (ETDEWEB)

    Hou, Gao-Lei [Physical; Govind, Niranjan [Environmental; Xantheas, Sotiris S. [Advanced; Department; Wang, Xue-Bin [Physical

    2018-01-16

    Four new Zeise’s family ions with mixed-halide ligands, i.e., PtClnX3-n(C2H4)- (X = Br, I; n = 1, 2), were synthesized via ligand-exchange reactions of KX salts with KPtCl3(C2H4) in aqueous solutions, and were detected in vacuum via electrospray ionization mass spectrometry. Their photoelectron spectra reveal a series of well-resolved spectral peaks with their electron binding energies (EBEs) decreasing with increasing halide size, with I having a much stronger effect than Br, i.e., 4.57 (–Cl3) > 4.56 (–Cl2Br) > 4.53 (–ClBr2) > 4.34 (–Cl2I) > 4.30 eV (–ClI2). Ab initio electronic structure calculations including spin-orbit coupling (SOC) predict that the cis- and trans-isomers are nearly isoenergetic with the cis-isomer for –Cl2X, and the trans-isomer for –ClX2 slightly favored, respectively. Excited-state spectra calculated with time-dependent density functional theory (TDDFT), and their comparison with the observed ones, suggest that for each species, both the cis- and trans-configurations coexist in the experiments and contribute to the observed spectra, a fact that clearly violates the prediction of the widely accepted trans-effect, which suggests that only one isomer would have formed.

  12. Polynuclear and mixed-ligand complexes of copper(II) and nickel(II) with (1-hydroxyethylidene)bisphosphonic acid

    Energy Technology Data Exchange (ETDEWEB)

    Amirov, R.R.; Saprykova, Z.A.

    1987-12-20

    The compositions and stabilities of heteronuclear and mixed-ligand copper(II) and nickel(II) (1-hydroxyethylidene)bisphosphonates were determined. Parameters of the compatibility of the ligands and central ions in the complexes were calculated. It was shown that the monoprotonated anion of (1-hydroxyethylidene)bisphosphonic acid is capable of terdentate coordination with the participation of the alcoholic hydroxy group. The acidities of the solutions were determined on a pH-673 meter. The spin-lattice relaxation time was measured on a pulse NMR spectrometer.

  13. X-ray absorption near edge structure (XANES) study of some hydroxamic mixed ligand copper complexes

    International Nuclear Information System (INIS)

    Mishra, A; Parsai, N; Shrivastava, B D; Soni, N

    2012-01-01

    With the advent of modern bright synchrotron radiation sources, X-ray absorption spectra has emerged as a powerful technique for local structure determination, which can be applied to any type of material. The X-ray absorption measurements of four hydroxamic mixed ligand copper complexes have been performed at the recently developed BL-8 Dispersive EXAFS beamline at 2.5 GeV Indus-2 synchrotron at RRCAT, Indore, India. The X-ray absorption near edge structure (XANES) data obtained has been processed using data analysis program Athena. The energies of the K absorption edge, chemical shifts, edge-widths, shifts of the principal absorption maximum in the complexes have been determined. The values of the chemical shift suggest that copper is in oxidation state +2 in all of the complexes. The chemical shift data has been utilized to estimate effective nuclear charge on copper atom. The order of the chemical shifts has been correlated to the relative ionic character of the bonding in these complexes.

  14. Chiral mixed ligand Co(II) and Ni(II) complexes: synthesis and biological activity.

    Science.gov (United States)

    Shivankar, Vitthal S; Thakkar, Narendra V

    2004-01-01

    Chiral mixed ligand (CML) transition metal complexes of the type MQL.2H2O, where M is Co(II)/Ni(II), Q is deprotonated 8-hydroxyquinoline and L is a deprotonated chiral saccharide such as (+)-glucose and (-)-fructose, have been synthesized. The metal complexes have been characterized on the basis of elemental analysis and various physicochemical techniques such as molar conductance, specific rotation measurements, magnetic, spectral and thermal studies. The cup-plate method has been used to study the antibacterial activity of the compounds against some of the pathogenic bacteria such as C. diphtheriae, E. coli, S. typhi, S. dysenteriae, S. aureus and V. cholerae. The antifungal activity of the complexes against some of the pathogenic fungi such as Candida albicans and Aspergillus niger has been studied by the tube dilution method. The results have been compared against those of controls, which were screened simultaneously. The complexes have been screened for acute oral toxicity in albino rats. The method of Litchfield and Wilcoxon has been used to determine the LD50 values.

  15. Synthesis and properties of mixed-ligand ruthenium(II) complexes containing 2-(2-pyridyl)-benzimidazole and related ligands

    International Nuclear Information System (INIS)

    Haga, Masaaki; Tanaka, Toshio.

    1979-01-01

    Mixed-ligand ruthenium(II) complexes of the [Ru(bpy) 2 L]sup(n+) (ClO 4 )sub(n) type, where bpy= 2,2'-bipyridine; L= 2-(2-pyridyl)-benzimidazole (PBImH) when n= 2, and L= 2-(2-pyridyl)-benzimidazolate (PBIm) and 2-(o-hydroxyphenyl)-benzimidazole (OBImH) when n= 1, were prepared. Anodic peak potentials and ruthenium-to-bipyridine charge transfer bands of these complexes are rationalized in terms of the donor ability of L. (author)

  16. Thermodynamics of mixed-ligand complex formation of zinc nitrilotriacetate with amino acids and dipeptides in solution

    Energy Technology Data Exchange (ETDEWEB)

    Pyreu, Dmitrii, E-mail: pyreu@mail.ru [Department of Inorganic and Analytic Chemistry, Ivanovo State UniversityErmak 39, Ivanovo 153025 (Russian Federation); Gruzdev, Matvey; Kumeev, Roman [G.A. Krestov Institute of Solution Chemistry of the Russian Academy of Sciences, Ivanovo (Russian Federation); Gridchin, Sergei [Ivanovo State University of Chemistry and Technology, Ivanovo (Russian Federation)

    2014-10-20

    Highlights: • Stable mixed ligand complexes of ZnNta with amino acids and dipeptides. • Histamine-like coordination mode of His in the complex ZnNtaHis. • Glycine-like coordination of Lys and Orn in the complexes ZnNtaL and ZnNtaHL • NH{sub 2}, CO-coordination mode of GlyGly in the complex ZnNtaGG. • NH{sub 2}, N{sup −} or NH2, N{sup −}, COO-coordination modes of GlyGly in the complex ZnNtaGGH{sub −1}. - Abstract: The isothermal calorimetry, pH-potentiometric titration and {sup 1}H and {sup 13}C NMR methods has been used to study the mixed-ligand complex formation in the systems Zn{sup 2+}–Nta{sup 3–}–L{sup −} (L = His, Orn, Lys, GlyGly, AlaAla) in aqueous solution at 298.15 K and the ionic strength of I = 0.5 (KNO{sub 3}). The thermodynamic parameters of formation of the mixed complexes have been determined. The relationship between the probable coordination modes of the complexone and amino acid or dipeptide molecules in the mixed-ligand complex and the thermodynamic parameters has been discussed.

  17. Thermal, spectroscopic, and solvent influence studies on mixed-ligand copper(II) complexes containing the bulky ligand: Bis[N-(p-tolyl)imino]acenaphthene.

    Science.gov (United States)

    El-Ayaan, Usama; Gabr, I M

    2007-05-01

    Four mixed-ligand copper(II) complexes containing the rigid bidentate nitrogen ligand bis[N-(p-tolyl)imino]acenaphthene (abb. p-Tol-BIAN) ligand are reported. These complexes, namely [Cu(p-Tol-BIAN)(2)](ClO(4))(2)1, [Cu(p-Tol-BIAN)(acac)](ClO(4)) 2, [Cu(p-Tol-BIAN)Cl(2)] 3 and [Cu(p-Tol-BIAN)(AcOH)(2)](ClO(4))(2)4 (where acac, acetylacetonate and AcOH, acetic acid) have been prepared and characterized by elemental analysis, spectroscopic, magnetic and molar conductance measurements. ESR spectra suggest a square planar geometry for complexes 1 and 2. In complexes 3 and 4, a distorted tetrahedral arrangement around copper(II) centre was suggested. Solvatochromic behavior of all studied complexes indicates strong solvatochromism of their solutions. The observed solvatochromism is mainly due to the solute-solvent interaction between the chelate cation and the solvent molecules. Thermal properties and decomposition kinetics of all complexes are investigated. The kinetic parameters (E, A, Delta H, Delta S and Delta G) of all thermal decomposition stages have been calculated using the Coats-Redfern and other standard equations.

  18. Poly(4-vinylpyridine): a polymeric ligand for mixed-mode protein chromatography.

    Science.gov (United States)

    Li, Yanying; Sun, Yan

    2014-12-19

    Poly(4-vinylpyridine) (P4VP) was proposed for use as a polymeric ligand of mixed-mode chromatography (MMC) of proteins. P4VP has linear hydrophobic chains with ionizable pyridyl groups in its backbone. The polymer was coupled onto Sepharose FF gel at a pyridyl group density of 190 μmol/mL (FF-P4VP-190) by the substitution reaction of pyridyl amines with brominated Sepharose gel. Thereby the immobilized ligand possesses the intrinsic hydrophobic nature as well as the newly obtained electrostatic interaction properties endowed from the substituted positively charged pyridyl amines. The pore size distribution was measured by inverse size exclusion chromatography, and the results revealed that P4VP formed a three-dimensional layer on the matrix surface with a maximum layer depth of 4.2 nm. The adsorption isotherms of γ-globulin and bovine serum albumin (BSA) to FF-P4VP-190 were determined under varying pH values and salt concentrations to provide insights into the adsorption properties of the medium. It was found that the adsorption capacity of γ-globulin and BSA both presented an increase with pH increasing from 8.0 to 9.0. Moreover, FF-P4VP-190 exhibited stronger adsorption for BSA than γ-globulin. The higher affinity for BSA might be attributed to its more net negative charges. Protein adsorption capacities to FF-P4VP-190 decreased with increasing NaCl concentration, but still manifested moderate levels at high salt concentration such as 75 mg/mL for γ-globulin and 14 mg/mL for BSA at 0.5 mol/L NaCl and pH 9.0. The capacity decreases with increasing ionic strength, indicating the dominant role of electrostatic interactions, while the moderate capacity values at 0.5 mol/L NaCl confirmed the presence of salt-tolerant feature of FF-P4VP-190, making it function as an MMC material. Column chromatography was conducted to investigate protein elution behavior. Efficient protein recovery was achieved at mild elution conditions such as pH 4.0 for γ-globulin and pH 4

  19. Structural, spectroscopic, and electrochemical behavior of trans-phenolato cobalt(III) complexes of asymmetric NN'O ligands as archetypes for metallomesogens.

    Science.gov (United States)

    Shakya, Rajendra; Imbert, Camille; Hratchian, Hrant P; Lanznaster, Mauricio; Heeg, Mary Jane; McGarvey, Bruce R; Allard, Marco; Schlegel, H Bernhard; Verani, Claudio N

    2006-06-07

    In order to understand and predict structural, redox, magnetic, and optical properties of more complex and potentially mesogenic electroactive compounds such as [Co(III)(L(t-BuLC))2]ClO4 (1), five archetypical complexes of general formula [Co(III)(L(RA))2]ClO4, where R = H (2), tert-butyl (3), methoxy (4), nitro (5), and chloro (6), were obtained and studied by means of several spectrometric, spectroscopic, and electrochemical methods. The complexes 2, 4, and 6 were characterized by single-crystal X-ray diffraction, and show the metal center in an approximate D2h symmetry. Experimental results support the fact that the electron donating or withdrawing nature of the phenolate-appended substituents changes dramatically the redox and spectroscopic properties of these compounds. The 3d6 electronic configuration of the metal ion dominates the overall geometry adopted by these compounds with the phenolate rings occupying trans positions to one another. Formation of phenoxyl radicals has been observed for 1, 3, and 6, but irreversible ligand oxidation takes place upon bulk electrolysis. These data were compared to detailed B3LYP/6-31G (d)-level computational calculations and have been used to account for the results observed. A comparison between compound 1 and archetype 3, validates the approach of using archetypical models to study metal-containing soft materials.

  20. Mixed-ligand copper(ii) Schiff base complexes: the role of the co-ligand in DNA binding, DNA cleavage, protein binding and cytotoxicity.

    Science.gov (United States)

    Lian, Wen-Jing; Wang, Xin-Tian; Xie, Cheng-Zhi; Tian, He; Song, Xue-Qing; Pan, He-Ting; Qiao, Xin; Xu, Jing-Yuan

    2016-05-31

    Four novel mononuclear Schiff base copper(ii) complexes, namely, [Cu(L)(OAc)]·H2O (), [Cu(HL)(C2O4)(EtOH)]·EtOH (), [Cu(L)(Bza)] () and [Cu(L)(Sal)] () (HL = 1-(((2-((2-hydroxypropyl)amino)ethyl)imino)methyl)naphthalene-2-ol), Bza = benzoic acid, Sal = salicylic acid), were synthesized and characterized by X-ray crystallography, elemental analysis and infrared spectroscopy. Single-crystal diffraction analysis revealed that all the complexes were mononuclear molecules, in which the Schiff base ligand exhibited different coordination modes and conformations. The N-HO and O-HO inter- and intramolecular hydrogen bonding interactions linked these molecules into multidimensional networks. Their interactions with calf thymus DNA (CT-DNA) were investigated by UV-visible and fluorescence spectrometry, as well as by viscosity measurements. The magnitude of the Kapp values of the four complexes was 10(5), indicating a moderate intercalative binding mode between the complexes and DNA. Electrophoresis results showed that all these complexes induced double strand breaks of pUC19 plasmid DNA in the presence of H2O2 through an oxidative pathway. In addition, the fluorescence spectrum of human serum albumin (HSA) with the complexes suggested that the quenching mechanism of HSA by the complexes was a static process. Moreover, the antiproliferative activity of the four complexes against HeLa (human cervical carcinoma) and HepG-2 (human liver hepatocellular carcinoma) cells evaluated by colorimetric cell proliferation assay and clonogenic assay revealed that all four complexes had improved cytotoxicity against cancer cells. Inspiringly, complex , with salicylic acid as the auxiliary ligand, displayed a stronger anticancer activity, suggesting that a synergistic effect of the Schiff base complex and the nonsteroidal anti-inflammatory drug may be involved in the cell killing process. The biological features of mixed-ligand copper(ii) Schiff base complexes and how acetic auxiliary

  1. Physico-chemical characterization of mixed-ligand complexes of Mn(III based on the acetylacetonate and maleic acid and its hydroxylamine derivative

    Directory of Open Access Journals (Sweden)

    Cakić Suzana M.

    2005-01-01

    Full Text Available Two new Mn(III mixed-ligand complexes with two acetylacetonate (acac ligands and one maleate ligand and its hydroxylamine derivative of the general formula [Mn(C5H7O22L] were prepared. Their structure was established by using elemental analysis, FTIR and UV/VIS spectroscopic methods, as well as magnetic measurement. Replacement of the acetylacetonate ligand by the corresponding acid ligand has been confirmed in Mn(III acetylacetonate. Based on the obtained experimental data and literature indications, structural formulae to these compounds were assigned.

  2. Mixed ligand complexes of cobalt(III) and iron(III) containing N2O2-chelating Schiff base: Synthesis, characterisation, antimicrobial activity, antioxidant and DFT study

    Science.gov (United States)

    Pramanik, Harun A. R.; Paul, Pradip C.; Mondal, Paritosh; Bhattacharjee, Chira R.

    2015-11-01

    Six mixed ligand complexes, namely, [Co(acac)L1] (1), [Fe(acac)L1] (2), [Co(acac)L2] (3), [Fe(acac)L2] (4), [Co(acac)L3] (5), and [Fe(acac)L3] (6) (H2L1 = NN/-bis(salicylidene)-trans 1,2 diaminocyclohexane, H2L2 = NN/-bis(salicylidene)-1,2 phenylenediamine, H2L3 = NN/-bis(salicylidene)-4-methyl-1,2-phenylenediamine) were synthesised and characterized using elemental analysis, IR spectra, UV-Vis spectra, mass spectra, magnetic susceptibility measurements, 1H and 13C NMR spectroscopy, thermogravimetric analysis. The molar conductance measurement confirmed the non-electrolytic nature of the complexes in DMF solution. Antioxidant activity of the complexes was studied using the 2, 2-diphenyl-1-picrylhydrazyl (DPPH) scavenging method. Biological studies of the complexes have been carried out in vitro for antimicrobial activity against some selected gram-positive and gram-negative bacteria. DFT calculations were performed using GAUSSIAN 09 program to ascertain the stable electronic structure, HOMO-LUMO energy gap, chemical hardness and dipole moment of the complexes.

  3. Conformational isomerism in mixed-ligand complexes of 2,2'-bipyridine and triphenylphosphine with copper(I) halides

    International Nuclear Information System (INIS)

    Barron, P.F.; Engelhardt, L.M.; Healy, P.C.; Kildea, J.D.; White, A.H.

    1988-01-01

    Mixed-ligand complexes of triphenylphosphine and 2,2'-bipyridine and copper(I) halides have been synthesized. The 31 P NMR spectra of the complexes were measured and are reported along with data for complete structural characterization of the complexes. The results indicate a novel dichotomy of conformational isomers to be present in the chloride lattice. The Cu-P bond length was found to not vary with different halides. 8 refs., 4 figs., 6 tabs

  4. Synthesis and characterization of mixed ligand Cu(II) complexes of salicylic acid derivatives with 2-aminobenzotiyazol derivatives

    OpenAIRE

    İlkimen, Halil; Yenikaya, Cengiz

    2018-01-01

    In thisstudy, mixed ligand transitionmetal complexes of Cu(II)have been prepared between salicylic acid derivatives [salicylic acid (H2sal) or acetylsalicylic acid (Hasal)] and 2-aminobenzothiazole derivatives[2-aminobenzothiazole (abt) or 2-amino-6-chlorobenzothiazole (Clabt) or2-amino-6-methylbenzothiazole (Meabt)]. The structures of amorphous metalcomplexes have been proposed by evaluating the data obtained from elementalanalysis, ICP-OES, FT-IR, UV-Vis, thermal analysis, magnetic suscepti...

  5. A Fast and Practical Yeast Transformation Method Mediated by Escherichia coli Based on a Trans-Kingdom Conjugal Transfer System: Just Mix Two Cultures and Wait One Hour.

    Directory of Open Access Journals (Sweden)

    Kazuki Moriguchi

    Full Text Available Trans-kingdom conjugation is a phenomenon by which DNA is transferred into a eukaryotic cell by a bacterial conjugal transfer system. Improvement in this method to facilitate the rapid co-cultivation of donor bacterial and recipient eukaryotic cell cultures could make it the simplest transformation method, requiring neither isolation of vector DNA nor preparation of competent recipient cells. To evaluate this potential advantage of trans-kingdom conjugation, we examined this simple transformation method using vector combinations, helper plasmids, and recipient Saccharomyces cerevisiae strains. Mixing donor Escherichia coli and recipient S. cerevisiae overnight cultures (50 μL each consistently yielded on the order of 10(1 transformants using the popular experimental strain BY4742 derived from S288c and a shuttle vector for trans-kingdom conjugation. Transformation efficiency increased to the order of 10(2 using a high receptivity trans-kingdom conjugation strain. In addition, either increasing the amount of donor cells or pretreating the recipient cells with thiols such as dithiothreitol improved the transformation efficiency by one order of magnitude. This simple trans-kingdom conjugation-mediated transformation method could be used as a practical yeast transformation method upon enrichment of available vectors and donor E. coli strains.

  6. A Fast and Practical Yeast Transformation Method Mediated by Escherichia coli Based on a Trans-Kingdom Conjugal Transfer System: Just Mix Two Cultures and Wait One Hour.

    Science.gov (United States)

    Moriguchi, Kazuki; Yamamoto, Shinji; Ohmine, Yuta; Suzuki, Katsunori

    2016-01-01

    Trans-kingdom conjugation is a phenomenon by which DNA is transferred into a eukaryotic cell by a bacterial conjugal transfer system. Improvement in this method to facilitate the rapid co-cultivation of donor bacterial and recipient eukaryotic cell cultures could make it the simplest transformation method, requiring neither isolation of vector DNA nor preparation of competent recipient cells. To evaluate this potential advantage of trans-kingdom conjugation, we examined this simple transformation method using vector combinations, helper plasmids, and recipient Saccharomyces cerevisiae strains. Mixing donor Escherichia coli and recipient S. cerevisiae overnight cultures (50 μL each) consistently yielded on the order of 10(1) transformants using the popular experimental strain BY4742 derived from S288c and a shuttle vector for trans-kingdom conjugation. Transformation efficiency increased to the order of 10(2) using a high receptivity trans-kingdom conjugation strain. In addition, either increasing the amount of donor cells or pretreating the recipient cells with thiols such as dithiothreitol improved the transformation efficiency by one order of magnitude. This simple trans-kingdom conjugation-mediated transformation method could be used as a practical yeast transformation method upon enrichment of available vectors and donor E. coli strains.

  7. Formation constants of lanthanide(III)- aminopolycarboxylate- ATP mixed ligand complexes and their systematics

    International Nuclear Information System (INIS)

    Verma, Sangeeta; Limaye, S.N.; Saxena, M.C.

    1993-01-01

    Formation constants (log Ksub(MAL)sup(MA), log Ksub(ML)sup(M) and log Ksub(ML)sup(ML) of mixed ligand lanthanide(III) complexes of the type [Ln(III).A.ATP[ 2 , where LN(III)=La 3+ , Ce 3+ , Pr 3+ , Nd 3+ , Sm 3+ , Eu 3+ , Gd 3+ , Tb 3+ or Dy 3+ ' A=NTA(nitrilotriacetate) or HEDTA (2-hydroxyethylethylenediamine triacetate) and ATP=adenosine 5'-triphosphate (L), and of the binary [Ln(III).ATP[ and [Ln(III).(ATP) 2 [ complexes have been determined by potentiometric pH titrations using the Irving-Rossotti approach at three temperatures 20, 30 and 40 degC and at a fixed ionic strength, I=0.2 mol dm -3 (NAclO 4 ). The solution stabilities (log Ksub(MAL)sup(MA) values) are influenced by the electrostatic effect involved in ternary complexation and increase with temperature. The enthalpy factor (ΔH) has been found to be small but unfavourable and the entropy factor (ΔS) large and favourable. The log Ksub(MAL)sup(MA) values lie in the order NTA>HEDTA with respect to A and La 3+ 3+ 3+ 3+ 3+ 3+ >Gd 3+ 3+ 3+ with respect to lanthanides. Tetrad effect is present in the formation constant values; its magnitude has been found to lie in the sequence f 7 >f 3 -f 4 ≅ f 10 -f 11 for the Ln(III) ions. Systematics in the formation constant values has been further studied by evaluating changes in the inter-electronic repulsion Racah parameters, extra stabilisation of specific 4f 9 -configurations and nephelauxetic ratio using experimental values of the formation constants. (author). 24 refs., 2 figs., 3 tabs

  8. Copper(ii) mixed-ligand polypyridyl complexes with doxycycline - structures and biological evaluation.

    Science.gov (United States)

    Abosede, Olufunso O; Vyas, Nilima A; Singh, Sushma B; Kumbhar, Avinash S; Kate, Anup; Kumbhar, Anupa A; Khan, Ayesha; Erxleben, Andrea; Smith, Peter; de Kock, Carmen; Hoffmann, Frank; Obaleye, Joshua A

    2016-02-21

    Mixed-ligand Cu(ii) complexes of the type [Cu(doxycycline)(L)(H2O)2](NO3)2, where doxycycline = [4-(dimethylamino)-3,5,10,12,12a-pentahydroxy-6-methyl-1,11-dioxo-1,4,4a,5,5a,6,11,12a-octahydrotetracene-2-carboxamide] and L = 2,2'-bipyridine (bpy, 1), 1,10-phenanthroline (phen, 2), dipyrido[3,2-d:2',3'-f]quinoxaline (dpq, 3) and dipyrido[3,2-a:2',3'-c]phenazine (dppz, 4) have been synthesised and characterised by structural, analytical, and spectral methods. The single-crystal X-ray structures of 1 and 2 exhibited two different geometries, distorted square-pyramidal and octahedral respectively as well as different coordination modes of doxycycline. Complexes 2-4 exhibit prominent plasmid DNA cleavage at significantly low concentrations probably by an oxidative mechanism. Matrix Metalloproteinase (MMP-2) inhibition studies revealed that all complexes inhibit MMP-2 similar to doxycycline which is a well-known MMP inhibitor with 3 being the most potent. IC50 values of doxycycline and 1-4 against MCF-7 (human breast cancer) and HeLa cell lines were almost equal in which 3 showed the highest efficiency (IC50 = 0.46 ± 0.05 μM), being consistent with its increased MMP inhibition potency. The antimalarial activities of these complexes against the chloroquine-sensitive Plasmodium falciparum NF54 and chloroquine-resistant Plasmodium falciparum Dd2 strains reveal that complex 3 exhibited a higher activity than artesunate drug against the chloroquine-resistant Dd2 strain.

  9. Dual salt mixtures in mixed mode chromatography with an immobilized tryptophan ligand influence the removal of aggregated monoclonal antibodies.

    Science.gov (United States)

    Vajda, Judith; Mueller, Egbert; Bahret, Eva

    2014-04-01

    In downstream processing of monoclonal antibodies, proper aggregate removal is crucial. Mixed mode ligands such as immobilized tryptophan have been developed to satisfy the need for efficient removal of antibody aggregates. However, method development for mixed mode applications is complicated, since protein binding and elution can be modulated by an increased set of parameters. In the current study, we investigate the effect of different dual salt mixtures on mixed mode chromatography using TOYOPEARL MX-Trp-650M resin, with respect to the dynamic binding capacity, resolution and monomer purity of two different humanized immunoglobulins. Binding capacities varying by more than 50% were observed for different salt mixtures. Furthermore, antibody monomer and aggregate resolution deviated by 30% for different salt mixtures and linear gradient elution. Similar trends were obtained using an immobilized carboxymethyl ligand for the same set of experiments, but the overall resolution was lower. Less kosmotropic salt systems emphasize the electrostatic binding of the relatively hydrophobic mAbs and reduce hydrophobic attraction to a selectivity-determining constraint. Kosmotropic salts such as citrate appear to cause dominating hydrophobic interactions in protein adsorption that hinder electrostatic protein-ligand interactions. This effect may depend on the ionic and hydrophobic site distribution of a protein. The data presented here are important for the further improvement of downstream processing of therapeutic monoclonal antibodies. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. DNA binding and gel electrophoresis studies of a copper (II) complex containing mixed aliphatic and aromatic dinitrogen ligands.

    Science.gov (United States)

    Shahabadi, Nahid; Darabi, Farivash; Maghsudi, Maryam; Kashanian, Soheila

    2010-06-01

    The interaction of a novel mixed ligand copper (II) complex, [Cu(N-N)(L)(EtOH)](NO(3))(2) . 2H(2)O, in which N-N indicates 2,9-dimethyl-1,10-phenanthroline and L indicates N,N-dimethyltrimethylenediamine with calf thymus DNA was investigated by absorption, circular dichroism, voltammetric, and viscosimetric techniques. The absorption spectra of the complex with calf thymus DNA showed a marked hypochromism in the pi --> pi* and metal to ligand charge transfer (MLCT) transitions, with no obvious red shift attributed to a partial intercalation. The intrinsic binding constant (K(b)) was determined as 2 x 10(5) M(-1). There was slight to appreciable changes in the relative viscosity of DNA, which is consistent with enhanced hydrophobic interaction of the methyl-substituted phen ring and partial intercalation mode of binding. Electrochemical studies showed a decrease in the peak current, which is ascribed to the strong binding between Cu (II) complex and DNA. The fluorescence spectral characteristics showed that the Cu (II) complex is able to displace the methylene blue bound to DNA, but not as complete as intercalative molecules. It is remarkable that this mixed ligand complex, in contrast to [Cu(2,9-dmp)(2)](+) (2,9-dmp = 2,9-dimethyl-1,10-phenanthroline), which fails to cleave DNA, has ability to cleave the supercoiled plasmid DNA.

  11. NMR Spectroscopic Characterization of Methylcobalt(III) Compounds with Classical Ligands. Crystal Structures of [Co(NH(3))(5)(CH(3))]S(2)O(6), trans-[Co(en)(2)(NH(3))(CH(3))]S(2)O(6) (en = 1,2-Ethanediamine), and [Co(NH(3))(6)]-mer,trans-[Co(NO(2))(3)(NH(

    DEFF Research Database (Denmark)

    Kofod, Pauli; Harris, Pernille; Larsen, Sine

    1997-01-01

    to the trans ligand is 0.170 Å in the trans-[Co(en)(2)(NH(3))(CH(3))](2+) cation. The structural trans influence appears to decrease with the overall charge of the coordination compound. Estimates of the scalar one-bond cobalt-carbon coupling constants, (1)J(Co)(-)(C), in the pentacyanomethylcobalt(III) anion......A series of methylcobalt(III) compounds with solely classical ligands such as NH(3), H(2)O, NO(2)(-), CN(-), and 1,2-ethanediamine (en) has been prepared by ligand substitution of the pentaamminemethylcobalt(III) cation. The new compounds have been characterized by (1)H, (13)C, and (59)Co nuclear......))(4)(NH(3))(2)] (3). Compound 1 is monoclinic, P2(1)/n, with cell dimensions a = 6.4856(9) Å, b = 18.0720(11) Å, c = 9.7854(14) Å, and beta = 98.280(13) degrees. Compound 2 is orthorhombic, P2(1)2(1)2, with cell dimensions a = 12.211(3) Å, b = 10.107(3) Å, and c = 11.514(3) Å. Compound 3 is monoclinic, P2...

  12. Studies on the mixed ligand complexes of copper(II involving a sulfa drug and some potentially bi or tridentate ligands under physiological conditions

    Directory of Open Access Journals (Sweden)

    S. Regupathy

    2014-12-01

    Full Text Available The stability constants of mixed ligand complexes formed in the Cu(II-sulfathiazole(stz(A-glycine(gly, dl-2-aminobutanoic acid(2aba, dl-3-aminobutanoic acid(3aba, 1,2-diaminopropane(dp, 1,3-diaminopropane(tp, dl-2,3-diaminopropanoic acid(dapa, dl-2,4-diaminobutanoic acid(daba, dl-2,5-diaminopentanoic acid(ornithine, orn(B systems have been determined pH-metrically at 37 °C and I = 0.15 mol dm−3 (NaClO4 using SCOGS program. Analysis of experimental data indicates the presence of CuABH, CuAB, CuAB2H2 or CuAB2 species. The Δlog K values demonstrate higher stabilities for the mixed ligand complexes compared to the binary analogues. The CuAB complexes with B = gly, 2aba, dapa & orn systems were isolated and characterized using micro analytical, magnetic moment, ESR, electrochemical studies, TG/DTA, power XRD and SEM analysis. Magnetic susceptibility and electronic spectral studies suggest square planar geometry for the CuAB complexes. The g values indicate that the unpaired electron lies in thedx2-y2 orbital. The TG/DTA studies reveal that the complexes are non hydrated and possesses high thermal stability. The powder XRD data suggest that the complex is microcrystalline. The antimicrobial activity and CT DNA cleavage studies of the complexes are also reported.

  13. Synthesis, characterization and cytotoxicity of mixed ligand Mn(II, Co(II and Ni(II complexes

    Directory of Open Access Journals (Sweden)

    Osman Souad A.

    2014-01-01

    Full Text Available Complexes of the type [ML'L(OH(H2O] {where M= Ni(II, Co(II or Mn(II, L'= isatin and HL= 3-(2-phenylhydrazonoacetylacetone, 3-(2-(4-chlorophenylhydrazonoacetylacetone or 3-(2-(4-bromophenylhydrazono-acetylacetone} have been synthesized by equimolar reaction of a metal(II chloride with isatin and 3-(2-(arylhydrazonoacetylacetone. The resulting complexes have been characterized by elemental analyses, molar conductivity, spectral data (IR, 1H NMR, mass and magnetic moments. Furthermore, the ligands and their metal complexes have been screened for their cytotoxicity against different human cancer cell lines by using SRB assay. The results showed that most of the mixed ligand metal complexes have high cytotoxicity in comparison with the reference drugs used.

  14. Mixed-mode solid-phase extraction followed by acetylation and gas chromatography mass spectrometry for the reliable determination of trans-resveratrol in wine samples

    International Nuclear Information System (INIS)

    Montes, R.; Garcia-Lopez, M.; Rodriguez, I.; Cela, R.

    2010-01-01

    This work presents an advantageous analytical procedure for the accurate determination of free trans-resveratrol in red and white wines. The proposed method involves solid-phase extraction (SPE), acetylation of the analyte in aqueous media and further determination by gas chromatography (GC) with mass spectrometry detection (MS). The use of a mixed-mode SPE sorbent provides an improvement in the selectivity of the extraction step; moreover, the presence of several intense ions in the electron impact mass spectra of its acetyl derivative guarantees the unambiguous identification of trans-resveratrol. Considering a sample intake of 10 mL, the method provides a limit of quantification (LOQ) of 0.8 ng mL -1 and linear responses for concentrations up to 2.5 μg mL -1 , referred to wine samples. The average recovery, estimated with samples fortified at different concentrations in the above range, was 99.6% and the inter-day precision stayed below 8%. Trans-resveratrol levels in the analyzed wines varied from 3.4 to 1810 ng mL -1 . Cis-resveratrol was also found in all samples. In most cases, equal or higher responses were measured for this latter form than for the trans-isomer. The reduced form of resveratrol, dihydro-resveratrol, was systematically identified in red wines.

  15. Mixed-mode solid-phase extraction followed by acetylation and gas chromatography mass spectrometry for the reliable determination of trans-resveratrol in wine samples

    Energy Technology Data Exchange (ETDEWEB)

    Montes, R.; Garcia-Lopez, M. [Departamento de Quimica Analitica, Nutricion y Bromatologia, Instituto de Investigacion y Analisis Alimentario, Universidad de Santiago de Compostela, Santiago de Compostela 15782 (Spain); Rodriguez, I., E-mail: isaac.rodriguez@usc.es [Departamento de Quimica Analitica, Nutricion y Bromatologia, Instituto de Investigacion y Analisis Alimentario, Universidad de Santiago de Compostela, Santiago de Compostela 15782 (Spain); Cela, R. [Departamento de Quimica Analitica, Nutricion y Bromatologia, Instituto de Investigacion y Analisis Alimentario, Universidad de Santiago de Compostela, Santiago de Compostela 15782 (Spain)

    2010-07-12

    This work presents an advantageous analytical procedure for the accurate determination of free trans-resveratrol in red and white wines. The proposed method involves solid-phase extraction (SPE), acetylation of the analyte in aqueous media and further determination by gas chromatography (GC) with mass spectrometry detection (MS). The use of a mixed-mode SPE sorbent provides an improvement in the selectivity of the extraction step; moreover, the presence of several intense ions in the electron impact mass spectra of its acetyl derivative guarantees the unambiguous identification of trans-resveratrol. Considering a sample intake of 10 mL, the method provides a limit of quantification (LOQ) of 0.8 ng mL{sup -1} and linear responses for concentrations up to 2.5 {mu}g mL{sup -1}, referred to wine samples. The average recovery, estimated with samples fortified at different concentrations in the above range, was 99.6% and the inter-day precision stayed below 8%. Trans-resveratrol levels in the analyzed wines varied from 3.4 to 1810 ng mL{sup -1}. Cis-resveratrol was also found in all samples. In most cases, equal or higher responses were measured for this latter form than for the trans-isomer. The reduced form of resveratrol, dihydro-resveratrol, was systematically identified in red wines.

  16. Crystal structures and luminescence of two cadmium-carboxylate cluster-based compounds with mixed ligands

    Energy Technology Data Exchange (ETDEWEB)

    Ma, Hui-Fang; Lei, Qian; Wang, Yu-Ling; Yin, Shun-Gao; Liu, Qing-Yan [College of Chemistry and Chemical Engineering and Key Lab. of Functional Small Organic Molecule of Ministry of Education, Jiangxi Normal Univ., Nanchang (China)

    2017-04-04

    Reactions of Cd(NO{sub 3}){sub 2}.4H{sub 2}O with 2-quinolinecarboxylic acid (H-QLC) in the presence of 1,4-benzenedicarboxylic acid (H{sub 2}-BDC) or 1,3,5-benzenetricarboxylic acid (H-BTC) in DMF/H{sub 2}O solvent afforded two compounds, namely, [Cd(QLC)(BDC){sub 1/2}(H{sub 2}O)]{sub n} (1) and [Cd(QLC)(BTC){sub 1/3}]{sub n} (2). Both compounds are two-dimensional (2D) frameworks but feature different cadmium-carboxylate clusters as a result of the presence of the polycarboxylate ligands with different geometries and coordination preference. The dinuclear Cd{sub 2}(QLC){sub 2} units in 1 are bridged by the pairs of bridging water ligands to give a one-dimensional (1D) chain, which is further linked by the second ligand of BDC{sup 2-} to form a 2D structure. Compound 2 is constructed from unique hexanuclear macrometallacyclic Cd{sub 6}(QLC){sub 6} clusters, which are linked by the surrounding BTC{sup 3-} ligands to generate a 2D structure. Photoluminescence studies showed both compounds exhibit ligand-centered luminescent emissions with emission maxima at 405 and 401 nm, respectively. (copyright 2017 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  17. Uranium-carbene-imido metalla-allenes: ancillary-ligand-controlled cis-/trans-isomerisation and assessment of trans influence in the R{sub 2}C=U{sup IV}=NR' unit (R=Ph{sub 2}PNSiMe{sub 3}; R'=CPh{sub 3})

    Energy Technology Data Exchange (ETDEWEB)

    Lu, Erli; Cooper, Oliver J.; Tuna, Floriana; Wooles, Ashley J.; Kaltsoyannis, Nikolas; Liddle, Stephen T. [School of Chemistry, The University of Manchester (United Kingdom)

    2016-08-08

    Uranium(IV)-carbene-imido complexes [U(BIPM{sup TMS})(NCPh{sub 3})(κ{sup 2}-N,N'-BIPY)] (2; BIPM{sup TMS}=C(PPh{sub 2}NSiMe{sub 3}){sub 2}; BIPY=2,2-bipyridine) and [U(BIPM{sup TMS})(NCPh{sub 3})(DMAP){sub 2}] (3; DMAP=4-dimethylamino-pyridine) that contain unprecedented, discrete R{sub 2}C=U=NR' units are reported. These complexes complete the family of E=U=E (E=CR{sub 2}, NR, O) metalla-allenes with feasible first-row hetero-element combinations. Intriguingly, 2 and 3 contain cis- and trans-C=U=N units, respectively, representing rare examples of controllable cis/trans isomerisation in f-block chemistry. This work reveals a clear-cut example of the trans influence in a mid-valent uranium system, and thus a strong preference for the cis isomer, which is computed in a co-ligand-free truncated model - to isolate the electronic trans influence from steric contributions - to be more stable than the trans isomer by approximately 12 kJ mol{sup -1} with an isomerisation barrier of approximately 14 kJ mol{sup -1}. (copyright 2016 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  18. Structure and biological properties of mixed-ligand Cu(II) Schiff base complexes as potential anticancer agents.

    Science.gov (United States)

    Gou, Yi; Li, Jinlong; Fan, Boyi; Xu, Bohui; Zhou, Min; Yang, Feng

    2017-07-07

    We synthesized two mixed-ligand Cu(II) complexes containing different aroylhydrazone ligands and a pyridine co-ligand, namely, [Cu(L1)(Py)] (C1) and [Cu(L2)(Py)(Br)] (C2) (L1 = (E)-2-hydroxy-N'-((2-hydroxynaphthalen-1-yl)methylene)benzohydrazide, Py = pyridine, L2 = (E)-2-hydroxy-N'-(phenyl(pyridin-2-yl)methylene)benzohydrazide), and assessed their chemical and biological properties to understand their marked activity. C2 showed better anticancer activity than C1 in various human cancer cell lines, including the cisplatin-resistant lung cancer cell line A549cisR. Both Cu(II) complexes, especially C2, displayed promising anti-metastatic activity against HepG2 cells. Spectroscopic titration and agarose gel electrophoresis experiments indicated that C2 exhibited binding affinity toward calf-thymus DNA and efficient pBR322 DNA-cleaving ability. Further mechanistic studies showed that C2 effectively induced DNA damage and thus led to cell cycle arrest at the G2/M phase, and also stimulated mitochondrial dysfunction mediated by reactive oxygen species and caspase-dependent apoptosis. Copyright © 2017 Elsevier Masson SAS. All rights reserved.

  19. Four Mixed-Ligand Zn(II Three-Dimensional Metal-Organic Frameworks: Synthesis, Structural Diversity, and Photoluminescent Property

    Directory of Open Access Journals (Sweden)

    Chih-Chieh Wang

    2017-11-01

    Full Text Available Assemblies of four three-dimensional (3D mixed-ligand coordination polymers (CPs having formulas, {[Zn2(bdc2(4-bpdh]·C2H5OH·2H2O}n (1, [Zn(bdc(4-bpdh]n (2, {[Zn2(bdc2(4-bpdh2]·(4-bpdh}n (3, and {[Zn(bdc(4-bpdh]·C2H5OH}n (4 (bdc2− = dianion of 1,4-benzenedicarboxylic acid, 4-bpdh = 2,5-bis(4-pyridyl-3,4-diaza-2,4-hexadiene have been synthesized and structurally characterized by single-crystal X-ray diffraction method. Structural determination reveals that the coordination numbers (geometry of Zn(II ions in 1, 2, 3, and 4 are five (distorted square-pyramidal (SP, six (distorted octahedral (Oh, five (trigonal-bipyramidal (TBP, and four (tetrahedral (Td, respectively, and are bridged by 4-bpdh with bis-monodentate coordination mode and bdc2− ligands with bis-bidentate in 1, chelating/bidentate in 2, bis-monodentate and bis-bidentate in 3, and bis-monodentate in 4, to generate two-fold interpenetrating 3D cube-like metal-organic framework (MOF with pcu topology, non-interpenetrating 3D MOF, two-fold interpenetrating 3D rectangular-box-like MOF with pcu topology and five-fold interpenetrating diamondoid-like MOF with dia topology, respectively. These different intriguing architectures indicate that the coordination numbers and geometries of Zn(II ions, coordination modes of bdc2− ligand, and guest molecules play important roles in the construction of MOFs and the formation of the structural topologies and interpenetrations. Thermal stabilities, and photoluminescence study of 1–4 were also studied in detail. The complexes exhibit ligands based photoluminescence properties at room temperature.

  20. Eight-Electron Silver and Mixed Gold/Silver Nanoclusters Stabilized by Selenium Donor Ligands.

    Science.gov (United States)

    Chang, Wan-Ting; Lee, Po-Yi; Liao, Jian-Hong; Chakrahari, Kiran Kumarvarma; Kahlal, Samia; Liu, Yu-Chiao; Chiang, Ming-Hsi; Saillard, Jean-Yves; Liu, C W

    2017-08-14

    The first atomically and structurally precise silver-nanoclusters stabilized by Se-donor ligands, [Ag 20 {Se 2 P(O i Pr) 2 } 12 ] (3) and [Ag 21 {Se 2 P(OEt) 2 } 12 ] + (4), were isolated by ligand replacement reaction of [Ag 20 {S 2 P(O i Pr) 2 } 12 ] (1) and [Ag 21 {S 2 P(O i Pr) 2 } 12 ] + (2), respectively. Furthermore, doping reactions of 4 with Au(PPh 3 )Cl resulted in the formation of [AuAg 20 {Se 2 P(OEt) 2 } 12 ] + (5). Structures of 3, 4, and 5 were determined by single-crystal X-ray diffraction. The anatomy of cluster 3 with an Ag 20 core having C 3 symmetry is very similar to that of its dithiophosphate analogue 1. Clusters 4 and 5 exhibit an Ag 21 and Au@Ag 20 core of O h symmetry composed of eight silver capping atoms in a cubic arrangement and encapsulating an Ag 13 and Au@Ag 12 centered icosahedron, respectively. Both ligand exchange and heteroatom doping result in significant changes in optical and emissive properties for chalcogen-passivated silver nanoparticles, which have been theoretically confirmed as 8-electron superatoms. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. DNA binding and biological activity of mixed ligand complexes of Cu(II, Ni(II and Co(II with quinolones and N donor ligand

    Directory of Open Access Journals (Sweden)

    S.M M Akram

    2015-10-01

    Full Text Available  AbstractMixed ligand complexes of  Cu(II, Ni(II and Co(II have been synthesized by using levofloxacin and bipyridyl and characterized using spectral and analytical techniques. The binding behavior of the Ni(II and Cu(II complexes with herring sperm DNA(Hs-DNA were determined using electronic absorption titration, viscometric measurements and cyclic voltammetry measurements. The binding constant calculated  for Cu(II and Ni(II complexes are 2.0 x 104 and 4.0 x 104 M-1 respectively. Detailed analysis reveals that these metal complexes interact with DNA through intercalative binding mode. The nuclease activity of  Cu(II and Ni(II complexes with ct-DNA was carried out using agarose gel electrophoresis technique. The antioxidant activities for the synthesized complexes have been tested and the antibacterial activity for Ni(II complex was also checked.Key words: Intercalation, hypochromism, red shift and  peak potential.

  2. Lanthanide mixed ligand chelates for DNA profiling and latent fingerprint detection

    Science.gov (United States)

    Menzel, E. R.; Allred, Clay

    1997-02-01

    It is our aim to develop a universally applicable latent fingerprint detection method using lanthanide (rare-earth) complexes as a source of luminescence. Use of these lanthanide complexes offers advantages on several fronts, including benefits from large Stokes shifts, long luminescence lifetimes, narrow emissions, ability of sequential assembly of complexes, and chemical variability of the ligands. Proper exploitation of these advantages would lead to a latent fingerprint detection method superior to any currently available. These same characteristics also lend themselves to many of the problems associated with DNA processing in the forensic science context.

  3. Theoretical and experimental evidence for a new kind of spin-coupled singlet species: Isomeric mixed-valent complexes bridged by a radical anion ligand

    Czech Academy of Sciences Publication Activity Database

    Sarkar, B.; Patra, S.; Fiedler, Jan; Sunoj, R. B.; Janardanan, D.; Mobin, S. M.; Niemeyer, M.; Lahiri, G. K.; Kaim, W.

    2005-01-01

    Roč. 44, č. 35 (2005), s. 5655-5658 ISSN 0044-8249 R&D Projects: GA AV ČR IAA400400505; GA ČR GA203/03/0821; GA MŠk LC510 Institutional research plan: CEZ:AV0Z40400503 Keywords : azobispyridine * bridging ligand s * mixed -valed complexes * N- ligand s Subject RIV: CF - Physical ; Theoretical Chemistry

  4. Hydrothermal syntheses, crystal structures, and photophysical properties of two coordination polymers with mixed ligands

    Science.gov (United States)

    Yan, Li; Liu, Chun-Ling

    2017-10-01

    Two novel metal-organic coordination polymers [Cd(ipdt)(m-BDC)·3H2O]n (1) and [Pb(mip)2(NTC) ·2H2O]n (2) [ipdt = 2,6-Dimethoxy-4-(1H-1,3,7,8-tetraaza-cyclopenta[l]phenanthren-2-yl)-phenol, mip = 2-(3-methoxyphenyl)-1H-imidazo[4,5-f][1,10]phenanthroline, m-BDC = isophthalic acid, NTC = nicotinic acid] have been synthesized by hydrothermal reactions and characterized by elemental analysis, thermogravimetric (TG) analysis, infrared spectrum (IR) and single-crystal X-ray diffraction. Single-crystal X-ray diffraction reveals that 1 exhibits two-dimensional (2D) layer architecture, and 2 shows 1D chain architecture. TG analysis shows clear courses of weight loss, which corresponds to the decomposition of different ligands. The luminescent properties for the ligand ipdt, mip and complexes 1-2 are also discussed in detail, which should be acted as potential luminescent material.

  5. Constructing two new crystalline metal–organic frameworks based on a mixed-donor ligand

    KAUST Repository

    Wang, Xiaofang

    2016-02-01

    © 2015 Elsevier B.V. All Rights Reserved. The self-assembly of a prominent ligand, 5-(4-(1H-tetrazolyl)phen)isophthalic acid (H3TZPI), with Zn2 +/Cu2 + centres generates two new MOFs, [Zn2(TZPI)(μ3-OH)(H2O)2]·2H2O (JUC-161) and [Cu(HTZPI)(μ2-H2O)0.5(H2O)1.5]·5(H2O) (JUC-162). JUC-161 exhibits fascinating three-dimensional structures containing rectangular channels with dimensions of 6.5 × 3.0 Å2, and JUC-162 displays 3D supramolecular structures with 12.5 × 14.6 Å2 hexagonal channels. The observed structural diversity in these frameworks is due to the two distinct coordinating moieties of the H3TZPI ligand. The photoluminescence of JUC-161 and the magnetic properties of JUC-162 are also measured at room temperature. Photoluminescence investigations reveal that JUC-161 displays a strong main emission spectrum peak at 388 nm. JUC-162 is found to exhibit an antiferromagnetic interaction between Cu2 + ions.

  6. Mixed-valency with cyanides as terminal ligands: Diruthenium(III,II) complexes with the 3,6-bis(2-pyridyl)-1,2,4,5-tetrazine bridge and variable co-ligands (CN- vs. bpy or NH3)

    Czech Academy of Sciences Publication Activity Database

    Vergara, M. M.; García Posse, M. E.; Fagalde, F.; Katz, N. E.; Fiedler, Jan; Sarkar, B.; Sieger, M.; Kaim, W.

    2010-01-01

    Roč. 363, č. 1 (2010), s. 163-167 ISSN 0020-1693 R&D Projects: GA MŠk OC 140; GA MŠk OC09043 Institutional research plan: CEZ:AV0Z40400503 Keywords : cyano ligands * mixed-valency * Ruthenium complexes Subject RIV: CG - Electrochemistry Impact factor: 1.899, year: 2010

  7. Synthesis, structure, spectroscopy and redox energetics of a series of uranium(4) mixed-ligand metallocene complexes

    Energy Technology Data Exchange (ETDEWEB)

    Thomson, R.K.; Scott, B.L.; Morris, D.E.; Kiplinger, J.L. [Los Alamos National Laboratory, Los Alamos, NM (United States)

    2010-06-15

    A series of uranium(IV) mixed-ligand amide-halide/pseudo-halide complexes (C{sub 5}Me{sub 5}){sub 2}U[N(SiMe{sub 3}){sub 2}](X) (X = F (1), Cl (2), Br (3), I (4), N{sub 3} (5), NCO (6)), (C{sub 5}Me{sub 5}){sub 2}U(NPh{sub 2})(X) (X = Cl (7), N{sub 3} (8)), and (C{sub 5}Me{sub 5}){sub 2}U[N(Ph)(SiMe{sub 3})](X) (X Cl (9), N{sub 3} (10)) have been prepared by one electron oxidation of the corresponding uranium(III) amide precursors using either copper halides, silver iso-cyanate, or triphenylphosphine gold(I)azide. Agostic U---H-C interactions and {eta}{sub 3}-(N,C,C') coordination are observed for these complexes in both the solid-state and solution. There is a linear correlation between the chemical shift values of the C{sub 5}Me{sub 5} ligand protons in the {sup 1}H NMR spectra and the U(IV)/U(III) reduction potentials of the (C{sub 5}Me{sub 5}){sub 2}U[N(SiMe{sub 3}){sub 2}](X) complexes, suggesting that there is a common origin, that is overall {sigma}-/{pi}-donation from the ancillary (X) ligand to the metal, contributing to both observables. Optical spectroscopy of the series of complexes 1-6 is dominated by the (C{sub 5}Me{sub 5}){sub 2}U[N(SiMe{sub 3}){sub 2}] core, with small variations derived from the identity of the halide/pseudo-halide. The considerable {pi}-donating ability of the fluoride ligand is reflected in both the electrochemistry and UV-visible-NIR spectroscopic behavior of the fluoride complex (C{sub 5}Me{sub 5}){sub 2}U[N(SiMe{sub 3}){sub 2}](F) (1). The syntheses of the new trivalent uranium amide complex, (C{sub 5}Me{sub 5}){sub 2}U[N(Ph)(SiMe{sub 3})](THF), and the two new weakly-coordinating electrolytes, [Pr{sub 4}N][B{l_brace}3,5-(CF{sub 3}){sub 2}C{sub 6}H{sub 3{r_brace}4}] and [Pr{sub 4}N][B(C{sub 6}F{sub 5}){sub 4}], are also reported. (authors)

  8. Synthesis, Characterization, Luminescence and Biological Activity of Two Lanthanide Complexes Involving Mixed Ligands

    Energy Technology Data Exchange (ETDEWEB)

    Ma, Deyun; Guo, Haifu; Qin, Liang [Zhaoqing Univ., Zhaoqing (China); Xu, Jun [Jinan Univ., Guangzhou (China)

    2013-09-15

    Two new isostructural dinuclear complexes, Ln{sub 2}(4-cpa){sub 6}(bpy){sub 2} (Ln = Eu (1); Tb (2), 4-cpa = 4-chlorophenyl-acetate, bpy = 2,2'-bipyridine), have been hydrothermally synthesized and characterized by IR spectroscopy, elemental analysis, thermogravimetric analysis (TGA), powder X-ray diffraction and single-crystal X-ray diffraction. The lanthanide ions are bridged by two bidentate and two terdentate carboxylate groups to give centrosymmetric dimers with Ln···Ln separations of 3.967(2) and 3.956(3) A, respectively. Each metal atom is nine-coordinate and exhibits a distorted tricapped trigonal prismatic geometry. Three-dimensional fluorescence spectra show that both 1 and 2 emit bright red and green luminescence at room temperature, with long lifetimes of up to 0.369 ms (at 614 nm) and 0.432 ms (at 543 nm), respectively. Moreover, poor luminescence efficiency has been noted for complex 2. The 4-Hcpa ligand and complexes 1-2 have been screened for their phytogrowth-inhibitory activities against Brassica napus L. and Echinochloa crusgalli L., and the results are compared with the activity of quizalofop-P-ethyl.

  9. Synthesis, structure, DNA binding and anticancer activity of mixed ligand ruthenium(II) complex

    Science.gov (United States)

    Gilewska, Agnieszka; Masternak, Joanna; Kazimierczuk, Katarzyna; Trynda, Justyna; Wietrzyk, Joanna; Barszcz, Barbara

    2018-03-01

    In order to obtain a potential chemotherapeutic which is not affected on the normal BALB/3T3 cell line, a new arene ruthenium(II) complex {[RuCl(L1)(η6-p-cymene)]PF6}2 · H2O has been synthesized by a direct reaction of precursor, [{(η6-p-cymene)Ru(μ-Cl)}2Cl2], with N,N-chelating ligand (L1 - 2,2‧-bis(4,5-dimethylimidazole). The compound has been fully characterized by elemental analysis, X-ray diffraction, IR, UV-Vis and 1H, 13C NMR spectroscopies. X-ray analysis have confirmed that the compound crystallized in the monoclinic group Cc as an inversion twin. The asymmetric unit contains two symmetrically independent cationic complexes [RuCl(L1)(η6-p-cymene)]+ whose charge is balanced by two PF6- counterions. The shape of each cationic coordination polyhedral can be described as a distorted dodecahedron and shows a typical piano-stool geometry. In addition, an analysis of the crystal structure and the Hirshfeld surface analysis were used to detect and visualize important hydrogen bonds and intermolecular interaction. Moreover, the antiproliferative behavior of the obtained complex was assayed against three human cells: MV-4-11, LoVo, MCF-7 and BALB/3T3 - normal mice fibroblast cells. To predict a binding mode, a potential interaction of ruthenium complex with calf thymus DNA (CT-DNA) has been explored using UV absorption and circular dichroism (CD).

  10. X-ray structures of progesterone receptor ligand binding domain in its agonist state reveal differing mechanisms for mixed profiles of 11beta-substituted steroids.

    NARCIS (Netherlands)

    Lusher, S.J.; Raaijmakers, H.C.A.; Vu-Pham, D.; Kazemier, B.; Bosch, R.; McGuire, R.; Azevedo, R.; Hamersma, H.; Dechering, K.; Oubrie, A.; Duin, M. van; Vlieg, J. de

    2012-01-01

    We present here the x-ray structures of the progesterone receptor (PR) in complex with two mixed profile PR modulators whose functional activity results from two differing molecular mechanisms. The structure of Asoprisnil bound to the agonist state of PR demonstrates the contribution of the ligand

  11. Reversible and pH dependent photophysical properties of mixed-ligand Ru(II) complexes containing 2,20-bipyridine and nitrosobarbiturate: Experimental and theoretical approach

    Czech Academy of Sciences Publication Activity Database

    Dixit, N.; Záliš, Stanislav; Maiti, B.; Mishra, L.

    2013-01-01

    Roč. 404, AUG 2013 (2013), s. 123-130 ISSN 0020-1693 Institutional support: RVO:61388955 Keywords : Mixed - ligand Ru(II) complex * spectroscopy * X-ray diffraction Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.041, year: 2013

  12. Thermostability and photophysical properties of mixed-ligand carboxylate/benzimidazole Zn(II)-coordination polymers

    Energy Technology Data Exchange (ETDEWEB)

    Barros, Bráulio Silva, E-mail: brauliobarros@ect.ufrn.br [School of Science and Technology, Federal University of Rio Grande do Norte (UFRN), Campus Universitário Lagoa Nova, 59078-970 Natal, RN (Brazil); Chojnacki, Jaroslaw [Department of Inorganic Chemistry, Chemical Faculty, Gdansk University of Technology, G. Narutowicza 11/12, 80-233 Gdansk (Poland); Macêdo Soares, Antonia Alice; Kulesza, Joanna; Lourenço da Luz, Leonis; Júnior, Severino Alves [Department of Fundamental Chemistry, Federal University of Pernambuco (UFPE), Av. Prof. Moraes Rego, 1235 – Cidade Universitária, 50670-901 Recife, PE (Brazil)

    2015-07-15

    The reaction between Zn(NO{sub 3}){sub 2}·6H{sub 2}O or Zn(CH{sub 3}COO){sub 2}·2H{sub 2}O and isophthalic acid (1,3-H{sub 2}bdc) in the presence of benzimidazole (Hbzim) in dimethylformamide (DMF)/ethanol (EtOH)/H{sub 2}O solvent mixture at room temperature yielded two structurally different coordination polymers: [Zn{sub 2}(1,3-bdc){sub 2}(Hbzim){sub 2}] (1) and [Zn{sub 2}(1,3-bdc)(bzim){sub 2}] (2). (1) is a 2D-layered framework with a molecule of benzimidazole coordinated to the Zn center, whereas (2) is a 3D framework with benzimidazolate species acting as a co-ligand and bridging two Zn(II) ions. Reactions performed at 90 °C led to the formation of coordination polymers structurally similar to (2), independently of the Zn(II) source used. In the absence of benzimidazole, the reaction between ZnAc{sub 2}.2H{sub 2}O and 1,3-H{sub 2}bdc at 90 °C resulted in the formation of (3), a 3D coordination polymer Zn(HCOO){sub 3}(Me{sub 2}NH{sub 2}{sup +}). It was observed that the thermostability and the photophysical properties of (1) and (2) are strongly dependent on the coordination modes and packing of benzimidazole in the solid state. These materials present photoluminescence in the wide range of the spectrum, from UV to IR. A full understanding of a physical process occurring in these intriguing systems, including complete energy level diagrams with possible transitions were provided. - Graphical abstract: Display Omitted - Highlights: • Structurally different Zn(II)-coordination polymers were prepared. • The formation of frameworks was counter anion and temperature dependent. • Photoluminescence in the wide range of the spectrum, from UV to IR was observed. • Thermostability and luminescence depended on bzim packing in the structure.

  13. Utilization of mixed ligands to construct diverse Ni(II)-coordination polymers based on terphenyl-2,2′,4,4′-tetracarboxylic acid and varied N-donor co-ligands

    International Nuclear Information System (INIS)

    Wang, Chao; Zhao, Jun; Xia, Liang; Wu, Xue-Qian; Wang, Jian-Fang; Dong, Wen-Wen; Wu, Ya-Pan

    2016-01-01

    Three new coordination polymers, namely, {[Ni(H 2 L)(bix)(H 2 O) 2 ]·2h 2 O} n (1), {[Ni(HL)(Hdpa)(H 2 O) 2 ]·H 2 O} n (2), {[Ni(L) 0.5 (bpp)(H 2 O)]·H 2 O} n (3) (H 4 L=terphenyl-2,2′,4,4′-tetracarboxylic acid; bix=1,4-bis(imidazol-1-ylmethyl)benzene; dpa =4,4′-dipyridylamine; bpp=1,3-bis(4-pyridyl)propane), based on rigid H 4 L ligand and different N-donor co-ligands, have been synthesized under hydrothermal conditions. Compound 1 features a 3D 4-connected 6 6 -dia-type framework with H 4 L ligand adopts a μ 2 -bridging mode with two symmetry-related carboxylate groups in μ 1 -η 1 :η 0 monodentate mode. Compound 2 displays a 1D [Ni(HL)(Hdpa)] n ribbon chains motif, in which the H 4 L ligand adopts a μ 2 -bridging mode with two carboxylate groups in μ 1 -η 1 :η 1 and μ 1 -η 1 :η 0 monodentate modes, while 3 possesses a (4,4)-connected 3D frameworks with bbf topology, with H 4 L ligand displays a μ 4 -bridging coordination mode. The H 4 L ligand displays not only different deprotonated forms but also diverse coordination modes and conformations. The structural diversities among 1–3 have been carefully discussed, and the roles of N-donor co-ligands in the self-assembly of coordination polymers have been well documented. - Graphical abstract: Three nickel coordination polymers with different architectures based on mixed ligand system were synthesized and structurally characterized. Topology analyses indicate that 1 shows the 4-connected 6 6 -dia net, 1D ribbon chains for 2 and 3D (4,4)-connected bbf network for 3. Display Omitted - Highlights: • Three Ni-based coordination polymers with distinct features have been prepared. • Compound 1 features a 3D 4-connected 66-dia-type framework, 2 displays a 1D [Ni(HL)(Hdpa)] n ribbon chains motif, while 3 possesses a (4,4)-connected 3D frameworks with bbf topology. • The “mixed ligand assembled” strategy is significant potential for network design.

  14. INTERACTION OF IRON(II MIXED-LIGAND COMPLEXES WITH DNA: BASE-PAIR SPECIFICITY AND THERMAL DENATURATION STUDIES

    Directory of Open Access Journals (Sweden)

    Mudasir Mudasir

    2010-06-01

    Full Text Available A research about base-pair specificity of the DNA binding of [Fe(phen3]2+, [Fe(phen2(dip]2+ and [Fe(phen(dip2]2+ complexes and the effect of calf-thymus DNA (ct-DNA binding of these metal complexes on thermal denaturation of ct-DNA has been carried out. This research is intended to evaluate the preferential binding of the complexes to the sequence of DNA (A-T or G-C sequence and to investigate the binding strength and mode upon their interaction with DNA. Base-pair specificity of the DNA binding of the complexes was determined by comparing the equilibrium binding constant (Kb of each complex to polysynthetic DNA that contain only A-T or G-C sequence. The Kb value of the interaction was determined by spectrophotometric titration and thermal denaturation temperature (Tm was determined by monitoring the absorbance of the mixture solution of each complex and ct-DNA at λ =260 nm as temperature was elevated in the range of 25 - 100 oC. Results of the study show that in general all iron(II complexes studied exhibit a base-pair specificity in their DNA binding to prefer the relatively facile A-T sequence as compared to the G-C one. The thermal denaturation experiments have demonstrated that Fe(phen3]2+ and [Fe(phen2(dip]2+ interact weakly with double helical DNA via electrostatic interaction as indicated by insignificant changes in melting temperature, whereas [Fe(phen2(dip]2+  most probably binds to DNA in mixed modes of interaction, i.e.: intercalation and electrostatic interaction. This conclusion is based on the fact that the binding of [Fe(phen2(dip]2+ to ct-DNA moderately increase the Tm value of ct- DNA   Keywords: DNA Binding, mixed-ligand complexes

  15. Functionalization of MOFs via a mixed-ligand strategy: enhanced CO2 uptake by pore surface modification.

    Science.gov (United States)

    Liu, Bo; Zhou, Hui-Fang; Hou, Lei; Wang, Yao-Yu

    2018-03-26

    A new Zn(ii) metal-organic framework (MOF) [Me2NH2][Zn2(BDPP)(HTZ)]·4DMF (1) (H4BDPP = 3,5-bis(3,5-dicarboxylphenyl)pyridine, HTZ = 1H-tetrazole) has been constructed under solvothermal conditions by using a mixed-ligand strategy. Structural analysis demonstrates that 1 is a 3D framework based on four kinds of secondary building units (SBUs), which presents a rare structure constructed from quaternary SBUs and shows an uncommon (3,3,4,6)-connected topology. In particular, 1 contains two shapes of 1D open channels with suitable pore sizes, high porosity, and a highly polar pore system decorated with uncoordinated N atoms and carboxylic O atoms, providing a good environment for selective adsorption of CO2. Inspired by the structure of 1 and reticular chemistry, 5-amino-1H-tetrazole (ATZ) was used to replace 1H-tetrazole to enhance CO2 sorption capacity by pore surface modification; as a result, an amino-functionalized MOF, [Me2NH2][Zn2(BDPP)(ATZ)]·4DMF (1-NH2) was successfully built. 1-NH2 exhibits multipoint interactions between the CO2 molecules and the framework, resulting in better CO2 uptake and selectivity for CO2 over CH4 than 1.

  16. Synthesis, DNA/HSA Interaction Spectroscopic Studies and In Vitro Cytotoxicity of a New Mixed Ligand Cu(II) Complex.

    Science.gov (United States)

    Gan, Qian; Fu, Xiabing; Chen, Weijiang; Xiong, Yahong; Fu, Yinlian; Chen, Shi; Le, Xueyi

    2016-05-01

    A new mixed ligand copper(II)-dipeptide complex with 2-(2'-pyridyl)benzothiazole (pbt), [Cu(Gly-L-leu)(pbt)(H2O)]·ClO4 (Gly-L-leu = Glycyl-L-leucine anion) was synthesized and characterized by various physico-chemical means. The DNA binding and cleavage properties of the complex investigated by viscosity, agarose gel electrophoresis and multi-spectroscopic techniques (UV, circular dichroism (CD) and fluorescence) showed that the complex was bound to CT-DNA through intercalation mode with moderate binding constant (K b = 3.132 × 10(4) M(-1)), and cleaved pBR322 DNA efficiently (~ 5 μM) in the presence of Vc, probably via an oxidative mechanism induced by •OH. Additionally, the interaction of the complex with human serum albumin (HSA) was explored by UV-visible, CD, fluorescence, synchronous fluorescence and 3D fluorescence spectroscopy. The complex exhibits desired affinity to HSA through hydrophobic interaction. Moreover, the cytotoxicity of the complex against three human carcinoma cell lines (HeLa, HepG2 and A549) was evaluated by MTT assay, which showed that the complex had effective cytotoxicity and higher inhibition toward A549 cell lines with IC50 of 38.0 ± 3.2 μM.

  17. Crystal structure of a mixed-ligand terbium(III coordination polymer containing oxalate and formate ligands, having a three-dimensional fcu topology

    Directory of Open Access Journals (Sweden)

    Chainok Kittipong

    2016-01-01

    Full Text Available The title compound, poly[(μ3-formato(μ4-oxalatoterbium(III], [Tb(CHO2(C2O4]n, is a three-dimensional coordination polymer, and is isotypic with the LaIII, CeIII and SmIII analogues. The asymmetric unit contains one TbIII ion, one formate anion (CHO2− and half of an oxalate anion (C2O42−, the latter being completed by application of inversion symmetry. The TbIII ion is nine-coordinated in a distorted tricapped trigonal–prismatic manner by two chelating carboxylate groups from two C2O42− ligands, two carboxylate oxygen atoms from another two C2O42− ligands and three oxygen atoms from three CHO2− ligands, with the Tb—O bond lengths and the O—Tb—O bond angles ranging from 2.4165 (19 to 2.478 (3 Å and 64.53 (6 to 144.49 (4°, respectively. The CHO2− and C2O42− anions adopt μ3-bridging and μ4-chelating-bridging coordination modes, respectively, linking adjacent TbIII ions into a three-dimensional 12-connected fcu topology with point symbol (324.436.56. The title compound exhibits thermal stability up to 623 K, and also displays strong green photoluminescence in the solid state at room temperature.

  18. Synthesis and characterization of two novel TcO and ReO mixed ligand complexes (3+1 combination, SNS/S) for hypoxia imaging

    International Nuclear Information System (INIS)

    Jaipetch, T.; Pirmettis, I.; Papadopoulos, M.; Nock, B.; Maina, T.; Raptopoulou, C.P.; Terzis, A.; Chiotellis, E.

    1998-01-01

    As part of our project to develop small-size, neutral, mixed ligand oxotechnetium and oxorhenium complexes of the general formula MOL 1 L 2 , we have synthesized and characterized two novel complexes of the general formula MO[EtN(CH 2 CH 2 S) 2 ][p-O 2 NC 6 H 4 S] where M=Re (complex 1) or M=Tc (complex 2) as a new approach for tissue hypoxia imaging. Complex 1 has been synthesized by exchange reaction in equimolar quantities of the tridentate and the monodentate ligand on ReOCl 3 (PPh 3 ) 2 . Only the syn isomer has been isolated and characterized by elemental analysis, IR, UV-vis, and 1 H NMR. Crystal data reveal a trigonal bipyramidal geometry around the metal. The basal plane is defined by the sulfur atoms of the tridentate ligand and the oxygen, while the two apical positions are occupied by the nitrogen of the tridentate ligand and the sulfur atom of the monodentate thiol. Complex 2 is prepared by exchange reaction using Tc-99m-glucoheptonate as precursor and equimolar quantities of the two ligands. Only one complex, the syn isomer, is formed. Its identity is confirmed by comparative HPLC studies with complex 1. (author)

  19. The structure of a mixed GluR2 ligand-binding core dimer in complex with (S)-glutamate and the antagonist (S)-NS1209

    DEFF Research Database (Denmark)

    Kasper, Christina; Pickering, Darryl S; Mirza, Osman

    2006-01-01

    of this novel class of antagonists. We present here the first X-ray structure of a mixed GluR2 ligand-binding core dimer, with the high-affinity antagonist (S)-8-methyl-5-(4-(N,N-dimethylsulfamoyl)phenyl)-6,7,8,9,-tetrahydro-1H-pyrrolo[3,2-h]-isoquinoline-2,3-dione-3-O-(4-hydroxybutyrate-2-yl)oxime [(S)-NS1209......] in one protomer and the endogenous ligand (S)-glutamate in the other. (S)-NS1209 stabilises an even more open conformation of the D1 and D2 domains of the ligand-binding core than that of the apo structure due to steric hindrance. This is the first time ligand-induced hyperextension of the binding...... domains has been observed. (S)-NS1209 adopts a novel binding mode, including hydrogen bonding to Tyr450 and Gly451 of D1. Parts of (S)-NS1209 occupy new areas of the GluR2 ligand-binding cleft, and bind near residues that are not conserved among receptor subtypes. The affinities of (RS)-NS1209 at the Glu...

  20. Group IB Organometallic Chemistry XIX.Synthesis and characterization of mixed-organocopper cluster compounds R4R'2Cu6 containing aryl and acetylide ligands.

    NARCIS (Netherlands)

    Koten, G. van; Hoedt, R.W.M. ten; Noltes, J.G.

    1977-01-01

    Mixed-organocopper cluster compounds Ar4Cu6(CCR)2 (Ar = 2-Me2NC6H4, R = phenyl, 4-tolyl, 2,4-xylyl or mesityl) have been prepared in high yield by the ligand-substitution reaction of Ar4Cu6Br2 with two equivalents of LiCCR. Ar4Cu6(CCC6H4CH3-4)2 has also been prepared via the aryl¡ªarylacetylide

  1. A new donor atom system [(SNN)(S)] for the synthesis of neutral oxotechnetium(V) mixed ligand complexes

    International Nuclear Information System (INIS)

    Papadopoulos, M.S.; Pirmettis, I.C.; Spyriounis, D.M.

    1996-01-01

    Oxotechnetium complexes ligated in a 3 + 1 inch fashion yielding TcOL1L2 complexes were prepared. The L1 tridentate ligand binds with a SNN donor set of atoms. L2 corresponds to a monodentate thiol ligand. Representative members of this group of compounds were chemically characterized by NMR and X-ray diffraction

  2. High Molar Extinction Coefficient Ru(II-Mixed Ligand Polypyridyl Complexes for Dye Sensitized Solar Cell Application

    Directory of Open Access Journals (Sweden)

    Malapaka Chandrasekharam

    2011-01-01

    Full Text Available Two new ruthenium(II mixed ligand terpyridine complexes, “Ru(Htcterpy(NCS(L1 (N(C4H94, mLBD1” and Ru(Htcterpy(NCS(L2(N(C4H94, mLBD2 were synthesized and fully characterized by UV-Vis, emission, cyclic voltammogram, and other spectroscopic means, and the structures of the compounds are confirmed by 1H-NMR, ESI-MASS, and FT-IR spectroscopes. The influence of the substitution of L1 and L2 on solar-to-electrical energy conversion efficiency (η of dye-sensitized solar cells (DSSCs was evaluated relative to reference black dye. The dyes showed molar extinction coefficients of 17600 M−1 cm−1 for mLBD1 and 21300 M−1 cm−1 for mLBD2 both at λ maximum of 512 nm, while black dye has shown 8660 M−1 cm−1 at λ maximum of 615 nm. The monochromatic incident photon-to-collected electron conversion efficiencies of 60.71% and 75.89% were obtained for mLBD1 and mLBD2 dyes, respectively. The energy conversion efficiencies of mLBD1 and mLBD2 dyes are 3.15% (SC=11.86 mA/cm2, OC=613 mV, ff=0.4337 and 3.36% (SC=12.71 mA/cm2, OC=655 mV, ff=0.4042, respectively, measured at the AM1.5G conditions, the reference black dye-sensitized solar cell, fabricated and evaluated under identical conditions exhibited η-value of 2.69% (SC=10.95 mA/cm2, OC=655 mV, ff=0.3750.

  3. Mixed-ligand copper(II) phenolate complexes: Synthesis, spectral characterization, phosphate-hydrolysis, antioxidant, DNA interaction and cytotoxic studies

    Science.gov (United States)

    Gurumoorthy, Perumal; Mahendiran, Dharmasivam; Prabhu, Durai; Arulvasu, Chinnasamy; Rahiman, Aziz Kalilur

    2015-01-01

    A series of phenol-based mixed-ligand copper(II) complexes of the type [CuL1-4(diimine)] (1-8), where L1-4 = N1,N2-bis(5-substituted-2-hydroxybenzylidene)-1,2-ethylene/phenylenediimine and diimine = 2,2‧-bipyridyl (bpy) or 1,10-phenanthroline (phen), have been isolated and fully characterized by analytical and spectral techniques. Electronic spectra of complexes suggest Cu(II) cation has a d9 electronic configuration, adopting distorted octahedral geometry with axial elongation, due to Jahn-Teller effect. Electrochemical studies of complexes evidenced one-electron irreversible reduction wave in the cathodic region. The observed rate constant (k) values for the hydrolysis of 4-nitrophenylphosphate (4-NPP) are in the range of 0.25-3.82 × 10-2 min-1. The obtained room temperature magnetic moment values (1.79-1.90 BM) lies within the range observed for octahedral copper(II) complexes. Antioxidant studies revealed that these complexes possess considerable radical scavenging potency against DPPH. The binding studies of complexes with calf thymus DNA (CT-DNA) revealed intercalation with minor-groove binding, and the complex 4 exhibits highest binding activity than the other complexes. The cleavage activity on supercoiled pBR322 DNA revealed the involvement of hydroxyl radical and singlet-oxygen as reactive oxygen species, and complexes encourage binding to minor-groove. Further, the cytotoxicity of complex 4 on human hepatocellular liver carcinoma HepG2 cell line implies the cell death through apoptosis.

  4. Formation of Mixed-Ligand Complexes of Pd2+ with Nucleoside 5'-Monophosphates and Some Metal-Ion-Binding Nucleoside Surrogates

    Directory of Open Access Journals (Sweden)

    Oleg Golubev

    2014-10-01

    Full Text Available Formation of mixed-ligand Pd2+ complexes between canonical nucleoside 5'-monophosphates and five metal-ion-binding nucleoside analogs has been studied by 1H-NMR spectroscopy to test the ability of these nucleoside surrogates to discriminate between unmodified nucleobases by Pd2+-mediated base pairing. The nucleoside analogs studied included 2,6-bis(3,5-dimethylpyrazol-1-yl-, 2,6-bis(1-methylhydrazinyl- and 6-(3,5-dimethylpyrazol-1-yl-substituted 9-(β-d-ribofuranosylpurines 1–3, and 2,4-bis(3,5-dimethylpyrazol-1-yl- and 2,4-bis(1-methylhydrazinyl-substituted 5-(β-d-ribofuranosyl-pyrimidines 4–5. Among these, the purine derivatives 1-3 bound Pd2+ much more tightly than the pyrimidine derivatives 4, 5 despite apparently similar structures of the potential coordination sites. Compounds 1 and 2 formed markedly stable mixed-ligand Pd2+ complexes with UMP and GMP, UMP binding favored by 1 and GMP by 2. With 3, formation of mixed-ligand complexes was retarded by binding of two molecules of 3 to Pd2+.

  5. Proton ligand stability constants of 7-iodo-8-hydroxyquinoline-5-sulphonic acid and metal-ligand stability constants of its complexes with lanthanides(III) in various mixed aqueous solvents

    International Nuclear Information System (INIS)

    Bandopadhyay, A.K.; Chaudhury, A.K.

    1987-01-01

    Proton-ligand formation constants of 7-iodo-8-hydroxyquinoline-5-sulphonic acid(L) have been measured in aqueous and mixed aqueous solvents. The trend in Psub(K)sup(H) values is interpreted in terms of the dielectric constants of the media and proton-solvent interactions. Stabilities of the binary complexes of the ligand with La, Pr, Nd, Sm, Gd, Tb, Dy have been measured in these media. Trend in stabilities with increase in 1/ε of the media is discussed. Step-wise stability constants for ternary complexes M-L-EDTA/NTA have also been measured. ΔH and ΔS values are interpreted in terms of charge neutralisation, steric effects, ion desolvation, etc. The ΔG and ΔH terms are further separated into electrostatic and cratic components. Results indicate that at the ternary step the bonding is more covalent. (author). 16 refs., 4 tables

  6. Trans* Leadership.

    Science.gov (United States)

    Jourian, T J; Simmons, Symone L

    2017-06-01

    Focusing on emerging literature on trans* and gender-nonconforming students and their leadership, this chapter outlines the ways trans* students are engaged in leadership in educational institutions and outside of them and discusses implications for staff and faculty regarding how to support and engage these students and their leadership. © 2017 Wiley Periodicals, Inc., A Wiley Company.

  7. Synthesis of divalent ligands of β-thio- and β-N-galactopyranosides and related lactosides and their evaluation as substrates and inhibitors of Trypanosoma cruzi trans-sialidase

    Directory of Open Access Journals (Sweden)

    María Emilia Cano

    2014-12-01

    Full Text Available In this work we describe the synthesis of mono- and divalent β-N- and β-S-galactopyranosides and related lactosides built on sugar scaffolds and their evaluation as substrates and inhibitors of the Trypanosoma cruzi trans-sialidase (TcTS. This enzyme catalyzes the transfer of sialic acid from an oligosaccharidic donor in the host, to parasite βGalp terminal units and it has been demonstrated that it plays an important role in the infection. Herein, the enzyme was also tested as a tool for the chemoenzymatic synthesis of sialic acid containing glycoclusters. The transfer reaction of sialic acid was performed using a recombinant TcTS and 3’-sialyllactose as sialic acid donor, in the presence of the acceptor having βGalp non reducing ends. The products were analyzed by high performance anion exchange chromatography with pulse amperometric detection (HPAEC-PAD. The ability of the different S-linked and N-linked glycosides to inhibit the sialic acid transfer reaction from 3’-sialyllactose to the natural substrate N-acetyllactosamine, was also studied. Most of the substrates behaved as good acceptors and moderate competitive inhibitors. A di-N-lactoside showed to be the strongest competitive inhibitor among the compounds tested (70% inhibition at equimolar concentration. The usefulness of the enzymatic trans-sialylation for the preparation of sialylated ligands was assessed by performing a preparative sialylation of a divalent substrate, which afforded the monosialylated compound as main product, together with the disialylated glycocluster.

  8. Bonds broken and formed during the mixed-linkage glucan : xyloglucan endotransglucosylase reaction catalysed by Equisetum hetero-trans-β-glucanase.

    Science.gov (United States)

    Simmons, Thomas J; Fry, Stephen C

    2017-03-08

    Mixed-linkage glucan∶xyloglucan endotransglucosylase (MXE) is one of the three activities of the recently characterised hetero-trans-β-glucanase (HTG), which among land plants is known only from Equisetum species. The biochemical details of the MXE reaction were incompletely understood - details that would promote understanding of MXE's role in vivo and enable its full technological exploitation. We investigated HTG's site of attack on one of its donor substrates, mixed-linkage (1→3),(1→4)-β-d-glucan (MLG), with radioactive oligosaccharides of xyloglucan as the acceptor substrate. Comparing three different MLG preparations, we showed that the enzyme favours those with a high content of cellotetraose blocks. The reaction products were analysed by enzymic digestion, thin-layer chromatography (TLC), high-pressure liquid chromatography (HPLC) and gel-permeation chromatography (GPC). Equisetum HTG consistently cleaved the MLG at the third consecutive β-(1→4)-bond following (towards the reducing terminus) a β-(1→3)-bond. It then formed a β-(1→4)-bond between the MLG and the non-reducing terminal glucose residue of the xyloglucan oligosaccharide, consistent with its xyloglucan endotransglucosylase/hydrolase subfamily membership. Using size-homogeneous barley MLG as the donor substrate, we showed that HTG does not favour any particular region of the MLG chain relative to the polysaccharide's reducing and non-reducing termini; rather, it selects its target cellotetraosyl unit stochastically along the MLG molecule. This work improves our understanding of how enzymes can exhibit promiscuous substrate specificities and provides the foundations to explore strategies for engineering novel substrate specificities into transglycanases. © 2017 The Author(s).

  9. Synthesis, characterization, DNA interaction and antimicrobial screening of isatin-based polypyridyl mixed-ligand Cu(II and Zn(II complexes

    Directory of Open Access Journals (Sweden)

    NATARAJAN RAMAN

    2010-06-01

    Full Text Available Several mixed ligand Cu(II/Zn(II complexes using 3-(phenyl-imino-1,3-dihydro-2H-indol-2-one (obtained by the condensation of isatin and aniline as the primary ligand and 1,10-phenanthroline (phen/2,2’-bipyridine (bpy as an additional ligand were synthesized and characterized analytically and spectroscopically by elemental analyses, magnetic susceptibility and molar conductance measurements, as well as by UV–Vis, IR, NMR and FAB mass spectroscopy. The interaction of the complexes with calf thymus (CT DNA was studied using absorption spectra, cyclic voltammetric and viscosity measurements. They exhibit absorption hypochromicity, and the specific viscosity increased during the binding of the complexes to calf thymus DNA. The shifts in the oxidation–reduction potential and changes in peak current on addition of DNA were shown by CV measurements. The Cu(II/Zn(II complexes were found to promote cleavage of pUC19 DNA from the supercoiled form I to the open circular form II and linear form III. The complexes show enhanced antifungal and antibacterial activities compared with the free ligand.

  10. Synthesis and Spectroscopic Studies of Mixed Ligand Complexes of Pt(II and Pd(II with Ethyl-α-Isonitrosoacetoacetate and Dienes

    Directory of Open Access Journals (Sweden)

    Anita Krishankant Taksande

    2015-12-01

    Full Text Available The mixed ligand complexes of the kind [M(L1 (L2] where M= Pt(II, Pd(II.L1 = primary ligand ethyl-α-isonitrosoacetoacetate derived from reaction between ethyl acetoacetate, acetic acid and sodium nitrite and L2=secondary ligand para-phenyldiamine (PPD are synthesized. All the prepared complexes were identified and confirmed by elemental analysis, molar conductance measurements, and infrared electronic absorption. Their complexes has been made based on elemental analysis, molar conductivity, UV-Vis, FT-IR and 1HNMR spectroscopy and magnetic moment measurements as well as thermal analysis (TGA and DTA. The elemental analysis information recommends that the stoichiometry of the complexes to be 1:2:1. The molar conductance measurements of the complexes indicate their non-electrolytic nature. The infrared spectral information showed the coordination sites of the free ligand with the central metal particle. The electronic absorption spectral information disclosed the existence of an octahedral geometry for Pt(II and Pd(II complexes. DOI: http://dx.doi.org/10.17807/orbital.v7i4.633 

  11. Transition metal complexes with thiosemicarbazide-based ligands. Part46. Synthesis and physico-chemical characterization of mixed ligand cobalt(III-complexes with salicylaldehyde semi-, thiosemi- and isothiosemicarbazone and pyridine

    Directory of Open Access Journals (Sweden)

    VUKADIN M. LEOVAC

    2003-12-01

    Full Text Available Mixed ligand octahedral cobalt(III complexes with the tridentate salicylaldehyde semi-, thiosemi- and isothiosemicarbazone and pyridine of general formula [CoIII(L11-3(py3]X (H2L1 = salicylaldehyde semicarbazone, X = [CoIICl3(py]-, ClO4- . H2O, I- . 0.5 I2; H2L2 = salicylaldehyde thiosemicarbazone, X = [CoIICl3(py]-, [CoIIBr3(py]-, ClO4- . H2O, I3-; H2L3 = salicylaldehyde S-methylisothiosemicarbazone, X = [ CoIIBr3(py ]-, ClO4- . H2O, BF4- were synthesized. The tridentate coordination of all the three dianionic forms of the ligands involves the phenol oxygen, hydrazine nitrogen and the chalcogen (O or S in case of salicylaldehyde semi-, thiosemicarbazone and the terminal nitrogen atom in the case of isothiosemicarbazone. For all the complexes, a meridial octahedral arrangement is proposed, which is a consequence of the planarity of the chelate ligand. The compounds were characterized by elemental analysis, molar conductivity, magnetic susceptibility, IR and electronic absorption spectra. The thermal decomposition of the complexes was investigated by thermogravimetry, coupled TG-MS measurements and DSC.

  12. Synthesis, spectral analysis, stability constants, antioxidant and biological activities of Co (II), Ni (II) and Cu (II) mixed ligand complexes of nicotinamide, theophylline and thiocyanate

    Science.gov (United States)

    Altun, Özlen; Şuözer, Mehtap

    2017-12-01

    In the present study, transition metal complexes or coordination entities with metal precursors such as Co (II), Ni (II) and Cu (II) of mixed ligands namely, nicotinamide (NA), theophylline (TP) and KSCN in water were synthesized under refluxing conditions. The optimization of the reactions to obtain the composition of complexes was performed. The structural elucidation of the complexes was undertaken by using physico-chemical and spectroscopic methods (UV/Vis, FT-IR, Mass and XRD) and thermal analysis. The spectral measurements of mixed ligands with the Co (II), Ni (II) and Cu (II) complexes are compared with each other in determining which atoms of the ligand are coordinated to the metal ion. Based on spectral and magnetic moment measurements, all the coordination entities were identified as in distorted octahedral structure and have the form [M(NA)2 (TP)2(SCN)2]·xH2O. In addition, K (stability constant) and ΔG (Gibbs free energy) values were calculated by using the Babko and Stanley & Turner's methods. Antioxidant, antibacterial and antifungal activities of the complexes were studied.

  13. Preparation and characterisation of mixed ligand complexes of Co(III), Fe(III) and Cr(III) containing phthalimide and phenols

    International Nuclear Information System (INIS)

    Miah, M.A.J.; Islam, M.S.; Pal, S.C.; Barma, T.K.

    1996-01-01

    Some novel mixed ligand complexes of Co(III), Fe(III) and Cr(III) containing phthalimide as primary and 2-aminophenol and 3-aminophenol as secondary ligands have been synthesized and characterised on the basis of elemental analyses, conductivity and magnetic measurements and infrared and electronic spectral studies. Complexes containing 2-aminophenol are 1:1 electrolyte in N,N dimethylformamide. Spectral studies indicate that all the complexes exhibit octahedral geometry. The complexes have the general composition; K[M(pim)/sub 2/(L)/sub 2/]; where m=Co(III), Fe(III) and Cr(III), pim-anion of phthalimamide and L=anion of 2-aminophenol and 3-aminophenol. (author)

  14. New mixed ligand cobalt(II/III) complexes based on the drug sodium valproate and bioactive nitrogen-donor ligands. Synthesis, structure and biological properties

    Science.gov (United States)

    Abu Ali, Hijazi; Abu Shamma, Amani; Kamel, Shayma

    2017-08-01

    New cobalt valproate complexes with different nitrogen based ligands were synthesized and characterized using various techniques such as IR, UV-Vis, single crystal X-ray diffraction as well as other physical properties. The general formula of the prepared complexes is [Con(valp)m(L)z], (n = 1, 2 …; m = 1, 2, …; Z = 1, 2 …). The complexes [Co2(valp)4] (1), [Co(valp)2(2-ampy)2] (2) and [Co2(valp)4(quin)2] (3) showed different carboxylate coordination modes. The crystal structures of the complexes 2 and 3 were determined using single crystal X-ray diffraction. Kinetic studies of hydrolysis reactions of BNPP [bis-(p-nitrophenyl)phosphate] with complexes 2 and 3 were performed. The hydrolysis rate of BNPP was studied at different temperatures, pH and concentrations by UV-Vis spectrophotometric method. The results showed that the hydrolysis rate of BNPP was 7.70 × 102 L mol-1 s-1 for (3) and 2.60 × 10-1 L mol-1 s-1 for (2).

  15. Crystal structure of a mixed-ligand silver(I complex of the non-steroidal anti-inflammatory drug diclofenac and pyrimidine

    Directory of Open Access Journals (Sweden)

    Sevim Hamamci Alisir

    2016-10-01

    Full Text Available In the title mixed-ligand silver(I coordination polymeric complex with the non-steroidal anti-inflammatory drug diclofenac (C14H11Cl2NO2 (diclH and pyrimidine (pym, namely poly[{μ2-2-[2-(2,6-dichloroanilinophenyl]acetato-κ2O:O′}(μ2-pyrimidine-κ2N1:N3silver(I], [Ag(C14H10Cl2NO2(C4H4N2]n or [Ag(μ-dicl(μ-pym]n, the very distorted tetrahedral AgN2O2 coordination centres comprise two N-atom donors from bridging pym ligands [Ag—N = 2.381 (3 and 2.412 (3 Å] and two carboxylate O-atom donors from dicl ligands [Ag—O = 2.279 (2 and 2.280 (2 Å], which bridge Ag atoms, giving a centrosymmetric dinuclear units with a short Ag...Ag separation [2.8931 (5 Å]. Within the units are short intraligand C—Cl...π(pym interactions [3.6409 (15 Å]. The units are linked through the bridging N atoms of the pym ligand into a two-dimensional sheet–polymer structure lying parallel to (100 and stabilized by inter-ring π–π interactions between the pym ligands [Cg...Cg = 3.4199 (17 Å]. Additional inter-unit C—H...O and C—H...Cg hydrogen-bonding interactions between the sheets give an overall three-dimensional structure.

  16. A one-dimensional cadmium(II complex supported by a sulfur–nitrogen mixed-donor ligand

    Directory of Open Access Journals (Sweden)

    Qian Gao

    2009-07-01

    Full Text Available In the title compound, catena-poly[cadmium(II-bis(μ-5-amino-1,3,4-thiadiazole-2-thiolato-κ2N3:S2;κ2S2:N3], [Cd(C2H2N3S22]n, the CdII ion is coordinated by two N atoms of the 1,3,4-thiadiazole rings from two ligands and two S atoms of sulfhydryl from two other ligands in a slightly distorted tetrahedral geometry. The ligands bridge CdII ions, forming one-dimensional chains along [001], which are connected by N—H...N and N—H...S hydrogen bonds into a three-dimensional network.

  17. Crystal structure of a mixed-ligand dinuclear Ba—Zn complex with 2-methoxyethanol having triphenylacetate and chloride bridges

    Directory of Open Access Journals (Sweden)

    Józef Utko

    2015-07-01

    Full Text Available The dinuclear barium–zinc complex, μ-chlorido-1:2κ2Cl:Cl-chlorido-2κCl-bis(2-methoxyethanol-1κObis(2-methoxyethanol-1κ2O,O′bis(μ-triphenylacetato-1:2κ2O:O′bariumzinc, [BaZn(C20H15O22Cl2(C3H8O24], has been synthesized by the reaction of barium triphenylacetate, anhydrous zinc chloride and 2-methoxyethanol in the presence of toluene. The barium and zinc metal cations in the dinuclear complex are linked via one chloride anion and carboxylate O atoms of the triphenylacetate ligands, giving a Ba...Zn separation of 3.9335 (11 Å. The irregular nine-coordinate BaO8Cl coordination centres comprise eight O-atom donors, six of them from 2-methoxyethanol ligands (four from two bidentate O,O′-chelate interactions and two from monodentate interactions, two from bridging triphenylacetate ligands and one from a bridging Cl donor. The distorted tetrahedral coordination sphere of zinc comprises two O-atom donors from the triphenylacetate ligands and two Cl donors (one bridging and one terminal. In the crystal, O—H...Cl, O—H...O and C—H...Cl intermolecular interactions form a layered structure, lying parallel to (001.

  18. A Fast and Practical Yeast Transformation Method Mediated by Escherichia coli Based on a Trans-Kingdom Conjugal Transfer System: Just Mix Two Cultures and Wait One Hour

    OpenAIRE

    Moriguchi, Kazuki; Yamamoto, Shinji; Ohmine, Yuta; Suzuki, Katsunori

    2016-01-01

    Trans-kingdom conjugation is a phenomenon by which DNA is transferred into a eukaryotic cell by a bacterial conjugal transfer system. Improvement in this method to facilitate the rapid co-cultivation of donor bacterial and recipient eukaryotic cell cultures could make it the simplest transformation method, requiring neither isolation of vector DNA nor preparation of competent recipient cells. To evaluate this potential advantage of trans-kingdom conjugation, we examined this simple transforma...

  19. Preparation, characterization and cytotoxicity studies of some transition metal complexes with ofloxacin and 1,10-phenanthroline mixed ligand

    Science.gov (United States)

    Sadeek, S. A.; El-Hamid, S. M. Abd

    2016-10-01

    [Zn(Ofl)(Phen)(H2O)2](CH3COO)·2H2O (1), [ZrO(Ofl)(Phen)(H2O)]NO3·2H2O (2) and [UO2(Ofl)(Phen)(H2O)](CH3COO)·H2O (3) complexes of fluoroquinolone antibacterial agent ofloxacin (HOfl), containing a nitrogen donor heterocyclic ligand, 1,10-phenathroline monohydrate (Phen), were prepared and their structures were established with the help of elemental analysis, molar conductance, magnetic properties, thermal studies and different spectroscopic studies like IR, UV-Vis., 1H NMR and Mass. The IR data of HOfl and Phen ligands suggested the existing of a bidentate binding involving carboxylate O and pyridone O for HOfl ligand and two pyridine N atoms for Phen ligand. The coordination geometries and electronic structures are determined from electronic absorption spectra and magnetic moment measurements. From molar conductance studies reveals that metal complexes are electrolytes and of 1:1 type. The calculated bond length and force constant, F(Udbnd O), in the uranyl complex are 1.751 Å and 641.04 Nm-1. The thermal properties of the complexes were investigated by thermogravimetry (TGA) technique. The activation thermodynamic parameters are calculated using Coats-Redfern and Horowitz-Metzger methods. Antimicrobial activity of the compounds was evaluated against some bacteria and fungi species. The activity data show that most metal complexes have antibacterial activity than that of the parent HOfl drug. The in vitro cytotoxicities of ligands and their complexes were also evaluated against human breast and colon carcinoma cells.

  20. Mixed-Valent Metals Bridged by a Radical Ligand: Fact, or Fiction Based on Structure-Oxidation State Correlations

    Czech Academy of Sciences Publication Activity Database

    Sarkar, B.; Patra, S.; Fiedler, Jan; Sunoj, R. B.; Janardanan, D.; Lahiri, G. K.; Kaim, W.

    2008-01-01

    Roč. 130, č. 11 (2008), s. 3532-3542 ISSN 0002-7863 R&D Projects: GA MŠk 1P05OC068; GA MŠk OC 140 Institutional research plan: CEZ:AV0Z40400503 Keywords : electron transfer series * quinone-related ligand s * ruthenium complexes Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 8.091, year: 2008

  1. Synthesis of mixed-ligand cobalt complexes and their applications in high cis-1,4-selective butadiene polymerization

    KAUST Repository

    Liu, Wen

    2015-08-03

    Incomplete oxidation of (N-di-tert-butylphosphino)-6-(2-methyl-2’H-benzoimidazole)-2-aminepyridine dichlorocobalt (PN3CoCl2) in DMF results in a unique co-crystal I formed with three parts including DMF, unit A and unit B complex with Co1 and Co2, respectively, (PN3 ligand in unit A: (N-di-tert-butylphosphino)-6-(2’-methyl-2’H-benzoimidazole)-2-aminepyridine, and O=PN3 ligand in unit B: (N-di-tert-butylphosphinoxide)-6-(2’-methyl-2’H-benzoimidazole)-2-aminepyridine) with 1:1:1 molar ratio. Co1 and Co2 complexes both display a five-coordinated distorted-square-pyramidal geometry around the metal center. The Co1 center is coordinated with PN3 ligand via two N atoms from pyridine, benzoimidazole moiety as well as one P atom, and the Co2 center is coordinated with the oxidized ligandO=PN3 via two N atoms from pyridine, benzoimidazole moiety as well as one O atom from DMF molecule, while the oxidized phosphine moiety (O=P) being excluded from the coordination sphere. Activated with AlEt2Cl, the co-crystallized complexes I are able to actively convert butadiene to polybutadiene, affording cis-1,4 polybutadiene with cis-1,4 unit up to 95.5-97.8% and number average molecular weight of cal. 105g/mol. The high cis-1,4 selectivity and monomodal GPC curve of resultant polymer imply that the identical active species generated from two distinctive cobalt centers.

  2. X-ray structures of progesterone receptor ligand binding domain in its agonist state reveal differing mechanisms for mixed profiles of 11β-substituted steroids.

    Science.gov (United States)

    Lusher, Scott J; Raaijmakers, Hans C A; Vu-Pham, Diep; Kazemier, Bert; Bosch, Rolien; McGuire, Ross; Azevedo, Rita; Hamersma, Hans; Dechering, Koen; Oubrie, Arthur; van Duin, Marcel; de Vlieg, Jacob

    2012-06-08

    We present here the x-ray structures of the progesterone receptor (PR) in complex with two mixed profile PR modulators whose functional activity results from two differing molecular mechanisms. The structure of Asoprisnil bound to the agonist state of PR demonstrates the contribution of the ligand to increasing stability of the agonist conformation of helix-12 via a specific hydrogen-bond network including Glu(723). This interaction is absent when the full antagonist, RU486, binds to PR. Combined with a previously reported structure of Asoprisnil bound to the antagonist state of the receptor, this structure extends our understanding of the complex molecular interactions underlying the mixed agonist/antagonist profile of the compound. In addition, we present the structure of PR in its agonist conformation bound to the mixed profile compound Org3H whose reduced antagonistic activity and increased agonistic activity compared with reference antagonists is due to an induced fit around Trp(755), resulting in a decreased steric clash with Met(909) but inducing a new internal clash with Val(912) in helix-12. This structure also explains the previously published observation that 16α attachments to RU486 analogs induce mixed profiles by altering the binding of 11β substituents. Together these structures further our understanding of the steric and electrostatic factors that contribute to the function of steroid receptor modulators, providing valuable insight for future compound design.

  3. Synthesis and characterization of new mixed ligand complexes of ruthenium(II) containing triphenylphosphine and 2'-hydroxychalcones

    International Nuclear Information System (INIS)

    Dharmaraj, N.; Natarajan, K.

    1994-01-01

    A few hexacoordinated ruthenium(II) complexes of the type [RuCl(CO) (HLL')(PPh 3 ) 2 ] and [RuCl(CO)(HLL')(B) (PPh 3 )] (where HLL' 2'-hydroxychalcone, 2'-hydroxy-4-methoxychalcone, 2'-hydroxy-3,4-dimethoxychalcone and B=pyridine(Py), piperidine(Pip), morpholine (Morph)) have been synthesised and characterized on the basis of their analytical and spectral data (IR, electronic and 1 H NMR). In all these complexes, the 2'-hydroxychalcones behave as a uninegative bidentate (OO - ) chelating ligand. (author). 17 refs., 1 tab

  4. Synthesis, Characterization, and Physicochemical Studies of Mixed Ligand Complexes of Inner Transition Metals with Lansoprazole and Cytosine

    Directory of Open Access Journals (Sweden)

    Sarika Verma

    2013-01-01

    Full Text Available Few complexes of inner transition metals [Th(IV, Ce(IV, Nd(III, Gd(III] have been synthesized by reacting their metal salts with lansoprazole, 2-([3-methyl-4-(2,2,2-trifluoroethoxypyridin-2-yl]methylsulfinyl-1H-benzoimidazole and cytosine. All the complexes were synthesized in ethanolic medium. The yield percentage rangs from 80 to 90%. The complexes are coloured solids. The complexes were characterized through elemental analyses, conductance measurements, and spectroscopic methods (FT IR, FAB Mass, 1H NMR and UV. An IR spectrum indicates that the ligand behaves as bidentate ligands. The metal complexes have been screened for their antifungal activity towards Aspergillus niger fungi. The interaction of inner transition metals with lansoprazole, in presence of cytosine, has also been investigated potentiometrically at two different temperatures 26±1°C and 36±1°C and at 0.1 M (KNO3 ionic strength. The stability constants of ternary complexes indicate the stability order as Th(IV < Ce(IV < Gd(III < Nd(III. logK values obtained are positive and suggest greater stabilization of ternary complexes. The values of thermodynamic parameters (free energy (ΔG, enthalpy (ΔH, and entropy (ΔS are also calculated.

  5. High-performance liquid chromatography separation of cis-trans anthocyanin isomers from wild Lycium ruthenicum Murr. employing a mixed-mode reversed-phase/strong anion-exchange stationary phase.

    Science.gov (United States)

    Jin, Hongli; Liu, Yanfang; Guo, Zhimou; Yang, Fan; Wang, Jixia; Li, Xiaolong; Peng, Xiaojun; Liang, Xinmiao

    2015-01-21

    The cis-trans isomerism is a common phenomenon for acylated anthocyanins. Nevertheless, few studies reported effective methods for the preparation of isomeric anthocyanins from natural products. In this work, a high-performance liquid chromatography (HPLC) method was developed to efficiently purify anthocyanin isomers from Lycium ruthenicum Murr. based on a mixed-mode reversed-phase/strong anion-exchange column (named XCharge C8SAX). Four commercially available columns were evaluated with a pair of isomeric anthocyanins, and the results demonstrated that the XCharge C8SAX column exhibited improved selectivity and column efficiency for the isomers. The chromatographic parameters, including pH, organic content, and ionic strength, were investigated. Optimal separation quality for the anthocyanin isomers was achieved on the XCharge C8SAX column. Six pure anthocyanins, including two pairs of cis-trans isomeric anthocyanins with one new anthocyanin, were purified from L. ruthenicum and identified. All of the results indicated that this method is an effective way to separate anthocyanins, especially for cis-trans isomers.

  6. Synthesis of an S T = 7 [Mn 3 ] Mixed-Valence Complex Based on 1,3-Propanediol Ligand Derivatives and Its One-Dimensional Assemblies

    KAUST Repository

    Huang, Jian

    2013-10-07

    Controlled organization of high-spin complexes and single-molecule magnets is a great challenge in molecular magnetism in order to study the effect of the intercomplex magnetic interactions on the intrinsic properties of a given magnetic object. In this work, a new ST = 7 trinuclear mixed-valence Mn complex, [MnIIIMnII 2(LA) 2(Br)4(CH3OH)6] ·Br· (CH3OH)1.5·(H2O)0.5 (1), is reported using a pyridinium-functionalized 1,3-propanediol ligand (H 2LABr = 1-(3-bromo-2,2-bis(hydroxymethyl)propyl)pyridinium bromide). Using azido anions as bridging ligands and different pyridinium-functionalized 1,3-propanediol ligands (H2LBBr = 1-(3-bromo-2,2-bis(hydroxymethyl)propyl)-4-picolinium bromide; H 2LCBr = 1-(3-bromo-2,2-bis(hydroxymethyl)propyl)-3,5- lutidinium bromide), the linear [MnIIIMnII 2L2X4]+ building block has been assembled into one-dimensional coordination networks: [MnIIIMn II 2(LA)2(Br)4(CH 3OH)4(N3)]·((C2H 5)2O)1.25 (2∞), [MnIIIMn II 2(LB)2(Br)4(C 2H5OH)(CH3OH)(H2O) 2(N3)]·(H2O)0.25 (3∞), and [MnIIIMnII 2(LC) 2(Cl)3.8(Br)0.2(C2H 5OH)3(CH3OH)(N3)] (4∞). The syntheses, characterization, crystal structures, and magnetic properties of these new [Mn3]-based materials are reported. © 2013 American Chemical Society.

  7. Synthesis, structure information, DNA/BSA binding affinity and in vitro cytotoxic studies of mixed ligand copper(II) complexes containing a phenylalanine derivative and diimine co-ligands.

    Science.gov (United States)

    Annaraj, B; Balakrishnan, C; Neelakantan, M A

    2016-07-01

    Binary [Cu(PAIC)(H2O)2]·H2O (1) and mixed ligand [Cu(PAIC)(L)]·2H2O complexes, where PAIC=phenylalanine imidazole carboxylic acid, L=diimine coligands [2,2'-bipyridine (bpy) (2) and 1,10-phenanthroline (phen) (3)] have been synthesized and fully characterized by analytical and spectral techniques. The X-ray structure of [Cu(PAIC)(phen)]·2H2O (3) shows a N4O coordination with square pyramidal geometry around the copper (II) atom. The spin Hamiltonian parameters calculated for the complexes account for the distorted square planar structure and rules out the possibility of a trigonal bipyramidal structure. Interaction of the complexes (1-3) with calf thymus DNA (CT DNA) was studied by using different techniques (absorption titration, fluorescence quenching and thermal melting) and the studies suggest that these complexes bind to CT DNA through intercalation. The DNA-binding affinity of the complexes has further been explained by DFT computational results. Binding activity of Bovine serum albumin (BSA) reveals that the complexes can strongly quench the intrinsic fluorescence of BSA through a static quenching mechanism. DNA cleavage experiments using plasmid DNA pUC 19 show that the complexes exhibit efficient chemical nuclease activity even in the absence of any external additives. The cytotoxicity of the complexes against human normal cell line (HBL 100) and human breast cancer cell line (MCF-7) shows that metal complexation of the ligands results in a significant enhancement in the cell death of MCF-7. Finally, docking studies on DNA and protein binding interactions were performed. Copyright © 2016 Elsevier B.V. All rights reserved.

  8. Nonlinear optical and G-Quadruplex DNA stabilization properties of novel mixed ligand copper(II) complexes and coordination polymers: Synthesis, structural characterization and computational studies

    Science.gov (United States)

    Rajasekhar, Bathula; Bodavarapu, Navya; Sridevi, M.; Thamizhselvi, G.; RizhaNazar, K.; Padmanaban, R.; Swu, Toka

    2018-03-01

    The present study reports the synthesis and evaluation of nonlinear optical property and G-Quadruplex DNA Stabilization of five novel copper(II) mixed ligand complexes. They were synthesized from copper(II) salt, 2,5- and 2,3- pyridinedicarboxylic acid, diethylenetriamine and amide based ligand (AL). The crystal structure of these complexes were determined through X-ray diffraction and supported by ESI-MAS, NMR, UV-Vis and FT-IR spectroscopic methods. Their nonlinear optical property was studied using Gaussian09 computer program. For structural optimization and nonlinear optical property, density functional theory (DFT) based B3LYP method was used with LANL2DZ basis set for metal ion and 6-31G∗ for C,H,N,O and Cl atoms. The present work reveals that pre-polarized Complex-2 showed higher β value (29.59 × 10-30e.s.u) as compared to that of neutral complex-1 (β = 0.276 × 10-30e.s.u.) which may be due to greater advantage of polarizability. Complex-2 is expected to be a potential material for optoelectronic and photonic technologies. Docking studies using AutodockVina revealed that complex-2 has higher binding energy for both G-Quadruplex DNA (-8.7 kcal/mol) and duplex DNA (-10.1 kcal/mol). It was also observed that structure plays an important role in binding efficiency.

  9. DNA cleavage, structural elucidation and anti-microbial studies of three novel mixed ligand Schiff base complexes of copper(II

    Directory of Open Access Journals (Sweden)

    N. RAMAN

    2007-10-01

    Full Text Available Three new copper complexes of mixed ligands derived from Schiff bases (condensation of p-aminoacetanilide and substituted benzaldehydes with 1,10-phenanthroline have been synthesized and characterized by elemental analysis, IR, UV–Vis, magnetic moments, conductivity and electrochemical measurements. The spectral techniques suggest that all the copper complexes exhibit octahedral geometry. The low electrical conductance of the complexes supports their neutral nature. The monomeric nature of the complexes was assessed from their magnetic susceptibility values. The in vitro biological screening effects of the investigated compounds were tested against the bacteria Escherichia coli, Staphylococcus aureus, and Salmonella typhi and the fungi Rhizopus stolonifer and Candida albicans by the serial dilution method. A comparative study of the MIC values of the Schiff bases and their copper complexes indicates that the metal complexes exhibited higher antibacterial activity than the free ligands. The DNA cleavage ability of the complexes was monitored by the gel electrophoresis technique. It was found that electron withdrawing group substituted copper complex had higher DNA cleavage activity than the other copper complexes.

  10. Reversible Single-Crystal-to-Single-Crystal Structural Transformation in a Mixed-Ligand 2D Layered Metal-Organic Framework: Structural Characterization and Sorption Study

    Directory of Open Access Journals (Sweden)

    Chih-Chieh Wang

    2017-12-01

    Full Text Available A 3D supramolecular network, [Cd(bipy(C4O4(H2O2]·3H2O (1 (bipy = 4,4′-bipyridine and C4O42− = dianion of H2C4O4, constructed by mixed-ligand two-dimensional (2D metal-organic frameworks (MOFs has been reported and structurally determined by the single-crystal X-ray diffraction method and characterized by other physicochemical methods. In 1, the C4O42− and bipy both act as bridging ligands connecting the Cd(II ions to form a 2D layered MOF, which are then extended to a 3D supramolecular network via the mutually parallel and interpenetrating arrangements among the 2D-layered MOFs. Compound 1 shows a two-step dehydration process with weight losses of 11.0% and 7.3%, corresponding to the weight-loss of three guest and two coordinated water molecules, respectively, and exhibits an interesting reversible single-crystal-to-single-crystal (SCSC structural transformation upon de-hydration and re-hydration for guest water molecules. The SCSC structural transformation have been demonstrated and monitored by single-crystal and X-ray powder diffraction, and thermogravimetic analysis studies.

  11. Syntheses, structures, and properties of a series of novel high-nuclear 3d-4f clusters with mixed amino acids as ligands: {Ln6Cu24}(Ln = Gd, Tb, Pr and Sm).

    Science.gov (United States)

    Shen, Chao-Jun; Hu, Sheng-Min; Sheng, Tian-Lu; Xue, Zhen-Zhen; Wu, Xin-Tao

    2015-04-14

    The first examples of high-nuclear 3d-4f heterometallic clusters with mixed amino acid ligands are reported. Four 30-nuclear clusters {Ln6Cu24}(Ln = Gd, Tb, Pr and Sm) were obtained through the self-assembly of Ln(III), Cu(II) and mixed amino acid ligands of glycine (HGly) and β-alanine (HAla). The metal skeleton of clusters may be described as a huge {Ln6Cu12} octahedron connected with 12 additional Cu(II) ions. The temperature dependence of magnetic susceptibilities of compounds were also studied.

  12. pH-metric studies on the mixed ligand-chelates of oxovanadium(IV) with 2,2'-bipyridyl and dicarboxylic or hydroxy acids

    International Nuclear Information System (INIS)

    Jain, A.K.; Kumari, V.; Chaturvedi, G.K.

    1978-01-01

    The interaction of vanadyl ion with 2,2'-bipyridyl and some dicarboxylic or hydroxy acids (where dicarboxylic acid = oxalic (OX), malonic (MALN), phthalic (PHA), maleic (MAL) acids; hydroxy acids salicylic (SA), 5-sulfosalicylic (5-SSA), mandelic (MAND) and glycollic (HG) acids was studied potentiometrically. pH-titrations of the reaction mixtures containing vanadyl sulphate, 2,2'-bipyridyl and one of the dicarboxylic or hydroxy acids (OX, MALN, PHA, MAL, SA, 5-SSA, MAND and HG acids) in equimolar ratio exhibited the formation of 1:1:1 mixed ligand chelates. The formation constants of the resulting biligand chelates were calculated, at 35 + -1 0 and 45 + -1 0 and also the thermodynamic functions viz. ΔF, ΔH and ΔS (μ=0.1M KNO 3 ) (auth.)

  13. Preparation and Single-Crystal X-Ray Structures of Four Related Mixed-Ligand 4-Methylpyridine Indium Halide Complexes

    Science.gov (United States)

    Hepp, Aloysius F.; Clark, Eric B.; Schupp, John D.; Williams, Jennifer N.; Duraj, Stan A.; Fanwick, Philip E.

    2013-01-01

    We describe the structures of four related indium complexes obtained during synthesis of solid-state materials precursors. Indium adducts of halides and 4-methylpyridine, InX3(pic)3 (X = Cl, Br; pic = 4-methylpyridine) consist of octahedral molecules with meridional (mer) geometry. Crystals of mer-InCl3(pic)3 (1) are triclinic, space group P1(bar) (No. 2), with a = 9.3240(3), b = 13.9580(6), c = 16.7268 (7) A, alpha = 84.323(2), beta = 80.938(2), gamma = 78.274(3)Z = 4, R = 0.035 for 8820 unique reflections. Crystals of mer-InBr3(pic)3 (2) are monoclinic, space group P21/n (No. 14), with a = 15.010(2), b = 19.938(2), c = 16.593(3), beta = 116.44(1)Z = 8, R = 0.053 for 4174 unique reflections. The synthesis and structures of related compounds with phenylsulfide (chloride) (3) and a dimeric complex with bridging hydroxide (bromide) (4) coordination is also described. Crystals of trans-In(SC6H5)Cl2(pic)3 (3) are monoclinic, space group P21/n (No. 14), with a = 9.5265(2), b = 17.8729(6), c = 13.8296(4), beta = 99.7640(15)Z = 4, R = 0.048 for 5511 unique reflections. Crystals of [In(mu-OH)Br2(pic)22 (4) are tetragonal, space group = I41cd (No. 110) with a = 19.8560(4), b = 19.8560(4), c = 25.9528(6), Z = 8, R = 0.039 for 5982 unique reflections.

  14. Synthesis, crystal structures, luminescence and catalytic properties of two d¹⁰ metal coordination polymers constructed from mixed ligands.

    Science.gov (United States)

    Wang, Xiao-xiao; Zhang, Ming-xi; Yu, Baoyi; Van Hecke, Kristof; Cui, Guang-hua

    2015-03-15

    Two new coordination polymers [Cd(bmb)(hmph)]n (1), {[Ag(bmb)]·H2btc}n (2) (bmb=1,4-bis(2-methylbenzimidazol-1-ylmethyl)benzene, H2hmph=homophthalic acid, H3btc=1,3,5-benzenetetracarboxylic acid) were synthesized under hydrothermal conditions and characterized by single-crystal X-ray diffraction methods, IR spectroscopy, TGA, XRPD and elemental analysis. Complex 1 features a 3D threefold interpenetrating dia array with a 4-connected 6(6) topology. Complex 2 shows a 1D helix chain structure connected by L1 ligands, which is finally extended into a rarely 2D 4L2 supramolecular network via C-H⋯O hydrogen bond interactions. In addition, the luminescence and catalytic properties of the two complexes for the degradation of the methyl orange azo dye in a Fenton-like process were presented. The degradation efficiency of the methyl orange azo dye for 1 and 2 are 56% and 96%, respectively. Copyright © 2014 Elsevier B.V. All rights reserved.

  15. Synthesis, characterization and thermal studies of nickel (II), copper (II), zinc (II) and cadmium (II) complexes with some mixed ligands

    International Nuclear Information System (INIS)

    Mitra, Samiran; Kundu, Parimal; Singh, Rajkumar Bhubon

    1998-01-01

    Dichloro-(DCA) and trichloroacetate(TCA) -cyclic ligand morpholine (Morph)/thiomorpholine (Tmorph)/methylmorpholine (Mmorph)/dimethyl-piperazine (DMP) complexes of nickel (II), copper (II), zinc (II) and cadmium (II) with the compositions [Ni(tmorph) 2 (DCA) 2 ], [Ni(tmorph) 2 (TCA) 2 ].2H 2 O, [Cu(DMP) 2 (TCA) 2 ],[ML 2 X 2 ].nH 2 O where M=Zn II or Cd II , L=Morph, DMP or tmorph and X=DCA or TCA and n=O except in case of [Cd (Morph) 2 (TCA) 2 ] where n=1 have been synthesised. Some intermediate complexes have been isolated by temperature arrest technique (pyrolysis) and characterised. Configurational and conformational changes have been studied by elemental analyses, IR and electronic spectra, magnetic moment data (in the case of Ni(II) and Cu(II) complexes) and thermal analysis. E a * , ΔH, and ΔS for the decomposition reaction of these complexes are evaluated and the stability of the complexes with respect to activation energy has also been compared. The linear correlation has been found between E a * and ΔS for the decomposition of the complexes. (author)

  16. Extraction of uranium and lead from mixed waste debris using a variety of metal/ligand complexes

    International Nuclear Information System (INIS)

    Needham, D.A.; Duran, B.L.; Ehler, D.S.; Sauer, N.N.

    1997-01-01

    To ensure the safety of our Nation's nuclear stockpile, Los Alamos National Laboratory is in the process of constructing the DARHT (Dual Axis Radiographic Hydrodynamic Test) facility. DARHT will examine the effects of aging and the stability of our stockpile. Contained testing will be phased in to reduce the impact of these tests, which contain depleted uranium, on our environment. The main focus of this research is to develop a treatment scheme for the recovery of depleted uranium and lead from shot debris that will result from these tests. The goals of this research are to optimize the conditions on a bench scale using a commercially available water soluble polymer to bind the lead and a variety of metal/ligand complexes such as 4,5-dihydroxy-1,3-benzene-disulfonic acid, dithionite, sodium carbonate/bicarbonate, and sodium hypochlorite to bind the uranium. Studies were conducted on a mixture of debris, such as wood, cable, paper towels, and tubing that contained both uranium and lead ranging in concentration from 10-1000's of ppm of contaminants. Experiments were done varying combinations and successions of extractant solutions as well as a number of sequential extractions. Studies show that a mixture of sodium hypochlorite and carbonate removed 90+% of both uranium and lead. We then focused on a separation scheme for the lead and uranium

  17. Mixed

    Directory of Open Access Journals (Sweden)

    Pau Baya

    2011-05-01

    Full Text Available Remenat (Catalan (Mixed, "revoltillo" (Scrambled in Spanish, is a dish which, in Catalunya, consists of a beaten egg cooked with vegetables or other ingredients, normally prawns or asparagus. It is delicious. Scrambled refers to the action of mixing the beaten egg with other ingredients in a pan, normally using a wooden spoon Thought is frequently an amalgam of past ideas put through a spinner and rhythmically shaken around like a cocktail until a uniform and dense paste is made. This malleable product, rather like a cake mixture can be deformed pulling it out, rolling it around, adapting its shape to the commands of one’s hands or the tool which is being used on it. In the piece Mixed, the contortion of the wood seeks to reproduce the plasticity of this slow heavy movement. Each piece lays itself on the next piece consecutively like a tongue of incandescent lava slowly advancing but with unstoppable inertia.

  18. Trinuclear Mixed-valent Manganese Complex with Non-schiff-base Tetradentate Ligand Showing a Ferromagnetic Coupling

    Directory of Open Access Journals (Sweden)

    Masahiro Mikuriya

    2017-12-01

    Full Text Available Mixed-valent trinuclear manganese complex with N,N’-bis(2-hydroxy-3,5-dimethylbenzyl-N,N’-dimethyl-1,2-ethanediamine (H2hdde, [Mn3(hdde2(CH3CO22(CH3O2], was synthesized. The X-ray crystal structure analysis revealed a linearly arrangement of MnIII-MnII-MnIIIcore, where a ferromagnetic coupling (J = 2.62 cm–1 between the MnIII and MnII ions.

  19. Syntheses, crystal structures, and properties of four coordination polymers based on mixed multi-N donor and polycarboxylate ligands

    Science.gov (United States)

    Chen, Shui-Sheng; Guo, Xing-Zhe; Zhao, Yue; Li, Wei-Dong

    2018-02-01

    Four new coordination polymers [Ni2(HL1)2(L1)3(BTC)2]·6H2O (1), [Ni2(L1)3(HBTC)2]·4H2O (2), [Cd2(L2)(BTC)(H2O)3]·2H2O (3) and [Cd2(HL2)(BTCA)] (4) were synthesized by reactions of nickel(II)/ cadmium(II) salts with rigid ligands of 1,4-di(1H-imidazol-4-yl)benzene (L1), 1,3-di(1-imidazolyl)-5-(4H-tetrazol-5-yl)benzene (HL2) and polycarboxylic acids of 1,3,5-benzenetricarboxylic acid (H3BTC), 1,2,4,5-benzenetetracarboxylic acid (H4BTCA), respectively. The structures of the complexes were determined by single crystal X-ray diffraction analysis. The complex 1 is one-dimensional (1D) chain while 2 is a (4, 4)-connected two-dimensional (2D) layered structure with 2D → 2D parallel interpenetration. Complex 3 is a rare tetranodal (3,4)-connected three-dimensional (3D) CrVTiSc architecture with Point (Schläfli) symbol of (4·82)(4·84·10)(42·82·102)(83), and compound 4 has the 2D network with (4,4) topology based on the [Cd2(COO)4] SBUs. The weak interactions such as hydrogen bonds and π···π stacking contribute to stabilize crystal structure and extend the low-dimensional entities into high-dimensional frameworks. The UV-vis absorption spectra of 1 - 4 are discussed. Moreover, the photo luminescent properties of 3 and 4 and gas sorption property of 2 have been investigated.

  20. Molecular Hybridization of Potent and Selective γ-Hydroxybutyric Acid (GHB) Ligands: Design, Synthesis, Binding Studies, and Molecular Modeling of Novel 3-Hydroxycyclopent-1-enecarboxylic Acid (HOCPCA) and trans-γ-Hydroxycrotonic Acid (T-HCA) Analogs

    DEFF Research Database (Denmark)

    Krall, Jacob; Jensen, Claus Hatt; Bavo, Francesco

    2017-01-01

    γ-Hydroxybutyric acid (GHB) is a neuroactive substance with specific high-affinity binding sites. To facilitate target identification and ligand optimization, we herein report a comprehensive structure–affinity relationship study for novel ligands targeting these binding sites. A molecular hybrid...... important for high-affinity binding, with high predictive validity. These findings will be valuable in the further processes of both target characterization and ligand identification for the high-affinity GHB binding sites....

  1. Extent of Intramolecular pi Stacks in Aqueous Solution in Mixed-Ligand Copper(II) Complexes Formed by Heteroaromatic Amines and 1-[2-(Phosphonomethoxy)ethyl]cytosine (PMEC), a Relative of Antivirally Active Acyclic Nucleotide Analogues (Part 72)

    Czech Academy of Sciences Publication Activity Database

    Blindauer, C. A.; Sigel, A.; Operschall, B. P.; Holý, Antonín; Sigel, H.

    2013-01-01

    Roč. 639, 8-9 (2013), s. 1661-1673 ISSN 0044-2313 Institutional support: RVO:61388963 Keywords : nucleotide analogues * antivirals * complex stabilities * isomers * equilibria * mixed ligand complexes Subject RIV: CC - Organic Chemistry Impact factor: 1.251, year: 2013

  2. Interplay of metalloligand and organic ligand to tune micropores within isostructural mixed-metal organic frameworks (M'MOFs) for their highly selective separation of chiral and achiral small molecules

    NARCIS (Netherlands)

    Das, M. C.; Guo, Q.; He, Y.; Kim, J.; Zhao, C.-G.; Hong, K.; Xiang, S.; Zhang, Z.; Thomas, K. M.; Krishna, R.; Chen, B.

    2012-01-01

    Four porous isostructural mixed-metal-organic frameworks (M′MOFs) have been synthesized and structurally characterized. The pores within these M′MOFs are systematically tuned by the interplay of both the metalloligands and organic ligands which have enabled us not only to direct their highly

  3. Photocytotoxic trans-diam(m)ine platinum(IV) diazido complexes more potent than their cis isomers.

    Science.gov (United States)

    Farrer, Nicola J; Woods, Julie A; Munk, Vivienne P; Mackay, Fiona S; Sadler, Peter J

    2010-02-15

    The photocytotoxicity of a series of anticancer trans-dihydroxido [Pt(N(3))(2)(OH)(2)(NH(3))(X)] (X = alkyl or aryl amine) platinum(IV) diazido complexes has been examined, and the influence of cis-trans isomerism has been investigated. A series of photoactivatable Pt(IV)-azido complexes has been synthesized: The synthesis, characterization, and photocytotoxicity of six mixed-ligand ammine/amine Pt(IV) diazido complexes, cis,trans,cis-[Pt(N(3))(2)(OH)(2)(NH(3))(X)] where X = propylamine (4c), butylamine (5c), or pentylamine (6c) and aromatic complexes where X = pyridine (7c), 2-methylpyridine (8c), or 3-methylpyridine (9c) are reported. Six all-trans isomers have also been studied where X = methylamine (2t), ethylamine (3t), 2-methylpyridine (8t), 4-methylpyridine (10t), 3-methylpyridine (9t), and 2-bromo-3-methylpyridine (11t). All of the complexes exhibit intense azide-to-Pt(IV) LMCT bands (ca. 290 nm for trans and ca. 260 nm for cis). When irradiated with UVA light (365 nm), the Pt(IV) complexes undergo photoreduction to Pt(II) species, as monitored by UV-vis spectroscopy. The trans isomers of complexes containing aliphatic or aromatic amines were more photocytotoxic than their cis isomers. One of the cis complexes (9c) was nonphotocytotoxic despite undergoing photoreduction. Substitution of NH(3) ligands by MeNH(2) or EtNH(2) results in more potent photocytotoxicity for the all-trans complexes. The complexes were all nontoxic toward human keratinocytes (HaCaT) and A2780 human ovarian cancer cells in the dark, apart from the 3-methylpyridine (9t), 2-bromo-3-methylpyridine (11t), and 4-methylpyridine (10t) derivatives.

  4. A THIOLATO-BRIDGED OCTANUCLEAR COPPER(I,II MIXED- VALENCE COMPLEX WITH N,N,S-TRIDENTATE LIGAND

    Directory of Open Access Journals (Sweden)

    Takanori Kotera

    2007-06-01

    Full Text Available Thiolato-bridged complex [CuI4CuII4(peampt4Cl8]·2H2O (Hpeampt = 1-(2-pyridylethylamino methylpropane-2-thiol has been synthesized and characterized by the elemental analysis, IR and UV-vis spectroscopies and magnetic susceptibility measurement. The X-ray crystal structure analysis of this complex shows a localized mixed-valence octanuclear cage structure made up of four trigonal-bipyramidal CuIIN2SCl2, two trigonal CuIS2Cl, and two tetrahedral CuIS2Cl2 coordination sites. Temperature dependence of magnetic susceptibility (4.5— 300 K shows that a fairly strong antiferromagnetic interaction is operating between the four CuII ions.

  5. Schiff base ligand derived from (±trans-1,2-cyclohexanediamine and its Cu(II, Co(II, Zn(II and Mn(II complexes: Synthesis, characterization, styrene oxidation and hydrolysis study of the imine bond in Cu(II Schiff base complex

    Directory of Open Access Journals (Sweden)

    Sarkheil Marzieh

    2016-01-01

    Full Text Available A Schiff base ligand (H2L derived from 2´-hydroxypropiophenone and (±trans-1,2-cyclohexanediamine was synthesized. The reactions of MCl2.xH2O (M =Cu(II, Co(II, Zn(II and Mn(IIwith the di-Schiff base ligand (H2L were studied. This ligand when stirred with 1 equivalent of CuCl2.2H2O in the solution of ethanol and chloroform undergoes partial hydrolysis of the imino bond and the resultant tridentate ligand (HL′immediately forms complex[CuL´Cl]∙3/2CHCl3(1with N2O coordination sphere. Under the same condition, the reaction of H2L with MCl2.xH2O (M = Co(II (3, Zn(II (4 and Mn(II (5 gave complexes[ML]•1/2CHCl3∙3/2H2O (3-5with N2O2 coordination sphere and no hydrolytic cleavage was occurred. Also, the reaction of H2L with CuCl2.2H2O in THF gave the complex CuL (2with N2O2 coordination sphere. The ligand and complexes were characterized by FTIR, UV-Vis, 1H NMRand elemental analysis. The homogeneous catalytic activity of the complexes1, 3 and 5wasevaluated for the oxidation of styrene using tert-butyl hydroperoxide (TBHP as oxidant. Finally, the copper(II complex(1encapsulated in the nanopores of zeolite-Y by flexible ligand method (CuL´-Yand its encapsulation was ensured by different studies. The catalytic performance of heterogeneous catalyst in the styrene oxidation with TBHP was investigated. The catalytic tests showed that the homogenous and heterogeneous catalysts were active in the oxidation of styrene.

  6. Synthesis, and structural characterization of mixed ligand copper(II) complexes of N,N,N‧,N'-tetramethylethylenediamine incorporating carboxylates

    Science.gov (United States)

    Batool, Syeda Shahzadi; Gilani, Syeda Rubina; Tahir, Muhammad Nawaz; Rüffer, Tobias

    2017-11-01

    Two ternary copper(II) complexes of N,N,N‧,N'-tetramethylethylenediamine (tmen = C6H16N2) with benzoic acid and p-aminobenzoic acid, having the formula [Cu(tmen)(BA)2(H2O)2] (1), and [Cu(tmen)(pABA)2]. 1/2 CH3OH (2) {(Where BA1- = benzoate1- (C6H5CO21-), pABA1- = p-aminobenzoate1- (p-H2NC6H5CO21-)} have been prepared and characterized by elemental combustion analysis, Uv-Visible spectroscopy, FT-IR spectroscopy, thermal, and single crystal X-ray diffraction analyses. The complex 1 is a monomer with distorted octahedral geometry. In its CuN2O4 chromophore, the Cu(II) centre is coordinated by two N atoms of a symmetrically chelating tmen ligand, by two carboxylate-O atoms from two monodentate benzoate1- anions, and by two apical aqua-O atoms, which define the distorted octahedral structure. The complex 2 is a monomer with a distorted square planar coordination geometry. In CuN2O2 chromophore, tmen is coordinated to Cu(II) ion in a chelating bidentate fashion, while the two p-aminobenzoate1- anions coordinate to Cu(II) centre through their carboxylate-O atoms in a monodentate manner, forming a square planar structure. The observed difference between asymmetric ѵas(OCO) and symmetric ѵs(OCO) stretching IR vibrations of the carboxylate moieties for 1 and 2 is 220 cm-1 and 232 cm-1, respectively, which suggests monodentate coordination mode (Δν OCO>200) of the carboxylate groups to Cu(II) ion. Thermogravimetric studies of 1 indicates removal of two water molecules at 171 °C, elimination of a tmen upto 529 °C and of two benzoate groups upto 931 °C. In tga curve of 2, methanol is lost upto 212 °C, while tmen is lost from 212 to 993 °C. The antibacterial activities of these new compounds against various bacterial strains were also investigated.

  7. Characterisation of the Novel Mixed Mu-NOP Peptide Ligand Dermorphin-N/OFQ (DeNo.

    Directory of Open Access Journals (Sweden)

    Mark F Bird

    Full Text Available Opioid receptors are currently classified as Mu (μ, Delta (δ, Kappa (κ plus the opioid related nociceptin/orphanin FQ (N/OFQ peptide receptor (NOP. Despite compelling evidence for interactions and benefits of targeting more than one receptor type in producing analgesia, clinical ligands are Mu agonists. In this study we have designed a Mu-NOP agonist named DeNo. The Mu agonist component is provided by dermorphin, a peptide isolated from the skin of Phyllomedusa frogs and the NOP component by the endogenous agonist N/OFQ.We have assessed receptor binding profile of DeNo and compared with dermorphin and N/OFQ. In a series of functional screens we have assessed the ability to (i increase Ca2+ in cells coexpressing recombinant receptors and a the chimeric protein Gαqi5, (ii stimulate the binding of GTPγ[35S], (iii inhibit cAMP formation, (iv activate MAPKinase, (v stimulate receptor-G protein and arrestin interaction using BRET, (vi electrically stimulated guinea pig ileum (gpI assay and (vii ability to produce analgesia via the intrathecal route in rats.DeNo bound to Mu (pKi; 9.55 and NOP (pKi; 10.22 and with reasonable selectivity. This translated to increased Ca2+ in Gαqi5 expressing cells (pEC50 Mu 7.17; NOP 9.69, increased binding of GTPγ[35S] (pEC50 Mu 7.70; NOP 9.50 and receptor-G protein interaction in BRET (pEC50 Mu 8.01; NOP 9.02. cAMP formation was inhibited and arrestin was activated (pEC50 Mu 6.36; NOP 8.19. For MAPK DeNo activated p38 and ERK1/2 at Mu but only ERK1/2 at NOP. In the gpI DeNO inhibited electrically-evoked contractions (pEC50 8.63 that was sensitive to both Mu and NOP antagonists. DeNo was antinociceptive in rats.Collectively these data validate the strategy used to create a novel bivalent Mu-NOP peptide agonist by combining dermorphin (Mu and N/OFQ (NOP. This molecule behaves essentially as the parent compounds in vitro. In the antonocicoeptive assays employed in this study DeNo displays only weak antinociceptive

  8. Multispectroscopic DNA-Binding studies and antimicrobial evaluation of new mixed-ligand Silver(I) complex and nanocomplex: A comparative study

    Science.gov (United States)

    Movahedi, Elaheh; Rezvani, Ali Reza

    2018-05-01

    A novel mixed-ligand Ag(I) complex, , has been synthesized and characterized by the elemental analysis, IR spectroscopy and 1HNMR. In the formula, dian and phen are N-(4,5-diazafluoren-9-ylidene)aniline and 1,10-phenanthroline, respectively. This complex also has been prepared at nano size by sonochemical technique and characterized by the FTIR and scanning electron microscopy (SEM). To evaluate the biological preferences of the Ag(I) complex and nanocomplex and verify the relationships between the structure and biological function, in vitro DNA binding and antibacterial experiments have been carried out. DNA-complex interaction has been pursued by electronic absorption titration, luminescence titration, competitive binding experiment, effect of ionic strength, thermodynamic studies, viscometric evaluation and circular dichroism spectroscopy in the physiological pH. Each compound displays significant binding trend to the CT-DNA. The mode of binding to the CT-DNA probably is a moderate intercalation mode with the partial insertion of the planar ligands between the base stacks of double-stranded DNA. The relative viscosities and circular dichroism spectra of the CT-DNA with the complex solutions, confirm the intense interactions of the Ag(I) complex and nanocomplex with DNA. An in vitro antibacterial test of the complex and nanocomplex on a series of the Gram-positive bacteria (Staphylococcus aureus, Enterococcus faecalis) and the Gram-negative bacteria (Escherichia coli, Pseudomonas aeruginosa) shows a remarkable antibacterial feature of the Ag(I) complex. The MIC values (minimum inhibitory concentration) of the compounds compare with silver nitrate and silver sulfadiazine. The bacterial inhibitions of the Ag(I) complex and nanocomplex are agreed to their DNA binding affinities.

  9. Unusual saccharin-N,O (carbonyl) coordination in mixed-ligand copper(II) complexes: Synthesis, X-ray crystallography and biological activity

    Science.gov (United States)

    Mokhtaruddin, Nur Shuhada Mohd; Yusof, Enis Nadia Md; Ravoof, Thahira B. S. A.; Tiekink, Edward R. T.; Veerakumarasivam, Abhi; Tahir, Mohamed Ibrahim Mohamed

    2017-07-01

    Three tridentate Schiff bases containing N and S donor atoms were synthesized via the condensation reaction between S-2-methylbenzyldithiocarbazate with 2-acetyl-4-methylpyridine (S2APH); 4-methyl-3-thiosemicarbazide with 2-acetylpyridine (MT2APH) and 4-ethyl-3-thiosemicarbazide with 2-acetylpyridine (ET2APH). Three new, binuclear and mixed-ligand copper(II) complexes with the general formula, [Cu(sac)(L)]2 (sac = saccharinate anion; L = anion of the Schiff base) were then synthesized, and subsequently characterized by IR and UV/Vis spectroscopy as well as by molar conductivity and magnetic susceptibility measurements. The Schiff bases were also spectroscopically characterized using NMR and MS to further confirm their structures. The spectroscopic data indicated that the Schiff bases behaved as a tridentate NNS donor ligands coordinating via the pyridyl-nitrogen, azomethine-nitrogen and thiolate-sulphur atoms. Magnetic data indicated a square pyramidal environment for the complexes and the conductivity values showed that the complexes were essentially non-electrolytes in DMSO. The X-ray crystallographic analysis of one complex, [Cu(sac)(S2AP)]2 showed that the Cu(II) atom was coordinated to the thiolate-S, azomethine-N and pyridyl-N donors of the S2AP Schiff base and to the saccharinate-N from one anion, as well as to the carbonyl-O atom from a symmetry related saccharinate anion yielding a centrosymmetric binuclear complex with a penta-coordinate, square pyramidal geometry. All the copper(II) saccharinate complexes were found to display strong cytotoxic activity against the MCF-7 and MDA-MB-231 human breast cancer cell lines.

  10. Structural, molecular orbital and optical characterizations of binuclear mixed ligand copper (II) complex of phthalate with N,N,N‧,N‧-tetramethylethylenediamine and its applications

    Science.gov (United States)

    Taha, A.; Farag, A. A. M.; Ammar, A. H.; Ahmed, H. M.

    2014-09-01

    A new binuclear mixed ligand complex, [Cu2(Phth)(Me4en)2(H2O)2(NO3)2]·H2O (where, Phth = phthalate, and (Me4en) = N,N,N‧,N‧tetramethylethylenediamine) was synthesized and characterized using analytical, spectral, magnetic, molar conductance, thermal gravimetric analysis (TGA), X-ray diffraction (XRD) and transmission electron microscope (TEM) measurements. The XRD data of Cu(II)-complex was analyzed on the basis of Williamson-Hall (W-H) and compared with TEM results. The results indicate that the complex is well crystalline and correspond to hexagonal crystal structure. Analysis of the absorption coefficient near the absorption edge reveals that the optical band gaps are indirect allowed transition with values of 1.17 and 1.78 eV. The d-d absorption bands of the complex (dissolved in various solvents) exhibit a color changes (solvatochromic). Specific and non-specific interactions of solvent molecules with the complex were investigated using Multiple Linear Regression Analysis (MLRA). Transient photocurrent characteristics of Cu(II)-complex/n-Si heterojunctions indicate that photocurrent under illumination increase with increasing of light intensity and explained by continuous distribution of traps. Structural parameters of the free ligands and their Cu(II) - complex were calculated on the basis of semi-empirical PM3 level and compared with the experimental data. The present copper (II) complex was screened for its antimicrobial activity against some Gram-positive and Gram-negative bacteria and fungus strain.

  11. Synthetic routes to mixed-ligand cobalt(III) dithiocarbamato complexes containing imidazole, amine and pyridine donors and the X-ray crystal structure of a cobalt(III) bis(dithiocarbamato) histamine complex.

    Science.gov (United States)

    Hodgson, Michael C; Brothers, Penelope J; Clark, George R; Ware, David C

    2008-04-01

    The binuclear cobalt complex [Co(2)(Me(2)dtc)(5)](+) reacts with a range of nitrogen donor ligands L' or L'' to form an equimolar mixture of Co(Me(2)dtc)(3) and the mixed-ligand complexes [Co(Me(2)dtc)(2)(L')(2)](+) or [Co(Me(2)dtc)(2)(L'')](+), where (L')(2) is two monodentate ligands and (L'') is one bidentate ligand. The complexes prepared by this route contain the monodentate ligands L'=1-methyl-imidazole, 1-methyl-5-nitro-imidazole and benzimidazole, all of which coordinate to cobalt through an imidazole nitrogen atom. Symmetrical bidentate ligand complexes contain the bisimidazole L''=2,2'-bis(4,5-dimethylimidazole), the diamine L''=1,2-diaminobenzene and the pyridine donors L''=2,2'-bipyridine, 4,4'-dimethyl-2,2'-bipyridine and 1,10-phenanthroline. Two examples of complexes with unsymmetrical bidentate imidazole-amine donors were prepared in which L''=4-(2-aminoethyl)imidazole (histamine) and 2-aminomethylbenzimidazole. All new complexes were fully characterised, and the X-ray crystal structure of the histamine complex [Co(Me(2)dtc)(2)(hist)]ClO(4) is also reported.

  12. DNA and protein binding, double-strand DNA cleavage and cytotoxicity of mixed ligand copper(II) complexes of the antibacterial drug nalidixic acid.

    Science.gov (United States)

    Loganathan, Rangasamy; Ganeshpandian, Mani; Bhuvanesh, Nattamai S P; Palaniandavar, Mallayan; Muruganantham, Amsaveni; Ghosh, Swapan K; Riyasdeen, Anvarbatcha; Akbarsha, Mohammad Abdulkader

    2017-09-01

    The water soluble mixed ligand complexes [Cu(nal)(diimine)(H 2 O)](ClO 4 ) 1-4, where H(nal) is nalidixic acid and diimine is 2,2'-bipyridine (1), 1,10-phenanthroline (2), 5,6-dimethyl-1,10-phenanthroline (3), and 3,4,7,8-tetramethyl-1,10-phenanthroline (4), have been isolated. The coordination geometry around Cu(II) in 1 and that in the Density Functional Theory optimized structures of 1-4 has been assessed as square pyramidal. The trend in DNA binding constants (K b ) determined using absorption spectral titration (K b : 1, 0.79±0.1base pair. In contrast, 3 and 4 are involved in intimate hydrophobic interaction with DNA through the methyl substituents on phen ring, which is supported by viscosity and protein binding studies. DNA docking studies imply that 4 is involved preferentially in DNA major groove binding while 1-3 in minor groove binding and that all the complexes, upon removing the axially coordinated water molecule, bind in the major groove. Interestingly, 3 and 4 display prominent double-strand DNA cleavage while 1 and 2 effect only single-strand DNA cleavage in the absence of an activator. The complexes 3 and 4 show cytotoxicity higher than 1 and 2 against human breast cancer cell lines (MCF-7). The complex 4 induces apoptotic mode of cell death in cancer cells. Copyright © 2017 Elsevier Inc. All rights reserved.

  13. Syntheses, structures, photoluminescence and photocatalysis of chiral 3D Cd(II) frameworks from achiral mixed flexible ligands by spontaneous resolution.

    Science.gov (United States)

    Sun, Yan-Qiong; Zhong, Jie-Cen; Ding, Ling; Chen, Yi-Ping

    2015-07-14

    Unprecedented two homochiral Cd(ii) enantiomers [Cd(dtba)(bpp)]n (1: 1P and 1M) (H2dtba = 2,2'-dithiodibenzoic acid, bpp = 1,3-bis(4-pyridyl)propane), were obtained by self-assembly with mixed achiral flexible ligands. Single-crystal X-ray diffraction analysis reveals that complexes 1P and 1M crystallize in trigonal space groups P3121 and P3221, respectively. The compounds are optically active, and their UV spectra in the solid state showed Cotton effects in the opposite directions. Compounds 1P and 1M present the examples of three-interpenetrating chiral frameworks with triangular and quasi-heart-like threefold helical chiral channels, chair-like twofold helical chiral channels and one type of threefold double-helical chain. The 3D metal-organic framework can be regarded as a bcu-type topology with the symbol of 8(6). The photoluminescent properties of compound 1 have been studied. Remarkably, compound 1 exhibits good photocatalytic activity for degradation of dyes under the simulated sunlight irradiation in the pH = 3 aqueous solution.

  14. Synthesis and Structure of a Ternary Copper(II) Complex with Mixed Ligands of Diethylenetriamine and Picrate: DNA/Protein-Binding Property and In Vitro Anticancer Activity Studies.

    Science.gov (United States)

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

    2015-05-01

    Based on the importance of the design and synthesis of transition metal complexes with noncovalent DNA/protein-binding abilities in the field of metallo pharmaceuticals, a new mononuclear ternary copper(II) complex with mixed ligands of diethylenetriamine (dien) and picrate anion (pic), identified as [Cu(dien)(pic)](pic), was synthesized and characterized by elemental analysis, molar conductivity measurement, infrared spectrum, electronic spectral studies, and single-crystal X-ray diffractometry. The structure analysis reveals that the copper(II) complex crystallizes in the monoclinic space group P21 /c, and the copper(II) ion has a distorted square pyramidal coordination geometry. A two-dimensional supramolecular structure is formed through hydrogen bonds. The DNA/bovine serum albumin (BSA)-binding properties of the complex are explored, indicating that the complex can interact with herring sperm DNA via intercalation mode and bind to BSA responsible for quenching of tryptophan fluorescence by static quenching mechanism. The in vitro anticancer activity shows that the copper(II) complex is active against the selected tumor cell lines. © 2015 Wiley Periodicals, Inc.

  15. A new set of Cd(ii)-coordination polymers with mixed ligands of dicarboxylate and pyridyl substituted diaminotriazine: selective sorption towards CO2and cationic dyes.

    Science.gov (United States)

    Chand, Santanu; Elahi, Syed Meheboob; Pal, Arun; Das, Madhab C

    2017-08-01

    On the basis of a mixed ligand system of L(NH 2 ) 2 (6-(pyridin-4-yl)-1,3,5-triazine-2,4-diamine) and dicarboxylic acids, three new Cd(ii) coordination polymers viz. {[Cd 0.5 (tdc) 0.5 (L(NH 2 ) 2 ) 0.5 (H 2 O)]·DMF·H 2 O} n (1), {[Cd 0.5 (bdc) 0.5 (L(NH 2 ) 2 )(H 2 O)]·DMF·H 2 O} n (2), and {[Cd(ipa)(L(NH 2 ) 2 )(DMF)]·H 2 O} n (3) (tdcH 2 = thiophene-2,5-dicarboxylic acid, bdcH 2 = benzene-1,4-dicarboxylic acid, ipaH 2 = benzene-1,3-dicarboxylic acid) were synthesized under diverse reaction conditions and characterized by single crystal X-ray diffraction, PXRD, elemental analysis, IR spectroscopy and TGA. While 1 and 2 revealed 1D chain structures, 3 acquired a 2D square net structural arrangement. Gas adsorption measurements of the desolvated framework 3 showed a moderate uptake of CO 2 under ambient conditions with good selectivity over N 2 and CH 4 . The solid state luminescence properties were studied for all three coordination polymers. Moreover, a dye adsorption study on 3 exhibited selective adsorption towards a cationic dye.

  16. Synthesis and evaluation of technetium-99m monocationic mixed ligand complexes of phenyl substituted/condensed tetradentate Schiff's bases and trimethylphosphine

    International Nuclear Information System (INIS)

    Goomer, N.C.; Kulkarni, P.V.; Constantinescu, A.; Antich, P.; Parkey, R.W.; Corbett, J.R.

    1992-01-01

    Tc-99m monocationic mixed ligand complexes of phenyl substituted/condensed Schiff's bases, N,N'-ethylene-bis-(benzoylacetone imine) (L b ) or N,N'-ethylene-bis-(salicyladehyde imine) (L c ) or N,N'-ethylene-bis-(2-hydroxyacetophenone imine) (L d ) and trimethylphosphine were synthesized to determine the influence of the presence of a phenyl group in these tracers on their heart uptake in rats. A new formulation procedure using aq. β-hydroxypropylcyclodextrin (HPB) solution was developed for intravenous administration of nonpolar 99m Tc complexes. Comparison of biodistribution data for the reference 99m Tc complex from N,N'-ethylene-bis-(acetylacetone imine) and trimethylphosphine using HPB formulation and alternate formulation (0.9% saline) showed the same results. Biodistribution of the title 99m Tc complexes, [ 99m Tc L b (PMe 3 ) 2 ] + , [ 99m Tc L c (PME 3 ) 2 ] + and [ 99m Tc L d (PME 3 ) 2 + showed heart-to-blood activity ratios of 1.7, 2.1 and 1.7, respectively, at 15 min post-injection in rats. (Author)

  17. Black cohosh (Actaea racemosa, Cimicifuga racemosa) behaves as a mixed competitive ligand and partial agonist at the human mu opiate receptor

    Science.gov (United States)

    Rhyu, Mee-Ra; Lu, Jian; Webster, Donna E.; Fabricant, Daniel S.; Farnsworth, Norman R.; Wang, Z. Jim

    2008-01-01

    Black cohosh is a commonly used botanical dietary supplement for the treatment of climacteric complaints. Since the opiate system in the brain is intimately associated with mood, temperature and sex hormonal levels, we investigated the activity of black cohosh extracts at the human μ opiate receptor (hMOR) expressed in Chinese hamster ovary cells. The 100% methanol-, 75% ethanol- and 40% 2-propanol- extracts of black cohosh effectively displaced the specific binding of [3H]DAMGO to hMOR. Further studies of the clinically used ethanol extract indicated that black cohosh acted as a mixed competitive ligand, displacing 77 ± 4% [3H]DAMGO to hMOR (Ki = 62.9 μg/ml). Using the [35S]GTPγS assay, the action of black cohosh was found to be consistent with an agonist, with an EC50 of 68.8 ± 7.7 μg/ml. These results demonstrate for the first time that black cohosh contains active principle(s) that activate hMOR, supporting its beneficial role in alleviating menopausal symptoms. PMID:17177511

  18. Trans-1,4 selective polymerization of 1,3-butadiene with symmetry pincer chromium complexes activated by MMAO

    KAUST Repository

    Gong, Dirong

    2014-09-01

    Tridentate chromium complexes (Cr1-Cr7) incorporated with symmetrical pincer ligand bis(arylimino)pyridine and bis(pyrzaolyl)pyridine have been synthesized and characterized by elemental analyis, FT-IR as well as ESI-MS. X-ray diffraction reveals solids-state structures of Cr2, Cr4 and Cr6 all adopt pseudo-octahedral coordination environment with respect to metal center. All complexes have been tested in stereoregulated polymerization of butadiene under various polymerization conditions. The trans-1,4 and cis-1,4 enchainment of resultant polymer are found to be dependent on the structure of ligand and amount of activator used. Under the optimized condition, free ortho-substitutes Cr catalysts Cr1, Cr3, Cr4 and Cr6 are capable of initiating high trans-1,4 selectivity (trans-1,4: 89.2%-92.0%) with good polymer yields (71.5%-78.0%), while counterparts with ortho-positioned alkyl groups Cr2, Cr5 and Cr7 display mixed selectivities with moderate polymer yields. The sterical effect of ligand and amount of MMAO on the catalytic performance, in particular, the stereoselectivity and polymer yield, has been also elucidated by conjugated diene polymerization mechanism. © 2014 Elsevier B.V. All rights reserved.

  19. Effects of trans fats on prostacyclin production.

    Science.gov (United States)

    Kummerow, Fred A; Mahfouz, Mohamedain; Zhou, Qi; Masterjohn, Christopher

    2013-12-01

    Prostacyclin is a prostanoid derived from arachidonic acid that prevents thrombosis and is thereby expected to protect against heart disease, while trans fats present in partially hydrogenated oils interfere with arachidonic acid metabolism. Therefore, the objective of the present study was to investigate how fats with different proportions of linoleic acid and trans-18:1 affect prostacyclin released by cultured endothelial cells, and to compare these proportions with those found in commercially available foods. Soybean oil and hydrogenated soybean oil (coating fat) were mixed in different proportions to yield seven fat mixtures with proportions of linoleic acid ranging from 54.1% to 5.7% and trans-18:1 acid ranging from 0.4% to 43.9%. Human endothelial cells were cultured in each of the mixtures, and their phospholipid fractions were then separated and their fatty acids were analyzed by gas chromatography. The prostacyclin released by the cells was measured using RIA kits. Margarines and processed foods were purchased from the supermarket for comparison. Our work revealed that as the percentage of trans fat was increased, the amount of prostacyclin released dose-dependently and significantly (P fats similar to those that suppressed prostacyclin by 35-54%. Most processed foods labeled as trans-free contained trans fats. Trans fatty acids suppress prostacyclin production at levels found in commercial margarines, and processed foods labeled as trans-free could contribute to this effect if consumed in multiple servings or in addition to foods containing larger amounts of trans fats.

  20. Self-assembly of novel supramolecular silver(I) compound based on mixed ligands bipy/TST3- H3TST=2,4,6-tris (4-sulfophenylamino)-1,3,5-triazine

    NARCIS (Netherlands)

    Yu, Yunfang; Wei, Yongqin; Broer, Ria; Wu, Kechen

    2007-01-01

    The novel supramolecular silver(I) compound with formula [Ag-6(TST)(2)(bipy)(6)(H2O)(2)](n) center dot 3nH(2)O (1) based on assembly of Ag(I) and mixed ligand bipy/TST3-, bipy = 2,2'-bipyridine, H3TST = 2,4,6-tris(4-sulfophenylamino)-1,3,5-triazine, has been prepared by hydrothermal method. In the

  1. Heteronuclear, mixed-metal Ag(I)-Mn(II) coordination polymers with bridging N-pyridinylisonicotinohydrazide ligands: synthesis, crystal structures, magnetic and photoluminescence properties.

    Science.gov (United States)

    Bikas, Rahman; Hosseini-Monfared, Hassan; Vasylyeva, Vera; Sanchiz, Joaquín; Alonso, Javier; Barandiaran, Jose Manuel; Janiak, Christoph

    2014-08-21

    Mixed-metal dicyanoargentate-bridged coordination polymers of Ag(i)-Mn(ii) have been prepared and their structure and magnetic properties were determined. Reaction of manganese(ii) chloride and potassium dicyanoargentate(i) with (X)(pyridin-2-ylmethylene)isonicotinohydrazide ligands (HL(1) X = Ph, HL(2) X = Me, HL(3) X = H) produced the coordination polymer 2D-[Mn(μ-L(1))(Cl)(μ-NCAgCN)Mn0.5(CH3OH)]n (), 1D-{[Mn(L(2))(Cl)(μ-NCAgCN)Mn0.5(CH3OH)]CH3OH}n () and [Mn(L(3))(Cl)(μ-NCAgCN)Mn0.5(CH3OH)]n () in good yields. Trinuclear {Mn(μ-L(1))Mn(μ-L(1))Mn} and [Ag(CN)2](-) building units form a two-dimensional slab in and 1D strands in . Variable temperature magnetic susceptibility measurements showed that despite the long distance among the high spin Mn(ii) ions [10.4676(12) Å and 10.522(1) Å, for and , respectively], weak antiferromagnetic coupling takes place through the long NC-Ag-CN bridge. The best fit parameters to the model led to the magnetic coupling constant of J = -0.1 and J = -0.47 cm(-1) for and , respectively. The photoluminescence behaviour of compounds and was studied. The spectrum of compound shows a broad emission centered at about 450 nm and two excitation maxima at 270 and 310 nm.

  2. Two Zinc(II) metal-organic frameworks with mixed ligands of 5-amino-tetrazolate and l,2,4,5-benzenetetracarboxylate: Synthesis, structural diversity and photoluminescent properties

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Xiao-Bing [Department of Chemistry, Shaoguan University, Shaoguan, Guangdong 512005 (China); Lu, Wen-Guan, E-mail: lwg@sgu.edu.cn [Department of Chemistry, Shaoguan University, Shaoguan, Guangdong 512005 (China); Zhong, Di-Chang [School of Chemistry and Chemical Engineering, Gannan Normal University, Ganzhou 341000 (China)

    2017-06-15

    The reactions of Zn(NO{sub 3}){sub 2}·6H{sub 2}O with mixed ligands of 5-amino-tetrazole (Hatz) and l,2,4,5-benzenetetracarboxylic acid (H{sub 4}btec) under hydro(solvo)thermal conditions, gave two three-dimensional (3D) porous metal-organic frameworks (MOFs) of ([Zn{sub 3}(atz){sub 2}(btec)(DMF){sub 2}]·DMF·2H{sub 2}O){sub n} (1) and [Zn{sub 2}(Hprz)(atz)(btec)(H{sub 2}O)]{sub n} (2) in the absence and presence of piperazine (prz), respectively. 1 and 2 were characterized by infrared spectra (IR), elemental analyses (EA) and single-crystal/powder X-ray diffraction. In 1, the adjacent 1D [Zn{sub 3}(btec)]{sub n}{sup 2n+} chains are linked together by atz{sup −} ligands to form a 3D porous MOF with 1D tetragonal channels filled with coordinated and guest DMF, and lattice water molecules. In 2, the adjacent 2D [Zn{sub 2}(btec)]{sub n} wavelike sheets are pillared through atz{sup −} ligands to generate a 3D layered-pillared porous MOF with 1D open channels, which are occupied by coordinated Hprz{sup +} cations and coordinated water molecules. Additionally, thermal stabilities and photoluminescent properties of both compounds in the solid-state at room temperature have been investigated and discussed in detail. - Graphical abstract: Two new MOFs constructed from Zn(II) salts with mixed ligands of 5-amino-tetrazole and l,2,4,5-benzenetetracarboxylic acid were synthesized under different reaction conditions. Structural diversities indicate that the reaction solvent system or the presence of organic base play crucial roles in modulating structures of these compounds. And more, their thermal stability and luminescence are also discussed. - Highlights: • Two new Zn(II) MOFs based on mixed ligands were synthesized. • The two Zn(II) MOFs exhibit different structural motifs. • The two Zn(II) MOFs are photoluminscent in the solid state at room temperature.

  3. Mixed ligand complexes of alkaline earth metals: Part XII. Mg(II, Ca(II, Sr(II and Ba(II complexes with 5-chlorosalicylaldehyde and salicylaldehyde or hydroxyaromatic ketones

    Directory of Open Access Journals (Sweden)

    MITHLESH AGRAWAL

    2002-04-01

    Full Text Available The reactions of alkaline earth metal chlorides with 5-chlorosalicylaldehyde and salicylaldehyde, 2-hydroxyacetophenone or 2-hydroxypropiophenone have been carried out in 1 : 1 : 1 mole ratio and the mixed ligand complexes of the type MLL’(H2O2 (where M = Mg(II, Ca(II, Sr(II and Ba(II, HL = 5-chlorosalicylaldehyde and HL’ = salicylaldehyde, 2-hydroxyacetophenone or 2-hydroxypropiophenone have been isolated. These complexes were characterized by TLC, conductance measurements, IR and 1H-NMR spectra.

  4. Deprotonation induced ligand-to-metal electron transfer: Synthesis of a mixed-valence Rh(-I,I) dinuclear compound and its reaction with dioxygen

    NARCIS (Netherlands)

    Tejel, C.; Ciriano, M.A.; del Río, M.P.; van den Bruele, F.J.; Hetterscheid, D.G.H.; Tsichlis i Spithas, N.; de Bruin, B.

    2008-01-01

    Treatment of bis(2-picolyl)amine (bpa) with [{Rh(nbd)(mu-OMe))(2)] leads to unexpected and unique redox asymmetric dinuclear Rh-I, Rh+I complex [{Rh(ndb)}(2)(bpa-2H)] (2) with a pi-coordinating imine bound to a tetrahedral low valent rhodate(-I). Mono-oxygenation of the deprotonated bpa ligand in 2

  5. Trans-Planckian wimpzillas

    CERN Document Server

    Kolb, E W; Tkachev, I I

    2007-01-01

    Two previously proposed conjectures--gravitational trans-Planckian particle creation in the expanding universe, and the existence of ultra-heavy stable particles with masses up to the Planck scale (wimpzillas)--are combined in a proposal for trans-Planckian particle creation of wimpzillas. It is shown that the trans-Planckian particle creation parameter should be rather small to avoid overproduction of such particles. This ensures that wimpzillas are mainly created at the end of primordial inflation. Conditions under which trans-Planckian wimpzillas can constitute the present dark matter are determined.

  6. A two-dimensional zinc(II) coordination polymer based on mixed dimethyl succinate and bipyridine ligands: synthesis, structure, thermostability and luminescence properties.

    Science.gov (United States)

    Liu, Yang; Feng, Yong Lan; Fu, Wei Wei

    2016-04-01

    From the viewpoint of crystal engineering, the construction of crystalline polymeric materials requires a rational choice of organic bridging ligands for the self-assembly process. Multicarboxylate ligands are of particular interest due to their strong coordination activity towards metal ions, as well as their various coordination modes and versatile conformations. The structural chemistry of dicarboxylate-based coordination polymers of transition metals has been developed through the grafting of N-containing organic linkers into carboxylate-bridged transition metal networks. A new luminescent two-dimensional zinc(II) coordination polymer containing bridging 2,2-dimethylsuccinate and 4,4'-bipyridine ligands, namely poly[[aqua(μ2-4,4'-bipyridine-κ(2)N:N')bis(μ3-2,2-dimethylbutanedioato)-κ(4)O(1),O(1'):O(4):O(4');κ(5)O(1):O(1),O(4):O(4),O(4')-dizinc(II)] dihydrate], {[Zn2(C6H8O4)2(C10H8N2)(H2O)]·2H2O}n, has been synthesized under hydrothermal conditions and characterized by single-crystal X-ray diffraction and elemental, IR and thermogravimetric analyses. In the structure, the 2,2-dimethylsuccinate ligands link linear tetranuclear Zn(II) subunits into one-dimensional chains along the c axis. 4,4'-Bipyridine acts as a tethering ligand expanding these one-dimensional chains into a two-dimensional layered structure. Hydrogen-bonding interactions between the water molecules (both coordinated and free) and carboxylate O atoms strengthen the packing of the layers. Furthermore, the luminescence properties of the complex were investigated. The compound exhibits a blue photoluminescence in the solid state at room temperature and may be a good candidate for potential hybrid inorganic-organic photoactive materials.

  7. The inverse-trans-influence in tetravalent lanthanide and actinide bis(carbene) complexes

    Science.gov (United States)

    Gregson, Matthew; Lu, Erli; Mills, David P.; Tuna, Floriana; McInnes, Eric J. L.; Hennig, Christoph; Scheinost, Andreas C.; McMaster, Jonathan; Lewis, William; Blake, Alexander J.; Kerridge, Andrew; Liddle, Stephen T.

    2017-02-01

    Across the periodic table the trans-influence operates, whereby tightly bonded ligands selectively lengthen mutually trans metal-ligand bonds. Conversely, in high oxidation state actinide complexes the inverse-trans-influence operates, where normally cis strongly donating ligands instead reside trans and actually reinforce each other. However, because the inverse-trans-influence is restricted to high-valent actinyls and a few uranium(V/VI) complexes, it has had limited scope in an area with few unifying rules. Here we report tetravalent cerium, uranium and thorium bis(carbene) complexes with trans C=M=C cores where experimental and theoretical data suggest the presence of an inverse-trans-influence. Studies of hypothetical praseodymium(IV) and terbium(IV) analogues suggest the inverse-trans-influence may extend to these ions but it also diminishes significantly as the 4f orbitals are populated. This work suggests that the inverse-trans-influence may occur beyond high oxidation state 5f metals and hence could encompass mid-range oxidation state actinides and lanthanides. Thus, the inverse-trans-influence might be a more general f-block principle.

  8. Synthesis, characterisation and antimicrobial activities of cobalt(II, copper(II and zinc(II mixed-ligand complexes containing 1,10-phenanthroline and 2,2’-bipyridine

    Directory of Open Access Journals (Sweden)

    A. Mohamadou

    2010-06-01

    Full Text Available Three new 1,10-phenanthroline and 2,2’-bipyridine mixed-ligand complexes of [Co(bpy(phen2](NO32.2H2O, [Cu(bpy(phen H2O 2]Cl2.2H2O, and [Zn(bpy2(phen]Cl2.6H2O were synthesized. The complexes were characterized by elemental, IR and visible spectroscopic analyses and the results indicate that both ligands are coordinated to the respective metal ions giving octahedral complexes. Antimicrobial studies showed that there is increased antimicrobial activity of the metal ions on coordination to the ligands. The water soluble complexes showed antimicrobial activities that are higher than those of the metal salts and 2,2’-bipyridine but lower than those of 1,10-phenanthroline. The copper complex [Cu(bpy(phen(H2O 2]Cl2.2H2O shows the highest activity.

  9. Trans as Contested Intelligibility

    DEFF Research Database (Denmark)

    Raun, Tobias

    2014-01-01

    Denne artikel rejser en række epistemologiske og metodologiske spørgsmål vedrørende læsningen af trans som identitetskategori. Disse spørgsmål er stærkt underbelyste i en skandinavisk akademisk kontekst, om end der el- lers i stigende grad produceres analyser af trans identitetsnarrativer. Artikl...

  10. New mixed ligand palladium(II) complexes based on the antiepileptic drug sodium valproate and bioactive nitrogen-donor ligands: Synthesis, structural characterization, binding interactions with DNA and BSA, in vitro cytotoxicity studies and DFT calculations

    Science.gov (United States)

    Tabrizi, Leila; Chiniforoshan, Hossein; Tavakol, Hossein

    2015-04-01

    The complexes [Pd(valp)2(imidazole)2] (1), [Pd(valp)2(pyrazine)2] (2) (valp is sodium valproate) have been synthesized and characterized using IR, 1H NMR, 13C{1H} NMR and UV-Vis spectrometry. The interaction of complexes with CT-DNA has been investigated using spectroscopic tools and viscosity measurement. In each case, the association constant (Kb) was deduced from the absorption spectral study and the number of binding sites (n) and the binding constant (K) were calculated from relevant fluorescence quenching data. As a result, a non-covalent interaction between the metal complex and DNA was suggested, which could be assigned to an intercalative binding. In addition, the interaction of 1 and 2 was ventured with bovine serum albumin (BSA) with the help of absorption and fluorescence spectroscopy measurements. Through these techniques, the apparent association constant (Kapp) and the binding constant (K) could be calculated for each complex. Evaluation of cytotoxic activity of the complexes against four different cancer cell lines proved that the complexes exhibited cytotoxic specificity and significant cancer cell inhibitory rate. Moreover, density functional theory (DFT) calculations were employed to provide more evidence about the observed data. The majority of trans isomers were supported not only by energies, but also by the similarity of its calculated IR frequencies, UV adsorptions and NMR chemical shifts to the experimental values.

  11. The trans influence in mer-trichloronitridobis(triphenylarsine)ruthenium(VI)

    DEFF Research Database (Denmark)

    Magnussen, Magnus; Bendix, Jesper

    2003-01-01

    The title compound, mer-[RuCl(3)N(C(18)H(15)As)(2)], is the first structurally characterized example of a nitride complex in which ruthenium is six-coordinated to monodentate ligands only. The Ru[triple-bond]N bond length [1.6161 (15) A] is relatively long, and the trans influence of the nitride...

  12. trans-Dichloridobis(3,4-dimethylpyridineplatinum(II

    Directory of Open Access Journals (Sweden)

    Alexander N. Chernyshev

    2009-01-01

    Full Text Available In the title compound, trans-[PtCl2(C7H9N2], the PtII atom is located on an inversion center and is coordinated by two 3,4-dimethylpyridine ligands and two chloride ligands, resulting in a typical slightly distorted square-planar geometry. The crystallographic inversion centre forces the value of the C—N—N—C torsion angle to be linear and the 3,4-dimethyl-pyridine ligands to be coplanar.

  13. DNA binding, cytotoxicity and apoptosis induction activity of a mixed-ligand copper(II) complex with taurine Schiff base and imidazole

    Science.gov (United States)

    Li, Mei; kong, Lin Lin; Gou, Yi; Yang, Feng; Liang, Hong

    2014-07-01

    A novel binuclear copper(II) complex (complex 1) with taurine Schiff base and imidazole has been synthesized and structurally characterized by single crystal X-ray diffraction, elemental analysis, ESI-MS spectrometry, UV-vis and IR spectroscopy. Single-crystal analysis revealed that 1 displays the sulfonate-bridged dinuclear copper(II) centers. Both copper atoms are five-coordinated and exhibit slightly distorted square pyramidal geometries. Each of copper atom is surrounded by three oxygen atoms and one nitrogen atom from different taurine Schiff base ligands, and one nitrogen atom from one imidazole ligand. The interaction between 1 and calf thymus DNA (CT-DNA) was investigated by UV-vis, fluorescence, circular dichroism (CD) spectra and agarose gel electrophoresis. The experimental results indicated that 1 could bind to CT-DNA via an intercalative mode and show efficient cleavage activity. In addition, 1 showed an antitumor effect on cell cycle and apoptosis. Flow cytometric analysis revealed that MGC-803 cells were arrested in the S phase after treatment with 1. Fluorescence microscopic observation indicated that 1 could induce apoptosis of MGC-803 cells.

  14. Ruthenium(II) bipyridine complexes bearing new keto-enol azoimine ligands: synthesis, structure, electrochemistry and DFT calculations.

    Science.gov (United States)

    Al-Noaimi, Mousa; Awwadi, Firas F; Mansi, Ahmad; Abdel-Rahman, Obadah S; Hammoudeh, Ayman; Warad, Ismail

    2015-01-25

    The novel azoimine ligand, Ph-NH-N=C(COCH3)-NHPh(C≡CH) (H2L), was synthesized and its molecular structure was determined by X-ray crystallography. Catalytic hydration of the terminal acetylene of H2L in the presence of RuCl3·3H2O in ethanol at reflux temperature yielded a ketone (L1=Ph-N=N-C(COCH3)=N-Ph(COCH3) and an enol (L2=Ph-N=N-C(COCH3)=N-PhC(OH)=CH2) by Markovnikov addition of water. Two mixed-ligand ruthenium complexes having general formula, trans-[Ru(bpy)(Y)Cl2] (1-2) (where Y=L1 (1) and Y=L2 (2), bpy is 2.2'-bipyrdine) were achieved by the stepwise addition of equimolar amounts of (H2L) and bpy ligands to RuCl3·3H2O in absolute ethanol. Theses complexes were characterized by elemental analyses and spectroscopic (IR, UV-Vis, and NMR (1D (1)H NMR, (13)C NMR, (DEPT-135), (DEPT-90), 2D (1)H-(1)H and (13)C-(1)H correlation (HMQC) spectroscopy)). The two complexes exhibit a quasi-reversible one electron Ru(II)/Ru(III) oxidation couple at 604 mV vs. ferrocene/ferrocenium (Cp2Fe(0/+)) couple along with one electron ligand reduction at -1010 mV. The crystal structure of complex 1 showed that the bidentate ligand L1 coordinates to Ru(II) by the azo- and imine-nitrogen donor atoms. The complex adopts a distorted trans octahedral coordination geometry of chloride ligands. The electronic spectra of 1 and 1+ in dichloromethane have been modeled by time-dependent density functional theory (TD-DFT). Copyright © 2014 Elsevier B.V. All rights reserved.

  15. Trans Fatty Acids

    Science.gov (United States)

    Doyle, Ellin

    1997-09-01

    Fats and their various fatty acid components seem to be a perennial concern of nutritionists and persons concerned with healthful diets. Advice on the consumption of saturated, polyunsaturated, monounsaturated, and total fat bombards us from magazines and newspapers. One of the newer players in this field is the group of trans fatty acids found predominantly in partially hydrogenated fats such as margarines and cooking fats. The controversy concerning dietary trans fatty acids was recently addressed in an American Heart Association (AHA) science advisory (1) and in a position paper from the American Society of Clinical Nutrition/American Institute of Nutrition (ASCN/AIN) (2). Both reports emphasize that the best preventive strategy for reducing risk for cardiovascular disease and some types of cancer is a reduction in total and saturated fats in the diet, but a reduction in the intake of trans fatty acids was also recommended. Although the actual health effects of trans fatty acids remain uncertain, experimental evidence indicates that consumption of trans fatty acids adversely affects serum lipid levels. Since elevated levels of serum cholesterol and triacylglycerols are associated with increased risk of cardiovascular disease, it follows that intake of trans fatty acids should be minimized.

  16. Structural, molecular orbital and optical characterizations of solvatochromic mixed ligand copper(II) complex of 5,5-Dimethyl cyclohexanate 1,3-dione and N,N,N";,N";N″-pentamethyldiethylenetriamine

    Science.gov (United States)

    Taha, A.; Farag, A. A. M.; Ammar, A. H.; Ahmed, H. M.

    2014-03-01

    In this work, a new solvatochromic mononuclear mixed ligand complex with the formula, Cu(DMCHD)(Me5dien)NO3 (where, DMCHD = 5,5-Dimethyl cyclohexanate 1,3-dione and (Me5dien) = N,N,N";,N";N″-pentamethyldiethylenetriamine was synthesized and characterized by analytical, spectral, magnetic, molar conductance, thermal gravimetric analysis (TGA), X-ray diffraction (XRD) and transmission electron microscope (TEM) measurements. The formation constant-value for copper (II)-DMCHD was found to be much lower than the expected for similar β-diketones, revealing monobasic unidentate nature of this ligand. The d-d absorption bands of the prepared complex exhibit a color changes in various solvent (solvatochromic). Specific and non-specific interactions of solvent molecules with the complex were investigated using Multi Parametric Linear Regression Analysis (MLRA). Structural parameters of the free ligands and their Cu (II) - complex were calculated on the basis of semi-empirical PM3 level and compared with the experimental data. The crystallite size and morphology of Cu(DMCHD)(Me5dien)NO3 were examined using XRD analysis and TEM, revealing that the complex is well crystalline and correspond to the monoclinic crystal structure. The lattice strain and mean crystallite size were estimated by Williamson-Hall (W-H) plot using X-ray diffraction data. The main important absorption parameters such as extinction molar coefficient, oscillator strength and electric dipole strength of the principal optical transitions in the UV-Vis region were calculated. The analysis of absorption coefficient near the fundamental absorption edge reveals that the optical band gaps are direct allowed transitions with values of 2.78 eV and 3.59 eV. The present copper (II) complex was screened for its antimicrobial activity against Staphylococcus Aureus and Bacillus Subtilis as Gram-positive bacteria, Escherichia Coli and Salmonella Typhimurium as Gram-negative bacteria and Candida Albicans as fungus

  17. Chapter 19. Design and evaluation of potential 99mTc radiopharmaceuticals based on the Tc-Carbonyl, 4 + 1 mixed ligand chelate system and Tc-nitrido approaches

    International Nuclear Information System (INIS)

    Giglio, J.; Muslera, A.; Leon, E.; Paolino, A.; Leon, A.; Rey, A.; Incerti, M.; Fernandez, R.; Manta, E.; Brugnini, A.; Chabalgoity, A.

    2007-01-01

    The aim of the work was to explore the possibilities of the novel labelling strategies in the development of 99m Tc labelled small biomolecules. Different steps required to fulfil this objective were undertaken: organic synthesis of glucose derivatives, optimization of labelling and in vitro and in vivo evaluation of Rd peptides and anne xin 13 derivatives using either the Hyonic bifunctional ligand, the Tc-tricarbonyl, the 4 + 1 mixed ligand or the Tc(V)-nitri do approaches. Glucose-O-hexyl bromide, glucose- O-butylbromide and glucose-O-butylamine were successfully synthesized, opening the possibility of introducing different chelators according to the desired labelling procedure. c(RGDyK) derivatives bearing different chelators were labelled with 99m Tc using novel approaches and evaluated both in vitro and in vivo in order to compare the effect of the chelator and labelling method on the physicochemical and biological behaviour. Annexin 13 peptides were also labelled using the HYNIC and Tc(I)-tricarbonyl approaches. A primary evaluation in normal animals and in a model of cardiac apoptosis is also presented. Cooperation with other participants was crucial to develop this work. (author)

  18. Polynuclear manganese complexes with the dicarboxylate ligand m-phenylenedipropionate: a hexanuclear mixed-valence (3Mn(III), 3Mn(IV)) complex.

    Science.gov (United States)

    Cañada-Vilalta, Cristina; Streib, William E; Huffman, John C; O'Brien, Ted A; Davidson, Ernest R; Christou, George

    2004-01-12

    The dicarboxylate group m-phenylenedipropionate (mpdp(2)(-)) has been used for the synthesis of four new Mn compounds of different nuclearities and oxidation states: [Mn(2)O(mpdp)(bpy)(2)(H(2)O)(MeCN)](ClO(4))(2) (3), [Mn(3)O(mpdp)(3)(py)(3)](ClO(4)) (4), [Mn(3)O(mpdp)(3)(py)(3)] (5), and [Mn(6)O(7)(mpdp)(3)(bpy)(3)](ClO(4)) (6). Compound 3 (2Mn(III)) contains a [Mn(2)(micro-O)](4+) core, whereas 5 (Mn(II), 2Mn(III)) and 4 (3Mn(III)) contain the [Mn(3)(micro(3)-O)](6+,7+) core, respectively. In all three compounds, the mpdp(2)(-) ligand is flexible enough to adopt the sites occupied by two monocarboxylates in structurally related compounds, without noticeable distortion of the cores. Variable-temperature magnetic susceptibility studies establish that 3 and 5 have ground-state spin values of S = 0 and S = 1/2, respectively. Compound 6 is a highly unusual 3Mn(III), 3Mn(IV) trapped-valent compound, and it is also a new structural type, with six Mn atoms disposed in a distorted trigonal antiprismatic topology. Its electronic structure has been explored by variable-temperature measurements of its dc magnetic susceptibility, magnetization vs field response, and EPR spectrum. The magnetic data indicate that it possesses an S = 3/2 ground state with an axial zero-field splitting parameter of D = -0.79 cm(-)(1), and this conclusion is supported by the EPR data. The combined results demonstrate the ligating flexibility of the mpdp(2)(-) ligand and its usefulness in the synthesis of a variety of Mn(x) species.

  19. Fluorescence and electron paramagnetic resonance studies of norfloxacin and N-donor mixed-ligand ternary copper(II) complexes: Stability and interaction with SDS micelles

    Science.gov (United States)

    Vignoli Muniz, Gabriel S.; Incio, Jimmy Llontop; Alves, Odivaldo C.; Krambrock, Klaus; Teixeira, Letícia R.; Louro, Sonia R. W.

    2018-01-01

    The stability of ternary copper(II) complexes of a heterocyclic ligand, L (L being 2,2‧-bipyridine (bipy) or 1,10-phenanthroline (phen)) and the fluorescent antibacterial agent norfloxacin (NFX) as the second ligand was studied at pH 7.4 and different ionic strengths. Fluorescence quenching upon titration of NFX with the binary complexes allowed to obtain stability constants for NFX binding, Kb, as a function of ionic strength. The Kb values vary by more than two orders of magnitude when buffer concentration varies from 0.5 to 100 mM. It was observed that previously synthesized ternary complexes dissociate in buffer according with the obtained stability constants. This shows that equimolar solutions of NFX and binary complexes are equivalent to solutions of synthesized ternary complexes. The interaction of the ternary copper complexes with anionic SDS (sodium dodecyl sulfate) micelles was studied by fluorescence and electron paramagnetic resonance (EPR). Titration of NFX-loaded SDS micelles with the complexes Cu:L allowed to determine the stability constants inside the micelles. Fluorescence quenching demonstrated that SDS micelles increase the stability constants by factors around 50. EPR spectra gave details of the copper(II) local environment, and demonstrated that the structure of the ternary complexes inside SDS micelles is different from that in buffer. Mononuclear ternary complexes formed inside the micelles, while in buffer most ternary complexes are binuclear. The results show that anionic membrane interfaces increase formation of copper fluoroquinolone complexes, which can influence bioavailability, membrane diffusion, and mechanism of action of the antibiotics.

  20. trans-Dichloridobis(quinoline-κNplatinum(II

    Directory of Open Access Journals (Sweden)

    Kwang Ha

    2012-05-01

    Full Text Available In the title complex, trans-[PtCl2(C9H7N2], the PtII ion is four-coordinated in an essentially square-planar coordination environment defined by two N atoms from two quinoline (qu ligands and two Cl− anions. The Pt atom is located on an inversion centre and thus the asymmetric unit contains one half of the complex; the PtN2Cl2 unit is exactly planar. The dihedral angle between the PtN2Cl2 unit and the quinoline ligand is 85.1 (1°. In the crystal, the complex molecules are stacked into columns along the b axis. In the columns, several intermolecular π–π interactions between the six-membered rings are present, the shortest ring centroid–centroid distance being 3.733 (5 Å between pyridine rings.

  1. Molecular Structures, Vibrational Spectroscopy, and Normal-Mode Analysis of M(2)(C&tbd1;CR)(4)(PMe(3))(4) Dimetallatetraynes. Observation of Strongly Mixed Metal-Metal and Metal-Ligand Vibrational Modes.

    Science.gov (United States)

    John, Kevin D.; Miskowski, Vincent M.; Vance, Michael A.; Dallinger, Richard F.; Wang, Louis C.; Geib, Steven J.; Hopkins, Michael D.

    1998-12-28

    on Mo(2)Cl(4)P(4), show that nu(a), nu(b), and nu(c) arise from modes of strongly mixed nu(Mo(2)), nu(MoC), and lambda(MoCC) character. The relative intensities of the resonance-Raman bands due to nu(a), nu(b), and nu(c) reflect, at least in part, their nu(M(2)) character. In contrast, the force field shows that mixing of nu(M(2)) and nu(C&tbd1;C) is negligible. The three-mode mixing is expected to be a general feature for quadruply bonded complexes with unsaturated ligands.

  2. A P,O,P′-tridentate mixed-donor scorpionate ligand: 6-[4,6-bis(diphenylphosphino-10H-phenoxazin-10-yl]hexan-1-ol

    Directory of Open Access Journals (Sweden)

    Holger B. Friedrich

    2008-10-01

    Full Text Available The title compound, C42H39NO2P2, is a P,O,P′-tridentate scorpionate-type ligand and has one molecule in the asymmetric unit. The angles involving the P atoms range from 100.21 (7 to 104.89 (7°. The N-hexanol group was found to be disordered and was refined over two positions with final occupancies of 0.683 (3 and 0.317 (3 which affected the C—O and C—N bond lengths. The bond lengths for C—O range from 1.402 (2 to 1.415 (2 Å and for C—N from 1.410 (2 to 1.448 (3 Å for the major disorder component; the corresponding ranges for the minor disorder component are 1.429 (3–1.408 (3 and 1.474 (3–1.474 (4 Å.

  3. Weakening of Carbide–Platinum Bonds as a Probe for Ligand Donor Strengths

    DEFF Research Database (Denmark)

    Reinholdt, Anders; Bendix, Jesper

    2017-01-01

    Functionalization of the terminal ruthenium carbide ligand in (Cy3P)2Cl2Ru≡C: with platinum and a range of ligands provides {Ru≡C−Pt−L} fragments with trans geometries. The bridging carbide exhibits chemical shifts and coupling constants to platinum, which are highly responsive to the degree of w...... of weakening of the RuC−Pt linkage induced by the trans ligands, making the terminal ruthenium carbide complex a sensitive probe for the electron donating abilities of other ligands.......Functionalization of the terminal ruthenium carbide ligand in (Cy3P)2Cl2Ru≡C: with platinum and a range of ligands provides {Ru≡C−Pt−L} fragments with trans geometries. The bridging carbide exhibits chemical shifts and coupling constants to platinum, which are highly responsive to the degree...

  4. trans-Dichloridobis(triphenylphosphane-κPpalladium(II benzene hemisolvate

    Directory of Open Access Journals (Sweden)

    Frank Meyer-Wegner

    2012-04-01

    Full Text Available The title complex, [PdCl2(C18H15P2]·0.5C6H6, has the PdII ion in a square-planar coordination mode (r.m.s. deviation for Pd, P and Cl atoms = 0.024 Å with the PPh3 and Cl ligands mutually trans. The benzene solvent molecule is located about a crystallographic inversion centre. The title complex is isostructural with trans-dichloridobis(triphenylphosphanepalladium(II 1,4-dichlorobenzene sesquisolvate [Kitano et al. (1983. Acta Cryst. C39, 1015–1017].

  5. Synthesis, Crystal Structure, and Electroconducting Properties of a 1D Mixed-Valence Cu(I–Cu(II Coordination Polymer with a Dicyclohexyl Dithiocarbamate Ligand

    Directory of Open Access Journals (Sweden)

    Kenji Nakatani

    2015-04-01

    Full Text Available A new mixed-valence Cu(I–Cu(II 1D coordination polymer, [CuI4CuIIBr4(Cy2dtc2]n, with an infinite chain structure is synthesized by the reaction of Cu(Cy2dtc2 (Cy2dtc− = dicyclohexyl dithiocarbamate, C13H22NS2 with CuBr·S(CH32. The as-synthesized polymer consists of mononuclear copper(II units of CuII(Cy2dtc2 and tetranuclear copper(I cluster units, CuI4Br4. In the cluster unit, all the CuI ions have distorted trigonal pyramidal coordination geometries, and the CuI–CuI or CuI–CuII distances between the nearest copper ions are shorter than the sum of van der Waals radii for Cu–Cu.

  6. Trans-Spatial Utopias

    Science.gov (United States)

    Kramsch, Claire

    2018-01-01

    The "trans-" perspectives offered in this special issue are heady stuff. Post-structuralism (philosophy) meets the digital age (electronics), meets globalization (economics), and meets translingual practice (linguistics) to create a perfectly utopian or placeless space for future exploration. I want to first add my voice to the…

  7. Low Trans Hydrogenation

    Science.gov (United States)

    Although hydrogenation has been the technology of choice for fat formulation for many years recent concerns over the health and nutrition of trans fatty acids have had a profound effect on the edible oil industry. Since Jan. 1, 2006, TFA has been required on nutrition labels along with saturated an...

  8. Microwave-assisted synthesis of mixed ligands organotin(IV) complexes of 1,10-phenanthroline and l-proline: Physicochemical characterization, DFT calculations, chemotherapeutic potential validation by in vitro DNA binding and nuclease activity.

    Science.gov (United States)

    Nath, Mala; Mridula; Kumari, Ranjana

    2017-09-01

    Diorganotin(IV) and triphenyltin(IV) derivatives of L-proline (HPro) having general formula R 2 Sn(Pro) 2 (R=n-Bu (1), Ph (2)) and Ph 3 Sn(Pro) (3), respectively, and the mixed ligands di-/triorganotin(IV) derivatives of L-proline and 1,10-phenanthroline (phen) with general formula [R 2 Sn(Pro)(Phen)Cl] and [R 3 Sn(Pro)(Phen)] (where R=Me (4 and 7), n-Bu (5 and 8), Ph (6 and 9)), respectively, have been synthesized by microwave-assisted method and characterized by elemental analysis, IR, NMR ( 1 H, 13 C and 119 Sn) and DART-mass spectral studies. The results suggest bicapped tetrahedron or a skew trapezoidal-bipyramid geometry for R 2 Sn(Pro) 2 , a distorted tetrahedral geometry for Ph 3 Sn(Pro) and a distorted octahedral geometry for [R 2 Sn(Pro)(Phen)Cl] and [Ph 3 Sn(Pro)(Phen)] around the Sn atom, and the same has been validated by density functional theory calculations (DFT). In vitro DNA binding studies of 1-9 have been investigated by UV-Vis, fluorescence and circular dichroism titrations, viscosity and DNA melting experiments. The observed hypochromic shift in UV-Vis and fluorescence studies evidenced a partial intercalative mode of binding of complexes to CT-DNA. The binding affinity and quenching ability have been quantified in terms of intrinsic binding constant (K b ) and Stern-Volmer quenching constant (Ksv). The determined values suggest that di- and triorganotin(IV) derivatives of L-proline possess lesser affinity to bind with CT-DNA in comparison to the mixed ligands di-/triorganotin(IV) derivatives of L-proline and 1,10-phenanthroline. The partial intercalative mode of binding of these complexes with CT DNA has also been supported by a change in the viscosity and melting point of DNA as well as a change in the intensity of positive and negative bands in circular dichroism spectra. The cleavage studies by agarose gel electrophoresis indicate effective cleavage of supercoiled plasmid DNA into its nicked form by all the complexes and even to its linear

  9. NMR spectroscopic and X-ray crystallographic study of methylcobalt(III) compounds with saturated amine ligands

    DEFF Research Database (Denmark)

    Kofod, Pauli; Harris, Pernille

    2004-01-01

    The C-13 chemical shifts of methylcobalt(III) compounds with saturated amine ligands in cis positions to the methyl group and a monodentate ligand, L = CN-, NH3, NO2, N-3(-), H2O, or OH-, in the trans position are reported. The amine ligands used, 1,2-ethanediamine (en), 1,3-propanediamine (tn), ...

  10. Preparation and Spectral Properties of Mixed-Ligand Complexes of VO(IV, Ni(II, Zn(II, Pd(II, Cd(II and Pb(II with Dimethylglyoxime and N-acetylglycine

    Directory of Open Access Journals (Sweden)

    Shayma A. Shaker

    2010-01-01

    Full Text Available A number of mixed-ligand complexes of the general formula [M(D(G] where D=dimethylglyoximato monoanion, G=N-acetylglycinato and M=VO(IV, Ni(II, Zn(II, Pd(II, Cd(II and Pb(II were prepared. Each complex was characterized by elemental analysis, determination of metal, infrared spectra, electronic spectra, (1H and 13C NMR spectra, conductivity and magnetic moments. All these complexes were not soluble in some of the organic solvent but highly soluble in dimethylformamide. The conductivity data showed the non-electrolytic nature of the complexes. The electronic spectra exhibited absorption bands in the visible region caused by the d-d electronic transition such as VO(IV, Ni(II and Pd(II. The IR and (1H, 13C NMR spectra which have indicate that the dimethylglyoxime was coordinated with the metal ions through the N and O atoms of the oxime group and N-acetylglycine was coordinated with metal ions through the N atom and terminal carboxyl oxygen atom.

  11. Anion controlled structural and magnetic diversity in unusual mixed-bridged polynuclear Ni(II) complexes with a versatile bis(2-methoxy phenol)diamine hexadentate ligand. An experimental and theoretical magneto-structural study.

    Science.gov (United States)

    Botana, Luis; Ruiz, José; Mota, Antonio J; Rodríguez-Diéguez, Antonio; Seco, José M; Oyarzabal, Itziar; Colacio, Enrique

    2014-09-28

    This work reports the syntheses, crystal structures, magnetic properties and DFT calculations of six novel polynuclear NiII compounds [Ni2(μ-HL1)2(μ-N3)]N3·(CH3OH)2·2H2O (1), [Ni2(μ-HL1)2(μ-N3)][Na2Ni2(μ-L1)2(μ-N3)2(CH3OH)(N3)]·4CH3OH (2), [Ni4(μ-L1)2(μ-N3)4(CH3OH)2]·2CH3OH (3), [Na2Ni4(μ-L1)2(μ-OAc)2(μ-N3)4(CH3OH)4]·2CH3OH (4), [Ni4(μ-L1)2(μ-Cl)2(Cl)2] (5), and [Ni3(μ-L1)2(acac)2(H2O)2] (6), with uncommon structures and rare mixed-bridges between NiII ions, which were prepared from the versatile polytopic Mannich base ligand N,N′-dimethyl-N,N′-bis(2-hydroxy-3-methoxy-5-methylbenzyl)ethylenediamine (H2L1). The anionic coligand (azide, chloride, acetate and acetylacetonate) and reaction conditions play crucial roles in determining the final structure of these compounds and consequently their magnetic properties. Compound 1 contains a Ni2 cationic unit with rare di-μ-phenoxido/μ1,1-azide triple mixed bridges whereas complex 2 is made from the same Ni2 cationic unit as 1, cocrystallized with Na2Ni2 neutral units, in which double μ1,1,1-azide bridges connect the NiII and NaI anions. Complexes 3 and 4 are Ni4 complexes with defective dicubane and linear structures, respectively. Complex 3 has two distinct types of mixed bridges, μ-phenoxido/μ1,1,1-azido and μ1,1-azido/μ1,1,1-azido and a double di-μ1,1,1-azido bridge, the latter connecting the face-sharing NiII ions. In 4, rare μ-phenoxido/μ1,1-azide/syn–syn acetate triple mixed bridges connect central and terminal NiII atoms whereas a double μ1,1-azide planar bridging fragment links the central NiII ions. Complex 5 has a defective-dicubane structure with double μ-phenoxido/μ3-chloro mixed bridges and di-μ3-chloro bridges, whereas complex 6 has a bent structure with very uncommon single μ-phenoxido bridges. The analysis of the magnetic properties reveals that in complexes 1–4 all magnetic pathways transmit ferromagnetic interactions leading to S = 2 ground states for 1 and 2 and

  12. Radioiodinated ligands for dopamine receptors

    International Nuclear Information System (INIS)

    Kung, H.F.

    1994-01-01

    The dopamine receptor system is important for normal brain function; it is also the apparent action site for various neuroleptic drugs for the treatment of schizophrenia and other metal disorders. In the past few years radioiodinated ligands for single photon emission tomography (SPECT) have been successfully developed and tested in humans: [ 123 I]TISCH for D1 dopamine receptors; [ 123 I]IBZM, epidepride, IBF and FIDA2, four iodobenzamide derivatives, for D2/D3 dopamine receptors. In addition, [ 123 I]β-CIT (RTI-55) and IPT, cocaine derivatives, for the dopamine reuptake site are potentially useful for diagnosis of loss of dopamine neurons. The first iodinated ligand, (R)trans-7-OH-PIPAT, for D3 dopamine receptors, was synthesized and characterized with cloned cell lines (Spodoptera frugiperda, Sf9) expressing the D2 and D3 dopamine receptors and with rat basal forebrain membrane preparations. Most of the known iodobenzamides displayed similar potency in binding to both D2 and D3 dopamine receptors expressed in the cell lines. Initial studies appear to suggest that by fine tuning the structures it may be possible to develop agents specific for D2 and D3 dopamine receptors. It is important to investigate D2/D3 selectivity for this series of potent ligands

  13. Trans-polar-fat

    DEFF Research Database (Denmark)

    Counil, Emilie; Dewailly, Eric; Bjerregaard, Peter

    2008-01-01

    As part of the rapid socio-cultural transition observed in Arctic populations, the Inuit diet is changing. We present original data derived from the baseline Inuit Health in Transition cohort study regarding biological levels of n-3 fatty acids and trans-fatty acids (TFA), lipids with opposite......-bought foods was high in both groups (77.5 % and 83.5 %), especially in youth. Our results call for action to rehabilitate and recover access to country foods and point to the importance for Nunavik and the entire circumpolar world to follow the example of Denmark and Greenland, which imposed a maximum content...

  14. Cis/trans Coordination in olefin metathesis by static and molecular dynamic DFT calculations

    KAUST Repository

    Poater, Albert

    2014-05-25

    In regard to [(N-heterocyclic carbene)Ru]-based catalysts, it is still a matter of debate if the substrate binding is preferentially cis or trans to the N-heterocyclic carbene ligand. By means of static and molecular dynamic DFT calculations, a simple olefin, like ethylene, is shown to be prone to the trans binding. Bearing in mind the higher reactivity of trans isomers in olefin metathesis, this insight helps to construct small alkene substrates with increased reactivity. © 2014 Springer Science+Business Media New York.

  15. A trans world journey

    DEFF Research Database (Denmark)

    Stender, Steen; Dyerberg, Jørn; Bysted, Anette

    2006-01-01

    A high intake of industrially produced trans fatty acids (IP-TFA) is associated with increased risk of coronary heart disease (CHD), and a daily intake as low as possible is required to minimize health risks. To achieve this at the individual level in Denmark, legislation limited IP-TFA in foods ...... to a maximum of 2% of fat content from 2004. We assessed the potential exposure of consumers to IP-TFA by analysing popular foods in Denmark, and in 25 other countries. Fifty-five servings of French fries and chicken nuggets, 87 packages of microwave popcorn, and 393 samples of biscuits....../cakes/wafers with "partially hydrogenated vegetable fat" listed high on the food label were bought between November 2004, and February 2006. The content of IP-TFA was analysed by standardized methodology. We defined a "high trans menu" as a large size serving of French fries and nuggets, 100 g of microwave popcorn, and 100 g...... 38, 37, and 36 g, respectively. The legislation in Denmark has reduced the exposure of IP-TFA at the individual level without noticeable effect on availability, price. and quality of foods previously containing high amounts of IP-TFA. The findings of high concentrations of IP-TFA in popular foods...

  16. Mixed-valent and radical states of complexes [(bpy)(2)M(.mu.-abpy)M´(bpy)(2)](n+), M,M´ = Ru or Os, abpy=2,2´-azobispyridine: Electron transfer vs. hole transfer mechanism in azo ligand-bridged complexes

    Czech Academy of Sciences Publication Activity Database

    Heilmann, M.; Frantz, S.; Kaim, W.; Fiedler, Jan; Duboc, C.

    2006-01-01

    Roč. 359, č. 3 (2006), s. 821-829 ISSN 0020-1693 R&D Projects: GA MŠk LC510; GA AV ČR IAA400400505; GA ČR GA203/03/0821 Institutional research plan: CEZ:AV0Z40400503 Keywords : mixed valency * osmium compounds * radical ligand s * ruthenium compounds * spectroslectrochemistry Subject RIV: CG - Electrochemistry Impact factor: 1.674, year: 2006

  17. Strong metal-metal coupling in mixed-valent intermediates [Cl(L)Ru(mu-tppz)Ru(L)Cl](+), L = beta-diketonato ligands, tppz=2,3,5,6-tetrakis(2-pyridyl)pyrazine

    Czech Academy of Sciences Publication Activity Database

    Kundu, T.; Schweinfurth, D.; Sarkar, B.; Mondal, T. K.; Fiedler, Jan; Mobin, S. M.; Puranik, V. G.; Kaim, W.; Lahiri, G. K.

    2012-01-01

    Roč. 41, č. 43 (2012), s. 13429-13440 ISSN 1477-9226 R&D Projects: GA AV ČR IAA400400802 Institutional support: RVO:61388955 Keywords : TRIDENTATE BRIDGING LIGAND * DENSITY-FUNCTIONAL THEORY * HYDRAZONE-BASED LIGAND S Subject RIV: CG - Electrochemistry Impact factor: 3.806, year: 2012

  18. mixed-ligand complexes of dimethylglyoxime

    African Journals Online (AJOL)

    STORAGESEVER

    2009-01-05

    Jan 5, 2009 ... [Co(Hdmg)2(dea)2] that was black maureen; Ni(II) complexes were red and those of Cu(II) were black, grey- ash and light green. The melting points/decomposition temperatures (M.P./D.T.) complexes are shown in Table. 1. Some are sharp and range within 130 - 304°C. Some however decomposed before ...

  19. Trans-sialidase-like gene from the bloodstream form of ...

    African Journals Online (AJOL)

    user

    2011-03-28

    Mar 28, 2011 ... vaccines (Holmberg et al., 2000). The involvement of TS in trypanosomal pathogenecity has been ... structure based trans-sialidase inhibitors as a therapy or vaccine for trypanosomiasis. ... 5.0 µl of 10 x PCR buffer with MgCl2; 1.0 µl of enzyme mix. Mix2; 15. µl nuclease free water; 4.0 µl dNTPs; 1.0 µl of ...

  20. Facts about trans fats

    Science.gov (United States)

    ... battered Shortening and stick margarine Cakes, cake mixes, pies, pie crust Animal foods, such as red meats ... nutrients and have extra calories from sugar: Cookies, pies, cakes, biscuits, sweet rolls, and donuts Breads and ...

  1. Mitochondrial protection by the mixed muscarinic/σ1 ligand ANAVEX2-73, a tetrahydrofuran derivative, in Aβ25-35 peptide-injected mice, a nontransgenic Alzheimer's disease model

    Directory of Open Access Journals (Sweden)

    Valentine eLahmy

    2015-01-01

    Full Text Available Alzheimer’s disease (AD, the most prevalent dementia in the elderly, is characterized by progressive synaptic and neuronal loss. Mitochondrial dysfunctions have been consistently reported as an early event in AD and appear before Aβ deposition and memory decline. In order to define a new neuroprotectant strategy in AD targeting mitochondrial alterations, we develop tetrahydro-N,N-dimethyl-2,2-diphenyl-3-furanmethanamine (ANAVEX2-73, AE37, a mixed muscarinic receptor ligand and a sigma-1 receptor (σ1R agonist. We previously reported that ANAVEX2-73 shows anti-amnesic and neuroprotective activities in mice injected ICV with oligomeric amyloid-β25-35 peptide (Aβ25-35. The σ1R is present at mitochondria-associated endoplasmic reticulum membranes, where it acts as a sensor/modulator of endoplasmic reticulum (ER stress responses and local Ca2+ exchanges with the mitochondria. We therefore evaluated the effect of ANAVEX2-73 and PRE-084, a reference σ1R agonist, on preservation of mitochondrial integrity in Aβ25-35-injected mice. In isolated mitochondria from hippocampus preparations of Aβ25-35 injected animals, we measured respiration rates, complex activities, lipid peroxidation, Bax/Bcl-2 ratios and cytochrome c release into the cytosol. Five days after Aβ25-35 injection, mitochondrial respiration in mouse hippocampus was altered. ANAVEX2-73 (0.01-1 mg/kg IP restored normal respiration and PRE-084 (0.5-1 mg/kg IP increased respiration rates. Both compounds prevented Aβ25-35-induced increases in lipid peroxidation levels, Bax/Bcl-2 ratio and cytochrome c release into the cytosol, all indicators of increased toxicity. ANAVEX2-73 and PRE-084 efficiently prevented the mitochondrial respiratory dysfunction and resulting oxidative stress and apoptosis. The σ1R, targeted selectively or non-selectively, therefore appears as a valuable target for protection against mitochondrial damages in AD.

  2. trans-Dichlorido­bis(3,4-dimethyl­pyridine)platinum(II)

    Science.gov (United States)

    Chernyshev, Alexander N.; Bokach, Nadezhda A.; Izotova, Youlia A.; Haukka, Matti

    2009-01-01

    In the title compound, trans-[PtCl2(C7H9N)2], the PtII atom is located on an inversion center and is coordinated by two 3,4-dimethyl­pyridine ligands and two chloride ligands, resulting in a typical slightly distorted square-planar geometry. The crystallographic inversion centre forces the value of the C—N—N—C torsion angle to be linear and the 3,4-dimethyl-pyridine ligands to be coplanar. PMID:21581530

  3. Synthesis, characterisation and antimicrobial studies of mixed nickel ...

    African Journals Online (AJOL)

    Conductance values indicated a 1:1 electrolyte for the complexes. The antimicrobial activities of the ligands and their mixed ligand complexes were screened using Agar diffusion method. It was found that the mixed metal complexes have higher antimicrobial activity than the free ligands. Keywords: Benzylhydrazone ...

  4. Modulation of multimetal complexation behavior of tetraoxime ligand by covalent transformation of olefinic functionalities.

    Science.gov (United States)

    Akine, Shigehisa; Kagiyama, Satoko; Nabeshima, Tatsuya

    2010-03-01

    A new multimetal complexation system that can change its complexation behavior by C-C bond formation has been developed. The acyclic tetraoxime ligand H(4)L(1) having two terminal allyl groups was synthesized. The olefin metathesis of H(4)L(1) selectively produced trans-H(4)L(2) while the reaction of [L(1)Zn(2)Ca] exclusively afforded cis-H(4)L(2). The saturated analogue H(4)L(3) was synthesized by hydrogenation. The complexation of the ligands H(4)L (L = L(1), trans-L(2), cis-L(2), L(3)) with zinc(II) acetate (3 equiv) yielded the trinuclear complexes [LZn(3)] with a similar trinuclear core bridged by acetato ligands. Whereas the formation process of [L(1)Zn(3)] having an acyclic ligand was highly cooperative, the macrocyclic analogues [LZn(3)] (L = trans-L(2), cis-L(2), L(3)) were formed in a stepwise fashion via the intermediate 2:3 complex [(HL)(2)Zn(3)]. The trinuclear complexes [LZn(3)] (L = L(1), trans-L(2), cis-L(2), L(3)) can recognize alkaline earth metal ions via site-selective metal exchange. The acyclic [L(1)Zn(3)] selectively recognizes Ca(2+), while the cyclic [trans-L(2)Zn(3)] showed a Ba(2+) selectivity. The metal exchange of [LZn(3)] (L = L(1), trans-L(2), cis-L(2), L(3)) with La(3+) efficiently occurred to give [LZn(2)La], but the trans-olefin linker of the [trans-L(2)Zn(2)La] significantly deforms the structure in such a way that one of the salicylaldoxime moieties does not participate in the coordination. Consequently, the chemical transformation of the olefinic moiety significantly affects the multimetal complexation behavior of the tetraoxime ligands.

  5. trans-K3[TcO2(CN4

    Directory of Open Access Journals (Sweden)

    Sayandev Chatterjee

    2010-08-01

    Full Text Available The structure of the title compound, tripotassium trans-tetracyanidodioxidotechnetate(V, is isotypic with its Re analogue. The [TcO2(CN4]3− trans-tetracyanidodioxidotechnetate anion has a slightly distorted octahedral configuration. The Tc atom is located on a center of inversion and is bound to two O atoms in axial and to four cyanide ligands in equatorial positions. The Tc—O distance is consistent with a double-bond character. The two potassium cations, one located on a center of inversion and one in a general position, reside in octahedral or tetrahedral environments, respectively. K...O and K...N interactions occur in the 2.7877 (19–2.8598 (15 Å range.

  6. N6-Benzyladenosine Derivatives as Novel N-Donor Ligands of Platinum(II Dichlorido Complexes

    Directory of Open Access Journals (Sweden)

    Ján Vančo

    2013-06-01

    Full Text Available The platinum(II complexes trans-[PtCl2(Ln2]∙xSolv 1–13 (Solv = H2O or CH3OH, involving N6-benzyladenosine-based N-donor ligands, were synthesized; Ln stands for N6-(2-methoxybenzyladenosine (L1, involved in complex 1, N6-(4-methoxy-benzyladenosine (L2, 2, N6-(2-chlorobenzyladenosine (L3, 3, N6-(4-chlorobenzyl-adenosine (L4, 4, N6-(2-hydroxybenzyladenosine (L5, 5, N6-(3-hydroxybenzyl-adenosine (L6, 6, N6-(2-hydroxy-3-methoxybenzyladenosine (L7, 7, N6-(4-fluoro-benzyladenosine (L8, 8, N6-(4-methylbenzyladenosine (L9, 9, 2-chloro-N6-(3-hydroxy-benzyladenosine (L10, 10, 2-chloro-N6-(4-hydroxybenzyladenosine (L11, 11, 2-chloro-N6-(2-hydroxy-3-methoxybenzyladenosine (L12, 12 and 2-chloro-N6-(2-hydroxy-5-methylbenzyladenosine (L13, 13. The compounds were characterized by elemental analysis, mass spectrometry, IR and multinuclear (1H-, 13C-, 195Pt- and 15N- and two-dimensional NMR spectroscopy, which proved the N7-coordination mode of the appropriate N6-benzyladenosine derivative and trans-geometry of the title complexes. The complexes 1–13 were found to be non-toxic in vitro against two selected human cancer cell lines (HOS and MCF7; with IC50 > 50.0 µM. However, they were found (by ESI-MS study to be able to interact with the physiological levels of the sulfur-containing biogenic biomolecule L-methionine by a relatively simple 1:1 exchange mechanism (one Ln molecule was replaced by one L-methionine molecule, thus forming a mixed-nitrogen/sulfur-ligand dichlorido-platinum(II coordination species.

  7. Ligands hybrides : synthèse et chimie de coordination

    OpenAIRE

    Massard, Alexandre

    2011-01-01

    This manuscript deals with the synthesis of hybrids ligands and their coordination ability. The first part is dedicated to Cp-imidazole, Cp-imidazolium and Cp-phosphine ligands. Several synthetic routes have been developed to reach these mixed ligands and their coordination chemistry has been studied with titanium. In a second part, a method developed in our laboratory to synthesize phosphine-olefines was applied to obtain a phosphino-diene bearing three potential coordination sites. We have ...

  8. Ligands in PSI structures

    International Nuclear Information System (INIS)

    Kumar, Abhinav; Chiu, Hsiu-Ju; Axelrod, Herbert L.; Morse, Andrew; Elsliger, Marc-André; Wilson, Ian A.; Deacon, Ashley

    2010-01-01

    A survey of the types and frequency of ligands that are bound to PSI structures is analyzed as well as their utility in functional annotation of previously uncharacterized proteins. Approximately 65% of PSI structures report some type of ligand(s) that is bound in the crystal structure. Here, a description is given of how such ligands are handled and analyzed at the JCSG and a survey of the types, variety and frequency of ligands that are observed in the PSI structures is also compiled and analyzed, including illustrations of how these bound ligands have provided functional clues for annotation of proteins with little or no previous experimental characterization. Furthermore, a web server was developed as a tool to mine and analyze the PSI structures for bound ligands and other identifying features

  9. trans-Carbonyl[dihydrobis(1,2,4-triazol-1-yl-κN2borato]hydridobis(triphenylphosphine-κPruthenium(II acetonitrile solvate

    Directory of Open Access Journals (Sweden)

    Seong Huh

    2008-02-01

    Full Text Available In the crystal structure of the title compound, [Ru(C4H6BN6H(C18H15P2(CO]·C2H3N, discrete mononuclear complexes are found in which the Ru atom is coordinated by two triphenylphosphine (PPh3 ligands, one dihydrobis(1,2,4-triazol-1-ylborate ligand, one carbonyl ligand and one hydride atom within slightly distorted octahedra. The two P atoms of the PPh3 ligands are trans positioned and the two N atoms of the chelating dihydrobis(1,2,4-triazol-1-ylborate ligand occupy cis positions.

  10. Trans fatty acid isomers and the trans-9/trans-11 index in fat containing foods

    Science.gov (United States)

    Kuhnt, Katrin; Baehr, Melanie; Rohrer, Carsten; Jahreis, Gerhard

    2011-01-01

    To determine trans fatty acid (TFA) distribution of contemporary foods, especially regarding individual trans octadecenoic acids (trans C18:1), 339 German foods of six categories (semi-solid fats, deep-fried potato products, bakery products, confectioneries, instant products and butter) were analysed using two GC methods. Results showed a high variation of TFA content between and within the categories containing between 0 and 40.5% of FAME except in butter, which is a source of natural TFA. The mean TFA values were below 2.0% of FAME, however, bakery products contained 4.5% and butter fat 3.2%, respectively. In addition, the distribution of individual trans C18:1 differed. In samples containing ruminant fat (butter and various confectioneries), vaccenic acid (t11-C18:1, t11) predominated, while in foods containing industrially hydrogenated fats, elaidic acid (trans-9, t9-) and t10-C18:1 were the major trans isomers.. This was reflected by a low t9/t11 index of 0.3 and 0.5 in butter and ruminant fat containing confectioneries, respectively, whilst the highest index was observed in shortenings and deep-fried potato products at 5.2 and 6.8, respectively. In conclusion, the TFA content of foods available on the German market is generally declining, but substantial variations are present. The t9/t11 index could be used as an indicator to determine ruminant fat. Practical applications: A number of studies provide evidence that a high TFA intake, particularly of industrial origin, adversely affects human health. The TFA content of foods could be reduced due to the introduction of several mandatory regulations and modifications regarding the hydrogenation process of oils. The most abundant dietary TFA are the isomers of trans C18:1. Unfortunately, the differentiation of these isomers is not yet very common, though the trans C18:1 profile differs depending on its origin (bacterial hydrogenation in the rumen or industrial hydrogenation). To date, data for TFA content

  11. What a Difference Ancillary Thienyl Makes: Unexpected Additional Stabilization of the Diruthenium(III,II) but Not the Diosmium(III,II) Mixed-Valent State in Tetrazine Ligand-Bridged Complexes

    Czech Academy of Sciences Publication Activity Database

    Sarkas, B.; Kaim, W.; Klein, A.; Schwederski, B.; Fiedler, Jan; Duboc-Toia, C.; Lahiri, G. K.

    2003-01-01

    Roč. 42, č. 20 (2003), s. 6172-6174 ISSN 0020-1669 R&D Projects: GA MŠk OC D15.10; GA MŠk OC D14.20 Institutional research plan: CEZ:AV0Z4040901 Keywords : donor ligand s * Ru * dimers Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 3.389, year: 2003

  12. Characterization of the Mixed-Valent Intermediate (n = 3) of the Complex Series {(.mu., .eta.3:.eta.3-L)[(Ru(terpy)]2}n+ with the Unsaturated Bridging Ligand N,N´-Bis-(.alpha.-picolinoyl)hydrazido(2-) = L2-

    Czech Academy of Sciences Publication Activity Database

    Knödler, A.; Fiedler, Jan; Kaim, W.

    2004-01-01

    Roč. 23, č. 4 (2004), s. 701-707 ISSN 0277-5387 R&D Projects: GA ČR GA203/03/0821; GA MŠk OC D15.10 Institutional research plan: CEZ:AV0Z4040901 Keywords : EPR spectroscopy * hydrazido ligand * spectroelectrochemistry Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 1.586, year: 2004

  13. Ru-Os dyads based on a mixed bipyridine-terpyridine bridging ligand: modulation of the rate of energy transfer and pH-induced luminescence switching in the infrared domain.

    Science.gov (United States)

    Bar, Manoranjan; Maity, Dinesh; Deb, Sourav; Das, Shyamal; Baitalik, Sujoy

    2017-10-03

    A series of heterobimetallic complexes of compositions [(bpy/phen) 2 Ru(dipy-Hbzim-tpy)Os (tpy-PhCH 3 /H 2 pbbzim)] 4+ (bpy = 2,2'-bipyridine, phen = 1,10-phenanthroline, tpy-PhCH 3 = 4'-(4-methylphenyl)-2,2':6',2''-terpyridine and H 2 pbbzim = 2,6-bis(benzimidazole-2-yl)pyridine)), derived from a heteroditopic bpy-tpy bridging ligand, were synthesized and thoroughly characterized in this work. The heterometallic complexes exhibit two successive one-electron reversible metal-centered oxidations corresponding to Os II /Os III at lower potential and Ru II /Ru III at higher potential. All the four dyads exhibit very intense, ligand centered absorption bands in the UV region and moderately intense MLCT bands in the visible region. The dyads also show intense infrared emission with the emission maximum spanning between 734 nm and 775 nm with reasonably long room temperature lifetimes varying between 30 ns and 104 ns. Both steady state and time resolved luminescence spectroscopic investigations indicate that efficient and fast intramolecular energy transfer from the 3 MLCT state of the Ru(ii) center to the Os-center takes place in all the four dyads. In addition, the rate of energy transfer was found to depend on the terminal ligand on the Os-site. Due to the presence of a number of imidazole NH protons in the dyads, significant modulation of both the ground and excited state properties of the complexes was made possible by varying the pH of the solution. By varying the terminal ligand, pH-induced "on-off", "off-off-on" and "on-off-on" emission switching of the complexes was nicely demonstrated in the infrared region.

  14. Effects of quinones and flavonoids on the reduction of all-trans retinal to all-trans retinol in pig heart.

    Science.gov (United States)

    Shimada, Hideaki; Hirashima, Takaomi; Imamura, Yorishige

    2006-07-01

    We have recently purified a tetrameric carbonyl reductase from the cytosolic fraction of pig heart (pig heart carbonyl reductase). Since pig heart carbonyl reductase efficiently reduces all-trans retinal as the endogenous substrate, it probably plays an important role in retinoid metabolism in the heart. The purpose of the present study was to evaluate the inhibitory effects of quinones and flavonoids on the reduction of all-trans retinal to all-trans retinol catalyzed by pig heart carbonyl reductase, using pig heart cytosol. Of quinones tested, 9,10-phenanthrenequinone, a component of diesel exhaust particles, was the most potent inhibitor for the all-trans retinal reduction, and a significant inhibition was also observed for plumbagin and menadione. The order of the inhibitory potencies for flavonoids was kaempferol > quercetin > genistein > myricetin = apigenin = daidzein. However, the inhibitory potencies of flavonoids were much lower than that of 9,10-phenanthrenequinone. 9,10-Phenanthrenequinone competitively inhibited the all-trans retinal reduction, whereas kaempferol exhibited a mixed-type inhibition. It is likely that 9,10-phenanthrenequinone strongly inhibits the reduction of all-trans retinal to all-trans retinol by acting as the substrate inhibitor of pig heart carbonyl reductase present in pig heart cytosol.

  15. A new CdIIcoordination polymer with a self-penetrating architecture induced by the molecular conformation of a rigid bithiophene ligand.

    Science.gov (United States)

    Ji, Ning Ning; Shi, Zhi Qiang; Hu, Hai Liang

    2018-02-01

    The design and synthesis of coordination polymers with a self-penetrating architecture has attracted much interest not only due to their interesting structures but also due to their potential applications. 5,5'-Bis(pyridin-4-yl)-2,2'-bithiophene (bpbp), as a conjugated bithiophene ligand, can exhibit trans and cis conformations and this can lead to the construction of a self-penetrating architecture. In addition, the semi-rigid ancillary ligand 4,4'-oxybis(benzoic acid) (H 2 oba) can adopt different coordination modes, resulting in coordination polymers with high-dimensional skeletons. A new Cd II coordination polymer based on mixed ligands, namely poly[diaquapentakis[μ-5,5'-bis(pyridin-4-yl)-2,2'-bithiophene-κ 2 N:N']bis(nitrato-κ 2 O,O')tetrakis(μ 3 -4,4'-oxydibenzoato)-κ 10 O:O,O':O'',O''';κ 6 O:O':O''-pentacadmium(II)], [Cd 5 (C 14 H 14 O 5 ) 4 (NO 3 ) 2 (C 18 H 12 N 2 S 2 ) 5 (H 2 O) 2 ] n , (I), has been synthesized under solvothermal conditions and characterized by single-crystal X-ray diffraction, IR spectroscopy and elemental analysis. Single-crystal X-ray diffraction indicates that there are three crystallographically independent Cd II cations, three bpbp ligands, two deprotonated oba 2- ligands, one nitrate ligand and one coordinated water molecule in the asymmetric unit. One Cd II centre is seven-coordinated, exhibiting a distorted {CdN 2 O 5 } pentagonal bipyramidal geometry, while the other two Cd centres are both six-coordinated, showing slightly distorted {CdN 2 O 4 } octahedral geometries. The most interesting feature is the co-existence of trans and cis conformations in a single net, allowing structural interpenetration via self-threading and yet the expected self-penetrating structure was obtained. Topological analysis shows that the whole three-dimensional framework can be classified as a 3-nodal (4,6,6)-c net with Schläfli symbol {6 13 .8 2 } 2 {6 6 }, which is a new topology. Furthermore, the luminescence properties of (I) were examined

  16. trans-Tetracarbonylbis[tris(3-fluorophenylphosphane]chromium(0

    Directory of Open Access Journals (Sweden)

    M. N. Norlidah

    2011-12-01

    Full Text Available In the title compound, [Cr(C18H12F3P2(CO4], the Cr atom is octahedrally coordinated by four carbonyl ligands and the two tertiary phosphanes, which are trans to each other. The three benzene rings in one phosphane ligand make dihedral angles of 53.50 (9, 75.51 (10 and 80.63 (10° with each other, while in the other ligand these angles are 51.92 (10, 78.56 (11 and 86.80 (10°. C—H...O and C—H...F interactions link the molecules into a three-dimensional network. Each of the F atoms is disordered over two positions with refined occupancies of 0.944 (3:0.056 (3, 0.702 (4:0.298 (4, 0.829 (4:0.171 (4, 0.567 (4:0.433 (4, 0.545 (4:0.455 (4 and 0.920 (4:0.080 (4.

  17. Effect of an in-plane ligand on the electronic structures of bromo-bridged nano-wire Ni-Pd mixed-metal complexes, [Ni(1-x)Pd(x)(bn)2Br]Br2 (bn = 2S,3S-diaminobutane).

    Science.gov (United States)

    Sasaki, Mari; Wu, Hashen; Kawakami, Daisuke; Takaishi, Shinya; Kajiwara, Takashi; Miyasaka, Hitoshi; Breedlove, Brian K; Yamashita, Masahiro; Kishida, Hideo; Matsuzaki, Hiroyuki; Okamoto, Hiroshi; Tanaka, Hisaaki; Kuroda, Shinichi

    2009-08-03

    Single crystals of quasi-one-dimensional bromo-bridged Ni-Pd mixed-metal complexes with 2S,3S-diaminobutane (bn) as an in-plane ligand, [Ni(1-x)Pd(x)(bn)(2)Br]Br(2), were obtained by using an electrochemical oxidation method involving mixed methanol/2-propanol (1:1) solutions containing different ratios of [Ni(II)(bn)(2)]Br(2) and [Pd(II)(bn)(2)]Br(2). To investigate the competition between the electron-correlation of the Ni(III) states, or Mott-Hubbard states (MH), and the electron-phonon interaction of the Pd(II)-Pd(IV) mixed valence states, or charge-density-wave states (CDW), in the Ni-Pd mixed-metal compounds, X-ray structure analyses, X-ray oscillation photograph, and Raman, IR, ESR, and single-crystal reflectance spectra were analyzed. In addition, the local electronic structures of Ni-Pd mixed-metal single crystals were directly investigated by using scanning tunneling microscopy (STM) at room temperature and ambient pressure. The oxidation states of [Ni(1-x)Pd(x)(bn)(2)Br]Br(2) changed from a M(II)-M(IV) mixed valence state to a M(III) MH state at a critical mixing ratio (x(c)) of approximately 0.8, which is lower than that of [Ni(1-x)Pd(x)(chxn)(2)Br]Br(2) (chxn = 1R,2R-diaminocyclohexane) (x(c) approximately 0.9) reported previously. The lower value of x(c) for [Ni(1-x)Pd(x)(bn)(2)Br]Br(2) can be explained by the difference in their CDW dimensionalities because the three-dimensional CDW ordering in [Pd(bn)(2)Br]Br(2) observed by using X-ray diffuse scattering stabilizes the Pd(II)-Pd(IV) mixed valence state more than two-dimensional CDW ordering in [Pd(chxn)(2)Br]Br(2) does, which has been reported previously.

  18. Synthesis, characterization and antimicrobial activity of mixed ...

    African Journals Online (AJOL)

    A new series of Mn(II), Fe(II), Co(II), Cu(II) and Zn(II) mixed ligands-metal complexes derived from salicylic acid (SA) and 1,10-phenanthroline (PHEN) have been synthesized and characterized by spectroscopic studies. The coordination of the two ligands towards central metal ions has been proposed in the light of ...

  19. Synthesis and Structures of Two Lanthanide Complexes Containing a Mixed Ligand System: [Ln(Phen)2(L)3(HL)]·H2O [Ln = La, Ce; Phen = Phenanthroline; HL = Salicylic Acid

    International Nuclear Information System (INIS)

    Iravani, Effat; Nami, Navabeh; Nabizadeh, Fatemeh; Bayani, Elham; Neumueller, Bernhard

    2013-01-01

    The reaction of LnCl 3 ·7H 2 O [Ln = La (1), Ce (2)] with salicylic acid (HL) and 1,10-phenanthroline (Phen) at 20 .deg. C in H 2 O/ethanol gave after work-up and recrystallization two novel lanthanide complexes with general formula [Ln(Phen) 2 (L) 3 (HL)]·H 2 O. Compounds 1 and 2 were characterized by IR and UV-Vis spectroscopy, TGA, CHN as well as by X-ray analysis. According to these results, compounds 1 and 2 are isostructural and contain Ln 3+ ions with coordination number nine. Complexes 1 and 2 consist of two Phen, one neutral HL and three L anions (two L anions act as monodentate ligands and the third one is chelating to Ln 3+ ). Thermal decomposition led to primary loss of the Phen molecules. Then HL molecules and finally L moieties left the material to give Ln 2 O 3

  20. Synthesis, Characterization and Antimicrobial Activity of Mixed ...

    African Journals Online (AJOL)

    ADOWIE PERE

    phenanthroline, Salicylic acid, Mixed ligands-metal complexes, Transition metal, ... Cobalt is present in vitamin B12, a co-enzyme that plays significant roles in some biochemical processes. There are numerous lists of transition metals which are effective.

  1. Studies on coordination and addition compounds and anti microbial activity of some mixed ligand complexes of Au(III), Mo(II), Co(II) and Cd(II) with dibasic acid and heterocyclic amines and addition compounds of As(III) and Sb(III) halides with benzamide and acetophenon

    International Nuclear Information System (INIS)

    Hossain, M.; Sultana, C.; Saidul Islam, M.; Zakaria, C.M.

    2008-06-01

    Three new mixed ligand complexes of Au(III) and Mo(II) with dibasic acid e.g., homophthalic acid, oxalic acid and heterocylic amines e.g., quinonine, iso-quinonine, bipyridine, Phenylanaline and the two new addition compounds of As(III) and Sb(III) halides with N-donor ligands viz. benzamide and acetophenone and one complex [Cd(DPH)(IQ) 2 ], where IQ = Iso-quinoline and DPH = Deprotonated phthalic acid have been prepared according to the procedure in the literature. Their conventional physical and chemical analyses have been done. Their antibacterial studies against nine gram positive and five gram negative pathogenic bacteria and antifungal activities against eight plant and three human fungi have been evaluated. Kanamycin and Nystatin have been used as a standard for carrying out experiments of antibacterial and antifungal activities, respectively. The minimum inhibitory concentration (MIC) values of these compounds, as antibiotic against two gram positive and two gram negative pathogenic bacteria, have also been carried out and in this case, Amoxacilin antibiotic has been used as a standard antibiotic. (author)

  2. Trans and cis influences and effects in cobalamins and in their simple models.

    Science.gov (United States)

    De March, Matteo; Demitri, Nicola; Geremia, Silvano; Hickey, Neal; Randaccio, Lucio

    2012-11-01

    The interligand interactions in coordination compounds have been principally interpreted in terms of cis and trans influences and effects, which can be defined as the ability of a ligand X to affect the bond of another ligand, cis or trans to X, to the metal. This review analyzes these effects/influences in cobalamins (XCbl) and their simple models cobaloximes, LCo(chel)X. Important properties of these complexes, such as geometry, stability, and reactivity, can be rationalized in terms of steric and electronic factors of the ligands. Experimental evidence of normal and inverse trans influence is described in alkylcobaloximes for the first time. The study of simple B(12) models has complemented that on the more complex cobalamins, with particular emphasis on the properties of the axial L-Co-X moiety. Some of the conclusions reached for the axial fragment of simple models have also been qualitatively detected in cobalamins and have furnished new insight into the as yet unestablished mechanism for the homolytic cleavage of the Co - C bond in the AdoCbl-based enzymes. Copyright © 2012 Elsevier Inc. All rights reserved.

  3. TransForm: TransAlta 2000 annual report

    International Nuclear Information System (INIS)

    2001-01-01

    Financial information from TransAlta Corp. was presented along with a review of their operations throughout 2000 and a summary of the how the electric utility is doing in terms of power generation, independent power producers, transmission and energy marketing. The utility has changed from a regulated vertically integrated utility into one of Canada's largest non-regulated electric power generators. The utility sold its retail businesses in Alberta and New Zealand and now focuses on coal and hydro generation, gas generation, high-voltage transmission and energy marketing. The newly constructed Centralia, Washington generation facility was brought on line with 1,340 MW in May 2000, on time and on budget. This was the platform to diversify their generation into the United States. The utility reported a solid financial year with $177.9 million in earnings from continuing operations, an 83 per cent increase from 1999, driven mostly by the results of Centralia and power marketing and trading businesses. A financial loss was suffered when the Wabamum power plant in Alberta was shut down for several months to repair a boiler. The utility made excellent progress toward their goal of 15,000 megawatts by 2005 by starting with the construction of what will be one of Canada's largest cogeneration facilities at Sarnia, Ontario. TransAlta also commissioned a 360 MW cogeneration facility at Poplar Creek at Suncor's Fort McMurray oil sand facility. TransAlta also has an excellent track record in developing power generation projects internationally. refs., tabs., figs

  4. Comment on "Conformational analysis of triphenylphosphine ligands in stereogenic monometallic complexes: tools for predicting the preferred configuration of the triphenylphosphine rotor" by J. F. Costello, S. G. Davies, E. T. F. Gould and J. E. Thomson, Dalton Trans., 2015, 44, 5451.

    Science.gov (United States)

    Brunner, Henri; Tsuno, Takashi

    2017-04-11

    In half-sandwich compounds of the type [Cp*ML 1 L 2 PPh 3 ] the PPh 3 propeller is stabilized by attractive CH/π interactions in which C o -H bonds specifically interact with the C i and C o atoms of neighbouring phenyl rings, as in the T-shaped benzene dimer (i/o = ipso/ortho). This stabilization was not taken into account in a recent conformational analysis based on van der Waals energy calculations and minimization of steric compression (Dalton Trans., 2015, 44, 5451-5466). It is shown that in all 116 structures discussed in this analysis the C o H-C i/o distances fall below the sum of the van der Waals radii, establishing attractive CH/π interactions, although the short contacts could easily be avoided by phenyl rotation to relieve steric strain. In 53 of the described structures there are acyl substituents which form conformation-determining C o -HO(acyl) hydrogen bonds that are not taken into account in the recent analysis. The steric-only model is not an adequate description of M-PPh 3 complexes.

  5. Syntheses, structures and photoelectrochemical properties of three water-stable, visible light absorbing mental-organic frameworks based on tetrakis(4-carboxyphenyl)silane and 1,4-bis(pyridyl)benzene mixed ligands

    Science.gov (United States)

    Guo, Tiantian; Yang, Xiaowei; Li, Ruyan; Liu, Xiaoyu; Gao, Yanling; Dai, Zhihui; Fang, Min; Liu, Hong-Ke; Wu, Yong

    2017-09-01

    Photovoltaics (PV), which directly convert solar energy into electricity generally using semiconductors, offer a practical and sustainable solution to the current energy shortage and environmental pollution crisis. Photovoltaic applications of metal-organic frameworks (MOFs) belong to a relatively new area of research. Given that UV light accounts for only 4% while visible light contributes 43% of solar energy, it is rather imperative to develop semiconductors with narrow band gaps so that they could absorb visible light. In this work, three water-stable, narrow band semiconducting MOFs of [Cu(H2TCS)(H2O)] (1), [Co(H2TCS)(BPB)] (2) and [Ni(H2TCS)(BPB)] (3) were synthesized using tetrakis(4-carboxyphenyl)silane (H4TCS) and 1,4-bis (pyridyl)benzene (BPB) in water, and structurally characterized by single-crystal X-ray diffractions. MOF 1 has a 2D structure. MOF 2 and 3 are isostructrual and have 3D frameworks formed by interwoven 2D layers. All three MOFs are stable in acidic water solutions and can be stable in water for 7 days. MOFs 1-3 absorb UV and visible light and have band gaps of 0.50, 1.77 and 1.49 eV, respectively. Rapid and stable photocurrent responses of MOFs 1-3 under UV and visible light illuminations are observed. This work demonstrates that using electron rich Cu2+, Co2+, or Ni2+ as metal nodes can effectively decrease the band gaps of MOFs to make them absorbing visible light. To increase the conjugation in the linker is generally considered to be the method to decrease the band gap of MOFs. The conjugation in H4TCS is not significant and this ligand basically only absorbs UV light. However, by using electron rich Cu2+ ions as metal nodes, the prepared [Cu(H2TCS)(H2O)]·H2O (1) absorbs broadly in the visible light region. Thus, this work suggests that by using electron rich Cu2+, many narrow-band semiconductor MOFs can be prepared even by using ligands which only absorbs UV light.

  6. Trans issues in Liz Lochhead's 'Not Changed'

    OpenAIRE

    Kaličanin Milena M.

    2017-01-01

    The paper is divided into four sections. In the first section entitled 'Introducing and Defining Trans (Issues)', the basic terms of transgender, transvestite, and transsexual are defined by relying on Stryker's Transgender History (2008). The second part of the paper, 'Trans Studies: In-Between Feminist and Queer Theory?', places transgender studies into an academic context by referring to the theoretical framework provided by trans theorists Stryker, Stone, and Ranck who unanimously claim t...

  7. Suicide Protective Factors Among Trans Adults

    OpenAIRE

    Moody, Ch?rie; Smith, Nathan Grant

    2013-01-01

    A recent study indicated a suicide attempt rate of 41?% among trans (e.g., trans, transgender, transexual/transsexual, genderqueer, two-spirit) individuals. Although this rate is alarming, there is a dearth of literature regarding suicide prevention for trans individuals. A vital step in developing suicide prevention models is the identification of protective factors. It was hypothesized that social support from friends, social support from family, optimism, reasons for living, and suicide re...

  8. Syntheses, crystal structures and magnetic properties of two mixed-valence Co(iii)Co(ii) compounds derived from Schiff base ligands: field-supported single-ion-magnet behavior with easy-plane anisotropy.

    Science.gov (United States)

    Mandal, Shuvankar; Mondal, Suraj; Rajnák, Cyril; Titiš, Ján; Boča, Roman; Mohanta, Sasankasekhar

    2017-10-14

    Two μ-phenoxo-μ 1,1 -azide dinuclear Co III Co II complexes [Co III (N 3 ) 2 L 1 (μ 1,1 -N 3 )Co II (N 3 )]·MeOH (1) and [Co III (N 3 ) 2 L 2 (μ 1,1 -N 3 )Co II (N 3 )]·MeOH (2) (HL 1 and HL 2 are two Schiff base ligands having N 2 O-N 2 O compartments) both possess one hexacoordinate Co(iii) and one pentacoordinate Co(ii) center. DC magnetic susceptibility and magnetization measurements show an appreciable amount of positive magnetic anisotropy (D/hc∼ 40 cm -1 ) that is also confirmed by ab initio CASSCF calculations. AC susceptibility measurements of 1 reveal that it exhibits a slow magnetic relaxation with two relaxation channels. The external magnetic field supports the low-frequency (LF) channel that escapes on heating more progressively than the high-frequency (HF) branch. The relaxation time is as slow as τ = 255 ms at T = 1.9 K and B DC = 0.6 T, where the LF mole fraction is 69%. The complex 2 also displays similar field-supported slow magnetic relaxation with two relaxation channels.

  9. The Danish trans-fatty acids ban

    DEFF Research Database (Denmark)

    Vallgårda, Signild

    2017-01-01

    In 2003 an executive order was issued banning industrially produced trans-fatty acids above a low level in food items in Denmark. To date, only a few other countries have followed Denmark’s example. The way health consequences of trans fats were translated by the different actors enabled the crea......In 2003 an executive order was issued banning industrially produced trans-fatty acids above a low level in food items in Denmark. To date, only a few other countries have followed Denmark’s example. The way health consequences of trans fats were translated by the different actors enabled...

  10. Single crystal EPR of the mixed-ligand complex of copper(II) with L-glutamic acid and 1,10-phenanthroline: a study on the narrowing of the hyperfine structure by exchange.

    Science.gov (United States)

    Neuman, Nicolás I; Franco, Vanina G; Ferroni, Felix M; Baggio, Ricardo; Passeggi, Mario C G; Rizzi, Alberto C; Brondino, Carlos D

    2012-12-20

    We report an EPR study at X- and Q-bands of polycrystalline and single crystal samples of the mixed copper(II) complex with L-glutamic acid (glu) and 1,10-phenantroline (phen), [Cu(glu)(phen)(H(2)O)](+) NO(3)(-)·2(H(2)O). The polycrystalline sample spectrum at Q-band showed well resolved g(∥ )and g(⊥) features and partially solved hyperfine structure at g(∥), typical for weakly exchange coupled systems. This is confirmed from the angular variation of the EPR spectra which shows for certain magnetic field orientations a partially solved hyperfine structure characteristic of weak exchange, whereas a single Lorentzian line corresponding to strong exchange is observed for others. Analysis and simulation of the single crystal EPR spectra were performed using the random frequency modulation model of Anderson. Numerical simulations of the angular variation of the EPR spectra showed that the narrowing of the hyperfine structure is due to an exchange-mediated mechanism in which transitions between any pair of lines are equally likely. The exchange interaction responsible for this process is mediated by hydrophobic interactions between two phen molecules and a mixed chemical path of the type CuA-O(ap)H···O-C-O(eq)-CuB, for which we evaluated an average isotropic exchange parameter |J| ≈ 25 × 10(-4) cm(-1).

  11. Efficient hierarchical trans-dimensional Bayesian inversion of magnetotelluric data

    Science.gov (United States)

    Xiang, Enming; Guo, Rongwen; Dosso, Stan E.; Liu, Jianxin; Dong, Hao; Ren, Zhengyong

    2018-02-01

    This paper develops an efficient hierarchical trans-dimensional (trans-D) Bayesian algorithm to invert magnetotelluric (MT) data for subsurface geoelectrical structure, with unknown geophysical model parameterization (the number of conductivity-layer interfaces) and data error models parameterized by an auto-regressive (AR) process to account for potential error correlations. The reversible-jump Markov-chain Monte Carlo algorithm, which adds/removes interfaces and AR parameters in birth/death steps, is applied to sample the trans-D posterior probability density for model parameterization, model parameters, error variance and AR parameters, accounting for the uncertainties of model dimension and data-error statistics in the uncertainty estimates of the conductivity profile. To provide efficient sampling over the multiple subspaces of different dimensions, advanced proposal schemes are applied. Parameter perturbations are carried out in principal-component space, defined by eigen-decomposition of the unit-lag model covariance matrix, to minimize the effect of inter-parameter correlations and provide effective perturbation directions and length scales. Parameters of new layers in birth steps are proposed from the prior, instead of focused distributions centred at existing values, to improve birth acceptance rates. Parallel tempering, based on a series of parallel interacting Markov chains with successively relaxed likelihoods, is applied to improve chain mixing over model dimensions. The trans-D inversion is applied in a simulation study to examine the resolution of model structure according to the data information content. The inversion is also applied to a measured MT data set from south-central Australia.

  12. Sterically demanding iminopyridine ligands

    NARCIS (Netherlands)

    Irrgang, Torsten; Keller, Sandra; Maisel, Heidi; Kretschmer, Winfried; Kempe, Rhett

    Two sterically demanding iminopyridine ligands, (2,6-diisopropylphenyl)[6-(2,4,6-triisopropylphenyl)pyridin-2-ylmeth- ylene]amine and (2,6-diisopropylphenyl)]6-(2,6-dimethylphenyl)pyridin-2-ylmethylene]amine, were prepared by a two-step process: first, condensation of 6-bromopyridine-2-carbaldehyde

  13. Suicide protective factors among trans adults.

    Science.gov (United States)

    Moody, Chérie; Smith, Nathan Grant

    2013-07-01

    A recent study indicated a suicide attempt rate of 41 % among trans (e.g., trans, transgender, transexual/transsexual, genderqueer, two-spirit) individuals. Although this rate is alarming, there is a dearth of literature regarding suicide prevention for trans individuals. A vital step in developing suicide prevention models is the identification of protective factors. It was hypothesized that social support from friends, social support from family, optimism, reasons for living, and suicide resilience, which are known to protect cis (non-trans) individuals, also protect trans individuals. A sample of self-identified trans Canadian adults (N = 133) was recruited from LGBT and trans LISTSERVs. Data were collected online using a secure survey platform. A three block hierarchical multiple regression model was used to predict suicidal behavior from protective factors. Social support from friends, social support from family, and optimism significantly and negatively predicted 33 % of variance in participants' suicidal behavior after controlling for age. Reasons for living and suicide resilience accounted for an additional 19 % of the variance in participants' suicidal behavior after controlling for age, social support from friends, social support from family, and optimism. Of the factors mentioned above, perceived social support from family, one of three suicide resilience factors (emotional stability), and one of six reasons for living (child-related concerns) significantly and negatively predicted participants' suicidal behavior. Overall, these findings can be used to inform the practices of mental health workers, medical doctors, and suicide prevention workers working with trans clients.

  14. Unscripting Curriculum: Toward a Critical Trans Pedagogy

    Science.gov (United States)

    Keenan, Harper Benjamin

    2017-01-01

    In this essay, Harper B. Keenan draws on his own experience as a white queer and trans educator to consider the meaning of a critical trans pedagogy. Amid dissonant narratives of equal rights and subjection, he explores how his classroom teaching is shaped by his own experience of gender conditioning as well as by the contemporary political…

  15. Trans Ova Genetics, L.C.

    Science.gov (United States)

    The EPA is providing notice of a proposed Administrative Penalty Assessment against Trans Ova Genetics, L.C., a business located at 2938 380th Street Sioux Center, IA 51250, for alleged violations at the Trans Ova Genetics, L.C.’s facility located in 12425

  16. TransAlta: More than a utility

    International Nuclear Information System (INIS)

    Mikalson, D.A.

    1991-01-01

    TransAlta Utilities Corporation is Canada's largest privately owned utility and is also a major coal mining company. In 1989, TransAlta produced 20.9% of all coal mined in Canada. A brief history of TransAlta is presented along with TransAlta's present coal operations and plans for the next three years. An overview is presented of how TransAlta Fuel Supply is organized to utilize contracted mining operation, engineering and environmental services and in-house capabilities. Recent strategic initiatives to improve organizational efficiency and the mining operations are discussed. These range from developing a common departmental vision to modifying major mining equipment. TransAlta's proactive role in clean coal combustion such as low NOx-SOx burner, integrated combined cycle gasification, and other energy research projects is reviewed. A summary is provided of recent participation of TransAlta in environmental management initiatives. Recent successes of TransAlta's unregulated subsidiary in the development of cogeneration facilities and the future of this area of business are discussed. 8 refs., 4 figs

  17. Synthesis through Trans-disciplinarity

    DEFF Research Database (Denmark)

    Hansen, Hanne Tine Ring

    2006-01-01

    , architecture and landscape provides a great architectural experience. Another is Jörn Utzon's church in Bagsvaerd, Denmark, where the treatment of construction, acoustics and daylight ingeniously fuses with the church's function and architectural expression, once again offering a unique architectural...... experience. In relation to ‘environmentally sustainable' architecture the importance of synthesis becomes even more apparent, however, as the success of the design depends on how, and if, a synthesis is achieved between technology and architectural design.[2] This understanding has led me to consider how...... synthesis is a requirement for creating successful ‘environmentally sustainable' architecture through the application of trans-disciplinarity, which leads to an increased awareness of the differences in decision-making as well as that of communication barriers between the different professions...

  18. Fragile X mental retardation protein regulates trans-synaptic signaling in Drosophila

    Directory of Open Access Journals (Sweden)

    Samuel H. Friedman

    2013-11-01

    Fragile X syndrome (FXS, the most common inherited determinant of intellectual disability and autism spectrum disorders, is caused by loss of the fragile X mental retardation 1 (FMR1 gene product (FMRP, an mRNA-binding translational repressor. A number of conserved FMRP targets have been identified in the well-characterized Drosophila FXS disease model, but FMRP is highly pleiotropic in function and the full spectrum of FMRP targets has yet to be revealed. In this study, screens for upregulated neural proteins in Drosophila fmr1 (dfmr1 null mutants reveal strong elevation of two synaptic heparan sulfate proteoglycans (HSPGs: GPI-anchored glypican Dally-like protein (Dlp and transmembrane Syndecan (Sdc. Our recent work has shown that Dlp and Sdc act as co-receptors regulating extracellular ligands upstream of intracellular signal transduction in multiple trans-synaptic pathways that drive synaptogenesis. Consistently, dfmr1 null synapses exhibit altered WNT signaling, with changes in both Wingless (Wg ligand abundance and downstream Frizzled-2 (Fz2 receptor C-terminal nuclear import. Similarly, a parallel anterograde signaling ligand, Jelly belly (Jeb, and downstream ERK phosphorylation (dpERK are depressed at dfmr1 null synapses. In contrast, the retrograde BMP ligand Glass bottom boat (Gbb and downstream signaling via phosphorylation of the transcription factor MAD (pMAD seem not to be affected. To determine whether HSPG upregulation is causative for synaptogenic defects, HSPGs were genetically reduced to control levels in the dfmr1 null background. HSPG correction restored both (1 Wg and Jeb trans-synaptic signaling, and (2 synaptic architecture and transmission strength back to wild-type levels. Taken together, these data suggest that FMRP negatively regulates HSPG co-receptors controlling trans-synaptic signaling during synaptogenesis, and that loss of this regulation causes synaptic structure and function defects characterizing the FXS disease state.

  19. trans-cis photoisomerization of azobenzene-conjugated dithiolato-bipyridine platinum(II) complexes: extension of photoresponse to longer wavelengths and photocontrollable tristability.

    Science.gov (United States)

    Sakamoto, Ryota; Kume, Shoko; Sugimoto, Manabu; Nishihara, Hiroshi

    2009-01-01

    Azobenzene derivatives modified with dithiolato-bipyridine platinum(II) complexes were synthesized, revealing their highly extended photoresponses to the long wavelength region as well as unique photocontrollable tristability. The absorptions of trans-1 and trans-2 with one azobenzene group on the dithiolene and bipyridine ligands, respectively, cover the range from 300 to 700 nm. These absorptions are ascribed, by means of time-dependent (TD)DFT calculations, to transitions from dithiolene(pi) to bipyridine(pi*), namely, interligand charge transfer (CT), pi-pi*, and n-pi* transitions of the azobenzene unit, and pi-pi* transitions of the bipyridine ligand. In addition, only trans-1 shows distinctive electronic bands, assignable to transitions from the dithiolene(pi) to azobenzene(pi*), defined as intraligand CT. Complex 1 shows photoisomerization behavior opposite to that of azobenzene: trans-to-cis and cis-to-trans conversions proceed with 405 and 312 nm irradiation, which correspond to excitation with the intraligand CT, and pi-pi* bands of the azobenzene and bipyridine units, respectively. In contrast, complex 2 shows photoisomerization similar to that of azobenzene: trans-to-cis and cis-to-trans transformations occur with 365 and 405 nm irradiation, respectively. Irradiation at 578 nm, corresponding to excitation of the interligand CT transitions, results in cis-to-trans conversion of both 1 and 2, which is the longest wavelength ever reported to effect the photoisomerization of the azobenzene group. The absorption and photochromism of 4, which has azobenzene groups on both the dithiolato and bipyridine ligands, have characteristics quite similar to those of 1 and 2, which furnishes 4 with photocontrollable tristability in a single molecule using light at 365, 405, and 578 nm. We also clarified that 1 and 2 have high photoisomerization efficiencies, and good thermal stability of the cis forms. Complexes 3 and 5 have almost the identical photoresponse to those

  20. Trans fat consumption and aggression.

    Directory of Open Access Journals (Sweden)

    Beatrice A Golomb

    Full Text Available Dietary trans fatty acids (dTFA are primarily synthetic compounds that have been introduced only recently; little is known about their behavioral effects. dTFA inhibit production of omega-3 fatty acids, which experimentally have been shown to reduce aggression. Potential behavioral effects of dTFA merit investigation. We sought to determine whether dTFA are associated with aggression/irritability. METHODOLGY/PRINICPAL FINDINGS: We capitalized on baseline dietary and behavioral assessments in an existing clinical trial to analyze the relationship of dTFA to aggression. Of 1,018 broadly sampled baseline subjects, the 945 adult men and women who brought a completed dietary survey to their baseline visit are the target of this analysis. Subjects (seen 1999-2004 were not on lipid medications, and were without LDL-cholesterol extremes, diabetes, HIV, cancer or heart disease. Outcomes assessed adverse behaviors with impact on others: Overt Aggression Scale Modified-aggression subscale (primary behavioral endpoint; Life History of Aggression; Conflict Tactics Scale; and self-rated impatience and irritability. The association of dTFA to aggression was analyzed via regression and ordinal logit, unadjusted and adjusted for potential confounders (sex, age, education, alcohol, and smoking. Additional analyses stratified on sex, age, and ethnicity, and examined the prospective association. Greater dTFA were strongly significantly associated with greater aggression, with dTFA more consistently predictive than other assessed aggression predictors. The relationship was upheld with adjustment for confounders, was preserved across sex, age, and ethnicity strata, and held cross-sectionally and prospectively.This study provides the first evidence linking dTFA with behavioral irritability and aggression. While confounding is always a concern in observational studies, factors including strength and consistency of association, biological gradient, temporality, and

  1. Mass spectrometry-based monitoring of millisecond protein–ligand binding dynamics using an automated microfluidic platform

    Energy Technology Data Exchange (ETDEWEB)

    Cong, Yongzheng; Katipamula, Shanta; Trader, Cameron D.; Orton, Daniel J.; Geng, Tao; Baker, Erin S.; Kelly, Ryan T.

    2016-01-01

    Characterizing protein-ligand binding dynamics is crucial for understanding protein function and developing new therapeutic agents. We have developed a novel microfluidic platform that features rapid mixing of protein and ligand solutions, variable incubation times, and on-chip electrospray ionization to perform label-free, solution-based monitoring of protein-ligand binding dynamics. This platform offers many advantages including automated processing, rapid mixing, and low sample consumption.

  2. Synthesis, characterization and antimicrobial activity of mixed ...

    African Journals Online (AJOL)

    Synthesis, characterization and antimicrobial activity of mixed ascorbic acid - nicotinamide metal complexes. ... The result of the antimicrobial studies showed that the mixed complexes have higher inhibitory activity than the original ligands against the tested bacteria and fungi species. KEY WORDS: Ascorbic acid, ...

  3. Analysis of macromolecules, ligands and macromolecule-ligand complexes

    Science.gov (United States)

    Von Dreele, Robert B [Los Alamos, NM

    2008-12-23

    A method for determining atomic level structures of macromolecule-ligand complexes through high-resolution powder diffraction analysis and a method for providing suitable microcrystalline powder for diffraction analysis are provided. In one embodiment, powder diffraction data is collected from samples of polycrystalline macromolecule and macromolecule-ligand complex and the refined structure of the macromolecule is used as an approximate model for a combined Rietveld and stereochemical restraint refinement of the macromolecule-ligand complex. A difference Fourier map is calculated and the ligand position and points of interaction between the atoms of the macromolecule and the atoms of the ligand can be deduced and visualized. A suitable polycrystalline sample of macromolecule-ligand complex can be produced by physically agitating a mixture of lyophilized macromolecule, ligand and a solvent.

  4. Trans* necropolitics. Gender Identity Law in Argentina

    Directory of Open Access Journals (Sweden)

    Martin De Mauro Rucovsky

    Full Text Available On May 9th, 2012, the Argentinean Senate converted into law the long collective process, driven by trans* activism, towards the legal recognition of gender identity. The Gender Identity Act (GIA meant a large contribution to the field of civil and sexual rights interationally, especially in the matter of trans* policy. Nevertheless, what was at stake in the approval of the GIA was not just a step forward in legal terms and at a personal level for trans* people, but a whole set of representations, desires and social stakes on trans* lives and population. Thus, as regards to the scope and achievements of the GIA and its social and parliamentary debates, we can assert that in that realm a specific trans* life does not qualify as a living life. This article addresses the specific ways of presentation and apprehension of trans* lives in parliamentary debates about the GIA, and in social disputes within trans* activism. A biopolitical analysis of gender identity leads us to rethink the social conditions that sustain life and, by the same token, the interpretative frameworks of death.

  5. Radiobiology with DNA ligands

    International Nuclear Information System (INIS)

    Weinreich, R.; Argentini, M.; Guenther, I.; Koziorowski, J.; Larsson, B.; Nievergelt-Egido, M.C.; Salt, C.; Wyer, L.; Dos Santos, D.F.; Hansen, H.J.

    1997-01-01

    The paper deals with the following topics: labelling of DNA ligands and other tumour-affinic compounds with 4.15-d 124 I, radiotoxicity of Hoechst 33258 and 33342 and of iodinated Hoechst 33258 in cell cultures, preparation of 76 Br-, 123 I-, and 221 At-labelled 5-halo-2'-deoxyuridine, chemical syntheses of boron derivatives of Hoechst 33258.III., Gadolinium neutron capture therapy

  6. Therapeutic androgen receptor ligands

    Science.gov (United States)

    Allan, George F.; Sui, Zhihua

    2003-01-01

    In the past several years, the concept of tissue-selective nuclear receptor ligands has emerged. This concept has come to fruition with estrogens, with the successful marketing of drugs such as raloxifene. The discovery of raloxifene and other selective estrogen receptor modulators (SERMs) has raised the possibility of generating selective compounds for other pathways, including androgens (that is, selective androgen receptor modulators, or SARMs). PMID:16604181

  7. The Trans-Pacific Partnership

    Directory of Open Access Journals (Sweden)

    Voon Tania

    2016-12-01

    Full Text Available This article provides an overview of the recently concluded Trans-Pacific Partnership Agreement (TPP, a treaty the parties have described as comprehensive and ambitious, yet also representing a balance of competing interests. The article focuses on the TPP’s chapters relating to investment, services, intellectual property and regulatory coherence, each of which provides insight into the motivations that drove the conclusion of the TPP and the negotiating dynamics that determined its final content. In areas such as investment, the TPP takes a more balanced approach than many earlier agreements, providing greater safeguards for the regulatory autonomy of states while still embodying core protections for foreign investors. In relation to intellectual property and services, the TPP goes beyond earlier agreements in several key respects, such as preventing the imposition of local presence requirements for service providers or requiring longer copyright terms than those demanded by other international treaties. The TPP chapter on regulatory coherence is one of the most novel features of the treaty, as regulatory coherence is not frequently included in earlier trade agreements, demonstrating the increased focus of states on addressing regulatory barriers to trade and investment. While all of these elements of the TPP are interesting in their own right, given the number and size of the parties involved in the agreement, they also provide valuable guidance about the direction of other ongoing and future preferential trade agreement negotiations, such as the proposed Transatlantic Trade and Investment Partnership (TTIP and Trade in Services Agreement (TiSA.

  8. Transsynaptic Mapping of Second-Order Taste Neurons in Flies by trans-Tango.

    Science.gov (United States)

    Talay, Mustafa; Richman, Ethan B; Snell, Nathaniel J; Hartmann, Griffin G; Fisher, John D; Sorkaç, Altar; Santoyo, Juan F; Chou-Freed, Cambria; Nair, Nived; Johnson, Mark; Szymanski, John R; Barnea, Gilad

    2017-11-15

    Mapping neural circuits across defined synapses is essential for understanding brain function. Here we describe trans-Tango, a technique for anterograde transsynaptic circuit tracing and manipulation. At the core of trans-Tango is a synthetic signaling pathway that is introduced into all neurons in the animal. This pathway converts receptor activation at the cell surface into reporter expression through site-specific proteolysis. Specific labeling is achieved by presenting a tethered ligand at the synapses of genetically defined neurons, thereby activating the pathway in their postsynaptic partners and providing genetic access to these neurons. We first validated trans-Tango in the Drosophila olfactory system and then implemented it in the gustatory system, where projections beyond the first-order receptor neurons are not fully characterized. We identified putative second-order neurons within the sweet circuit that include projection neurons targeting known neuromodulation centers in the brain. These experiments establish trans-Tango as a flexible platform for transsynaptic circuit analysis. Copyright © 2017 Elsevier Inc. All rights reserved.

  9. Structures, magnetochemistry, spectroscopy, theoretical study, and catechol oxidase activity of dinuclear and dimer-of-dinuclear mixed-valence Mn(III)Mn(II) complexes derived from a macrocyclic ligand.

    Science.gov (United States)

    Jana, Arpita; Aliaga-Alcalde, Núria; Ruiz, Eliseo; Mohanta, Sasankasekhar

    2013-07-01

    The work in this paper presents syntheses, characterization, magnetic properties (experimental and density functional theoretical), catecholase activity, and electrospray ionization mass spectroscopic (ESI-MS positive) studies of two mixed-valence dinuclear Mn(III)Mn(II) complexes, [Mn(III)Mn(II)L(μ-O2CMe)(H2O)2](ClO4)2·H2O·MeCN (1) and [Mn(III)Mn(II)L(μ-O2CPh)(MeOH)(ClO4)](ClO4) (2), and a Mn(III)Mn(II)Mn(II)Mn(III) complex, [{Mn(III)Mn(II)L(μ-O2CEt)(EtOH)}2(μ-O2CEt)](ClO4)3 (3), derived from the Robson-type macrocycle H2L, which is the [2 + 2] condensation product of 2,6-diformyl-4-methylphenol and 2,2-dimethyl-1,3-diaminopropane. In 1 and 2 and in two Mn(III)Mn(II) units in 3, the two metal centers are bridged by a bis(μ-phenoxo)-μ-carboxylate moiety. The two Mn(II) centers of the two Mn(III)Mn(II) units in 3 are bridged by a propionate moiety, and therefore this compound is a dimer of two dinuclear units. The coordination geometry of the Mn(III) and Mn(II) centers are Jahn-Teller distorted octahedral and distorted trigonal prism, respectively. Magnetic studies reveal weak ferro- or antiferromagnetic interactions between the Mn(III) and Mn(II) centers in 1 (J = +0.08 cm(-1)), 2 (J = -0.095 cm(-1)), and 3 (J1 = +0.015 cm(-1)). A weak antiferromagnetic interaction (J2 = -0.20 cm(-1)) also exists between the Mn(II) centers in 3. DFT methods properly reproduce the nature of the exchange interactions present in such systems. A magneto-structural correlation based on Mn-O bridging distances has been proposed to explain the different sign of the exchange coupling constants. Utilizing 3,5-di-tert-butyl catechol (3,5-DTBCH2) as the substrate, catecholase activity of all the three complexes has been checked in MeCN and MeOH, revealing that all three are active catalysts with Kcat values lying in the range 7.5-64.7 h(-1). Electrospray ionization mass (ESI-MS positive) spectra of the complexes 1-3 have been recorded in MeCN solutions, and the positive ions have been

  10. Segregation of Axial Motor and Sensory Pathways via Heterotypic Trans-Axonal Signaling

    Science.gov (United States)

    Gallarda, Benjamin W.; Bonanomi, Dario; Müller, Daniel; Brown, Arthur; Alaynick, William A.; Andrews, Shane E.; Lemke, Greg; Pfaff, Samuel L.; Marquardt, Till

    2011-01-01

    Execution of motor behaviors relies on circuitries effectively integrating immediate sensory feedback to efferent pathways controlling muscle activity. It remains unclear how, during neuromuscular circuit assembly, sensory and motor projections become incorporated into tightly coordinated, yet functionally separate pathways. We report that, within axial nerves, establishment of discrete afferent and efferent pathways depends on coordinate signaling between coextending sensory and motor projections. These heterotypic axon-axon interactions require motor axonal EphA3/EphA4 receptor tyrosine kinases activated by cognate sensory axonal ephrin-A ligands. Genetic elimination of trans-axonal ephrin-A → EphA signaling in mice triggers drastic motor-sensory miswiring, culminating in functional efferents within proximal afferent pathways. Effective assembly of a key circuit underlying motor behaviors thus critically depends on trans-axonal signaling interactions resolving motor and sensory projections into discrete pathways. PMID:18403711

  11. Profile of trans fatty acids (FAs) including trans polyunsaturated FAs in representative fast food samples.

    Science.gov (United States)

    Tyburczy, Cynthia; Delmonte, Pierluigi; Fardin-Kia, Ali Reza; Mossoba, Magdi M; Kramer, John K G; Rader, Jeanne I

    2012-05-09

    The content of trans fat in foods is most commonly determined by summing the levels of individual trans fatty acids (FAs), analyzed as FA methyl esters (FAME) by gas chromatography. Current Official Methods of the American Oil Chemists' Society (AOCS) enable quantitation of total trans fat in foods but were not designed for the determination of transFA isomeric compositions. In the present study, the content of trans fat in 32 representative fast food samples ranged from 0.1 to 3.1 g per serving, as determined according to AOCS Official Method Ce 1j-07. Further analysis of FAME using the 200 m SLB-IL111 ionic liquid column yielded quantitative results of total, trans, saturated, and cis unsaturated fat that were comparable to those of Method Ce 1j-07 and also allowed for the complementary determination of individual trans 18:1, trans 18:2, and trans 18:3 FA isomeric compositions under conditions suitable for routine sample analysis.

  12. Mixed and Mixing Systems Worldwide

    African Journals Online (AJOL)

    Sean.Donlan

    MIXED AND MIXING SYSTEMS WORLDWIDE: A PREFACE. 2012 VOLUME 15 No 3 ... dissenters, Mixed Jurisdictions Worldwide galvanised scholarship on mixed systems, especially for jurists in those ... Comparative Law, the International Association of Legal Science and numerous law faculties across the classical ...

  13. Bexarotene ligand pharmaceuticals.

    Science.gov (United States)

    Hurst, R E

    2000-12-01

    Bexarotene (LGD-1069), from Ligand, was the first retinoid X receptor (RXR)-selective, antitumor retinoid to enter clinical trials. The company launched the drug for the treatment of cutaneous T-cell lymphoma (CTCL), as Targretin capsules, in the US in January 2000 [359023]. The company filed an NDA for Targretin capsules in June 1999, and for topical gel in December 1999 [329011], [349982] specifically for once-daily oral administration for the treatment of patients with early-stage CTCL who have not tolerated other therapies, patients with refractory or persistent early stage CTCL and patients with refractory advanced stage CTCL. The FDA approved Targretin capsules at the end of December 1999 for once-daily oral treatment of all stages of CTCL in patients refractory to at least one prior systemic therapy, at an initial dose of 300 mg/m2/day. After an NDA was submitted in December 1999 for Targretin gel, the drug received Priority Review status for use as a treatment of cutaneous lesions in patients with stage IA, IB or IIA CTCL [354836]. The FDA issued an approvable letter in June 2000, and granted marketing clearance for CTCL in the same month [370687], [372768], [372769], [373279]. Ligand had received Orphan Drug designation for this indication [329011]. At the request of the FDA, Ligand agreed to carry out certain post-approval phase IV and pharmacokinetic studies [351604]. The company filed an MAA with the EMEA for Targretin Capsules to treat lymphoma in November 1999 [348944]. The NDA for Targretin gel is based on a multicenter phase III trial that was conducted in the US, Canada, Europe and Australia involving 50 patients and a multicenter phase I/II clinical program involving 67 patients. Targretin gel was evaluated for the treatment of patients with early stage CTCL (IA-IIA) who were refractory to, intolerant to, or reached a response plateau for at least 6 months on at least two prior therapies. Efficacy results exceeded the protocol-defined response

  14. Does your organization use gender inclusive forms? Nurses' confusion about trans* terminology.

    Science.gov (United States)

    Carabez, Rebecca; Pellegrini, Marion; Mankovitz, Andrea; Eliason, Mickey; Scott, Megan

    2015-11-01

    To describe nurses confusion around trans* terminology and to provide a lesson in Trans* 101 for readers. Of the estimated 9 million persons in the United States of America who are identified as lesbian, gay, bisexual and transgender, about 950,000 (0.2-0.5% of adult population) are identified as trans* (a term that encompasses the spectrum, including transgender, transsexual, trans man, trans woman and other terms). The Institute of Medicine (2011, The health of lesbian, gay, bisexual and transgender people: Building a foundation for better understanding. The National Academies Press, Washington, DC) identified transgender persons as an understudied population with significant need for health research, yet the nursing literature contains little guidance for educating nurses on trans* issues. This is a mixed methods structured interview design with nurse key informants. The scripted interview was based on the Health Care Equality Index, which evaluates patient-centred care to lesbian, gay, bisexual and transgender patients and families. These data were part of a larger research study that explored the current state of lesbian, gay, bisexual and transgender-sensitive nursing practice. Undergraduate nursing students recruited and interviewed 268 nurse key informants about gender inclusive forms (capable of identifying trans* patients) at their agencies. Only 5% reported use of gender inclusive forms, 44% did not know about inclusive forms, 37% did not understand what a gender inclusive form was and 14% confused gender with sexual orientation. The study demonstrated a critical need for education in gender identity and sexual orientation terminology. The lack of understanding of concepts and terminology may affect basic care of lesbian, gay, bisexual and transgender patients especially those who identify as transgender. © 2015 John Wiley & Sons Ltd.

  15. trans-Bis(perchlorato-κOtetrakis(1H-pyrazole-κN2copper(II

    Directory of Open Access Journals (Sweden)

    Viktor Zapol'skii

    2008-10-01

    Full Text Available The title compound, [Cu(ClO42(C3H4N24], was obtained unexpectedly by the reaction of copper(II perchlorate hexahydrate with equimolar amounts of 1-chloro-1-nitro-2,2,2-tripyrazolylethane in methanol solution. The crystal structure comprises octahedrally coordinated Cu2+ ions, located on an inversion centre, with four pyrazole ligands in the equatorial plane. The average Cu—N distance is 2.000 (1 Å. Two perchlorate ions are coordinated to copper in trans positions [Cu—O = 2.4163 (11 Å].

  16. Using phosphine ligands with a biological role to modulate reactivity in novel platinum complexes

    Science.gov (United States)

    Echeverri, Marcelo; Alvarez-Valdés, Amparo; Navas, Francisco; Perles, Josefina; Sánchez-Pérez, Isabel; Quiroga, A. G.

    2018-02-01

    Three platinum complexes with cis and trans configuration cis-[Pt(TCEP)2Cl2], cis-[Pt(tmTCEP)2Cl2] and trans-[Pt(TCEP)2Cl2], where TCEP is tris(2-carboxyethyl)phosphine, have been synthesized and fully characterized by usual techniques including single-crystal X-ray diffraction for trans-[Pt(TCEP)2Cl2] and cis-[Pt(tmTCEP)2Cl2]. Here, we also report on an esterification process of TCEP, which takes place in the presence of alcohols, leading to a platinum complex coordinated to an ester tmTCEP (2-methoxycarbonylethyl phosphine) ligand. The stability in solution of the three compounds and their interaction with biological models such as DNA (pBR322 and calf thymus DNA) and proteins (lysozyme and RNase) have also been studied.

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

    KAUST Repository

    Leitgeb, Anita

    2012-01-01

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

  18. Electron and ligand transfer reactions between cyclometallated platinum(II) compounds and thallium(III) carboxylates

    NARCIS (Netherlands)

    Koten, G. van; Ploeg, A.F.M.J. van der; Vrieze, K.

    1982-01-01

    Reaction of trans-[(2-Me{2}NCH{2}C{6}H{4}{2}Pt}I{}I{] with Tl}I{}I{}I{(O{2}CR){3} (R = Me, i-Pr) gave direct elimination of Tl}I{(O{2}CR) and formation of the oxidative addition product [(2-Me{2}NCH{2}C{6}H{4}){2}Pt}I{}V{ (O{2}CR){2}], in two isomeric forms. A structure with the carbon ligands in

  19. Synthesis of cis - and trans-diisothiocyanato-bis(NHC) complexes of nickel(II) and applications in the Kumada-Corriu reaction

    KAUST Repository

    Jothibasu, Ramasamy

    2010-09-13

    Metathetical reaction of AgSCN with a series of trans-dihalido-bis(carbene) nickel(II) complexes in CH3CN readily afforded the novel diisothiocyanato-bis(carbene) complexes [Ni(NCS)2(NHC)2] (trans-2a, NHC = 1,3-diisopropylbenzimidazolin-2-ylidene; trans-2b, NHC = 1,3-diisobutylbenzimidazolin-2-ylidene; trans-2c, NHC = 1,3- dibenzylbenzimidazolin-2-ylidene; cis-2d, NHC = 1,3-di(2-propenyl) benzimidazolin-2-ylidene; cis-2e, NHC = 1-propyl-3-methylbenzimidazolin-2- ylidene) as greenish-yellow powders in moderate to good yields. While dihalido-bis(carbene) Ni(II) complexes exclusively form trans-complexes, a trans-cis isomerization occurs upon halido-isothiocyanato exchange with complexes bearing less bulky carbene ligands, i.e., cis-2d/e. DFT calculations indicated that this isomerization can be attributed to a reduced energy difference between trans- and cis-isomers of diisothiocyanato complexes. All complexes have been characterized by multinuclear NMR spectroscopy, ESI mass spectrometry, and X-ray diffraction analysis. A catalytic study revealed that cis-complexes generally exhibit greater activities in the Kumada-Corriu coupling reaction. © 2010 American Chemical Society.

  20. Ligand Depot: a data warehouse for ligands bound to macromolecules.

    Science.gov (United States)

    Feng, Zukang; Chen, Li; Maddula, Himabindu; Akcan, Ozgur; Oughtred, Rose; Berman, Helen M; Westbrook, John

    2004-09-01

    Ligand Depot is an integrated data resource for finding information about small molecules bound to proteins and nucleic acids. The initial release (version 1.0, November, 2003) focuses on providing chemical and structural information for small molecules found as part of the structures deposited in the Protein Data Bank. Ligand Depot accepts keyword-based queries and also provides a graphical interface for performing chemical substructure searches. A wide variety of web resources that contain information on small molecules may also be accessed through Ligand Depot. Ligand Depot is available at http://ligand-depot.rutgers.edu/. Version 1.0 supports multiple operating systems including Windows, Unix, Linux and the Macintosh operating system. The current drawing tool works in Internet Explorer, Netscape and Mozilla on Windows, Unix and Linux.

  1. Mixed Metal Complexes of Isoniazid and Ascorbic Acid: Chelation ...

    African Journals Online (AJOL)

    HP

    these ligands and their metal complexes have revealed the bi-dentate coordination of isoniazid ligand to ... of the drugs on coordination with a metal is enhanced ..... James, O.O., Nwinyi, C.O. and. Allensela, M.A. (2008). Cobalt(II) complexes of mixed antibiotics: Synthesis,. Characterization, antimicrobial potential and their.

  2. Effects of ligand substitution on the excited state dynamics of the Ru(dcbpy)(CO) 2I 2 complex

    Science.gov (United States)

    Lehtovuori, Viivi; Kallioinen, Jani; Myllyperkiö, Pasi; Haukka, Matti; Korppi-Tommola, Jouko

    2003-11-01

    Spectroscopic evidence suggest [PCCP 3 (2001) 1992] that illumination with visible light of the [ trans-I-Ru(dcbpy)(CO) 2I 2] (dcbpy= 4,4 '-dicarboxy-2,2 '-bipyridine) complex in solution induces dissociation of a CO group followed by reorganization of the ligands and attachment of a solvent molecule. In the present study, we report results on excited state dynamics of this ruthenium complex and its photoproduct. Femtosecond transient absorption measurements reveal dominance of excited state absorption of the reactant and the photoproduct [ cis-I-Ru(dcbpy)(CO)(Sol)I 2] (Sol=ethanol or acetonitrile) in the visible spectral region. The time-resolved measurements for the reactant at 77 K indicate interligand charge transfer from mixed Ru-I states to empty dcbpy orbitals. For the photoproduct, no such transfer was observed. In both complexes recovery from the lowest energy excited triplet state to the ground state occurs via two channels: radiative relaxation and a parallel barrier controlled non-radiative relaxation. The barrier is much higher in the reactant (about 850 cm -1) than in the product. A combination of DFT and ZINDO/CI calculations was used to estimate excited singlet and triplet spectra of the reactant and the product molecules. Calculated singlet-triplet difference spectra qualitatively match the observed transient spectra 500 fs after excitation supporting the idea that observed excited state relaxation occurs from the triplet states in both complexes.

  3. Effects of ligand substitution on the excited state dynamics of the Ru(dcbpy)(CO)2I2 complex

    International Nuclear Information System (INIS)

    Lehtovuori, Viivi; Kallioinen, Jani; Myllyperkioe, Pasi; Haukka, Matti; Korppi-Tommola, Jouko

    2003-01-01

    Spectroscopic evidence suggest [PCCP 3 (2001) 1992] that illumination with visible light of the [trans-I-Ru(dcbpy)(CO) 2 I 2 ] (dcbpy4,4 ' -dicarboxy-2,2 ' -bipyridine) complex in solution induces dissociation of a CO group followed by reorganization of the ligands and attachment of a solvent molecule. In the present study, we report results on excited state dynamics of this ruthenium complex and its photoproduct. Femtosecond transient absorption measurements reveal dominance of excited state absorption of the reactant and the photoproduct [cis-I-Ru(dcbpy)(CO)(Sol)I 2 ] (Sol=ethanol or acetonitrile) in the visible spectral region. The time-resolved measurements for the reactant at 77 K indicate interligand charge transfer from mixed Ru-I states to empty dcbpy orbitals. For the photoproduct, no such transfer was observed. In both complexes recovery from the lowest energy excited triplet state to the ground state occurs via two channels: radiative relaxation and a parallel barrier controlled non-radiative relaxation. The barrier is much higher in the reactant (about 850 cm -1 ) than in the product. A combination of DFT and ZINDO/CI calculations was used to estimate excited singlet and triplet spectra of the reactant and the product molecules. Calculated singlet-triplet difference spectra qualitatively match the observed transient spectra 500 fs after excitation supporting the idea that observed excited state relaxation occurs from the triplet states in both complexes

  4. Cis-trans photoisomerization of abscisic acid

    International Nuclear Information System (INIS)

    Brabham, D.E.; Biggs, R.H.

    1981-01-01

    An important regulator of numerous physiological processes in higher plants is abscisic acid (ABA), which is photoisomerized from the more biologically active cis isomer to the nearly inactive trans isomer by natural sunlight. It is possible that this photoisomerization is a UV control mechanism in functions regulated by ABA. The quantum yields of both the cis to trans and trans to cis photoisomerizations were measured under various conditions of pH and oxygen concentration at room temperature. The yield for photoisomerization of cis-ABA ranged from 0.25 at pH 3.0 to 0.11 at pH 7.0. Oxygen partially quenched the process. The quantum yield varied only slightly with wavelength. The quantum yield of photolysis of cis-ABA was reported for pH 3.0 as 0.06. This yield also varied slightly with wavelength and was relatively insensitive to oxygen. This relatively high yield explains the loss of potency of ABA during UV irradiation. Phosphorescence of cis- and trans-ABA was observed in methanol at 77 K. Onset of the emission was at 350 nm. The emission spectra were the same for both isomers. From these results a mechanism of UV action on plants based on the photoisomerization of the inactive trans-ABA to the biologically active cis isomer is proposed. (author)

  5. Trans issues in Liz Lochhead's 'Not Changed'

    Directory of Open Access Journals (Sweden)

    Kaličanin Milena M.

    2017-01-01

    Full Text Available The paper is divided into four sections. In the first section entitled 'Introducing and Defining Trans (Issues', the basic terms of transgender, transvestite, and transsexual are defined by relying on Stryker's Transgender History (2008. The second part of the paper, 'Trans Studies: In-Between Feminist and Queer Theory?', places transgender studies into an academic context by referring to the theoretical framework provided by trans theorists Stryker, Stone, and Ranck who unanimously claim that transgender studies should have a place of its own within the academia and that trans theory should solely be written by transsexuals. These ideas are applied in the interpretation of Lochhead's story 'Not Changed' in the third segment of the paper. The critical insights of Butler (Gender Trouble, 1990; Undoing Gender, 2004 are found to be most helpful in the interpretation of Lochhead's story about Michael who has willingly undergone Hormone Replacement Therapy to become transsexual Michele. Finally, in the concluding remarks, Lochhead's story is viewed as a trans woman manifesto, urging both non-transsexual and transsexual persons to embrace new beginnings in their relationship.

  6. Melatonin: functions and ligands.

    Science.gov (United States)

    Singh, Mahaveer; Jadhav, Hemant R

    2014-09-01

    Melatonin is a chronobiotic substance that acts as synchronizer by stabilizing bodily rhythms. Its synthesis occurs in various locations throughout the body, including the pineal gland, skin, lymphocytes and gastrointestinal tract (GIT). Its synthesis and secretion is controlled by light and dark conditions, whereby light decreases and darkness increases its production. Thus, melatonin is also known as the 'hormone of darkness'. Melatonin and analogs that bind to the melatonin receptors are important because of their role in the management of depression, insomnia, epilepsy, Alzheimer's disease (AD), diabetes, obesity, alopecia, migraine, cancer, and immune and cardiac disorders. In this review, we discuss the mechanism of action of melatonin in these disorders, which could aid in the design of novel melatonin receptor ligands. Copyright © 2014 Elsevier Ltd. All rights reserved.

  7. Arch development with trans-force lingual appliances.

    Science.gov (United States)

    Clark, William J

    2005-01-01

    Trans-Force lingual appliances are designed to correct arch form in patients with contracted dental arches. Interceptive treatment with this new series of pre-activated lingual appliances offers new possibilities for arch development, in combination with fixed appliances. Palatal and lingual appliances insert in horizontal lingual sheaths in molar bands. No activation is required after the appliance is fitted, and this principle is extended to a series of appliances for sagittal and transverse arch development. Both sagittal and transverse appliances have additional components to achieve 3-way expansion where this is indicated. The invisible lingual appliances may be used in correction of all classes of malocclusion at any stage of development, from mixed dentition through permanent dentition, and this approach has wide indications in adult treatment.

  8. Speciation of cadmium mixed ligand complexes in salt water lakes

    Directory of Open Access Journals (Sweden)

    John L. Kituyi

    2003-06-01

    Full Text Available Amalgam voltammetry has been used to study heavy metal interaction in model lake water in KNO3 at 23 oC at concentration levels of genuine lake water. The hanging drop amalgam electrode was prepared in situ before exchanging the medium for the sample solution. Half-wave potentials at two metal ion concentrations were measured, one at the actual concentration in the lake while the other at a much lower one. The experimentally determined shifts in half-wave potentials are used to compute several formation constants. At the natural [CO32-] of 0.5 M in the lake, the main contributor to the speciation of cadmium is [Cd(CO3Cl2]2-. At high [Cd2+], the DPASV detects the presence of free Cd2+ ions, hence, potential polluting effect, while the amalgam reports [Cd(CO32Cl] 3- to be dominant above [CO32-] = 0.8 M. There is a variation in the number of complexes detected, their stabilities and percentage distribution in the two methods. Cd2+ ion concentration also affects the number of complexes formed and their stabilities.

  9. Speciation of Zinc Mixed Ligand Complexes in Salt Water Systems ...

    African Journals Online (AJOL)

    Half-wave potentials at the actual metal ion concentration in the lake and at a much lower one (10-2 times) were experimentally determined. Shifts in half-wave potentials are used to compute metal complex formation constants. The study reveals the existence of various species and a prediction is made of the distribution of ...

  10. Speciation of Zinc Mixed Ligand Complexes in Salt Water Systems ...

    African Journals Online (AJOL)

    Shifts in half-wave potentials are used to compute metal complex formation constants. The study reveals the existence of various species and a prediction is made of the distribution of the major labile complex species of Zn2+ present in the lake water. The concentration level of Zn2+ ions in the lake seems to play a role in ...

  11. Speciation of cadmium mixed ligand complexes in salt water lakes ...

    African Journals Online (AJOL)

    The experimentally determined shifts in half-wave potentials are used to compute several formation constants. At the natural [CO32-] of 0.5 M in the lake, the main contributor to the speciation of cadmium is [Cd(CO3Cl2)]2-. At high [Cd2+], the DPASV detects the presence of free Cd2+ ions, hence, potential polluting effect, ...

  12. Mixed-ligand complexes of ruthenium (II) incorporating a diazo ...

    Indian Academy of Sciences (India)

    Journal of Chemical Sciences. Current Issue : Vol. 130, Issue 1 · Current Issue Volume 130 | Issue 1. January 2018. Home · Volumes & Issues · Special Issues · Forthcoming Articles · Search · Editorial Board · Information for Authors · Subscription ...

  13. SPECIATION OF CADMIUM MIXED LIGAND COMPLEXES IN SALT ...

    African Journals Online (AJOL)

    a

    ABSTRACT. Amalgam voltammetry has been used to study heavy metal interaction in model lake water in KNO3 at 23 oC at concentration levels of genuine lake water. The hanging drop amalgam electrode was prepared in situ before exchanging the medium for the sample solution. Half-wave potentials at two metal ion ...

  14. A ligand channel through the G protein coupled receptor opsin.

    Directory of Open Access Journals (Sweden)

    Peter W Hildebrand

    Full Text Available The G protein coupled receptor rhodopsin contains a pocket within its seven-transmembrane helix (TM structure, which bears the inactivating 11-cis-retinal bound by a protonated Schiff-base to Lys296 in TM7. Light-induced 11-cis-/all-trans-isomerization leads to the Schiff-base deprotonated active Meta II intermediate. With Meta II decay, the Schiff-base bond is hydrolyzed, all-trans-retinal is released from the pocket, and the apoprotein opsin reloaded with new 11-cis-retinal. The crystal structure of opsin in its active Ops* conformation provides the basis for computational modeling of retinal release and uptake. The ligand-free 7TM bundle of opsin opens into the hydrophobic membrane layer through openings A (between TM1 and 7, and B (between TM5 and 6, respectively. Using skeleton search and molecular docking, we find a continuous channel through the protein that connects these two openings and comprises in its central part the retinal binding pocket. The channel traverses the receptor over a distance of ca. 70 A and is between 11.6 and 3.2 A wide. Both openings are lined with aromatic residues, while the central part is highly polar. Four constrictions within the channel are so narrow that they must stretch to allow passage of the retinal beta-ionone-ring. Constrictions are at openings A and B, respectively, and at Trp265 and Lys296 within the retinal pocket. The lysine enforces a 90 degrees elbow-like kink in the channel which limits retinal passage. With a favorable Lys side chain conformation, 11-cis-retinal can take the turn, whereas passage of the all-trans isomer would require more global conformational changes. We discuss possible scenarios for the uptake of 11-cis- and release of all-trans-retinal. If the uptake gate of 11-cis-retinal is assigned to opening B, all-trans is likely to leave through the same gate. The unidirectional passage proposed previously requires uptake of 11-cis-retinal through A and release of photolyzed all-trans

  15. cis,trans-Dicarbonyldichlorido(1,10-phenanthroline-5,6-dione-κ2N,N′ruthenium(II

    Directory of Open Access Journals (Sweden)

    Tsugiko Takase

    2017-02-01

    Full Text Available In the title compound, [RuCl2(C12H6N2O2(CO2], the RuII atom (site symmetry ..2 adopts a distorted octahedral coordination sphere defined by two carbonyl C atoms, two Cl− anions and two N atoms from the chelating 1,10-phenanthroline-5,6-dione (phendione ligand. The carbonyl ligands are cis to each other, while the Cl atoms are trans. In the phendione ligand, the C=O [1.239 (5 Å] and the C—C [1.537 (5 Å] bond lengths in the diketone moiety have typical values. In the crystal, C—H...Cl and C—H...O hydrogen bonds lead to the formation of a three-dimensional supramolecular network.

  16. TransAlta retires Wabamun power plant

    Energy Technology Data Exchange (ETDEWEB)

    Anon.

    2010-06-15

    The Wabamun power plant has been shut down after 54 years of service in Alberta. The phased shut-down of the 4-unit plant was announced in 2002, and the last operating unit ended commercial operation on March 11, 2010. As the owners of the facility, TransAlta will now complete the remediation and reclamation work required by the government of Alberta. The 537 MW generating facility has helped to fuel Alberta's economic growth over the last 54 years. TransAlta plans to modernize its coal fleet with the Keephill 3 plant and add more renewable energy sources in the future. The Keephill 3 is a joint venture between TransAlta and Capital Power Corporation. The 450 MW coal-fired power plant is equipped with super-critical technology. The new plant will also be the test site for Project Pioneer, a carbon capture and storage (CCS) initiative.

  17. Technical aspects of trans reduction in margarines

    Directory of Open Access Journals (Sweden)

    Van Duijn Gerrit

    2000-01-01

    Full Text Available The opinion of nutritional science on the effect of trans fatty acids on blood cholesterol has drastically changed during the last decade. As a reaction to these new findings, the European margarine industry decided in the mid nineties to eliminate trans containing components from their margarine fat phase compositions. This excluded practically the use of partially hydrogenated oils and fats. Trans-free margarines have been introduced with optimised fat crystal structures stabilising a maximum of water in oil emulsion with a minimum of solid fat phase. These fat crystal structures are formed by fat phase components obtained from interesterification and/or fractionation of non-hydrogenated and/or fully hydrogenated feedstocks.

  18. Mixed Potential Energy Surfaces of the Ultrafast Isomerization of Retinal in Bacteriorhodopsin

    OpenAIRE

    Prokhorenko Valentyn I.; Morizumi Takefumi; Halpin Alexei; Johnson Philip J. M.; Ernst Oliver P.; Dwayne Miller R. J.

    2013-01-01

    We observe, using electronic two-dimensional photon echo spectroscopy, that the cis and trans potential energy surfaces of the ultrafast isomerization of retinal in bacteriorhodopsin are mixed via the hydrogen out of plane (HOOP) mode.

  19. Mixed Potential Energy Surfaces of the Ultrafast Isomerization of Retinal in Bacteriorhodopsin

    Directory of Open Access Journals (Sweden)

    Prokhorenko Valentyn I.

    2013-03-01

    Full Text Available We observe, using electronic two-dimensional photon echo spectroscopy, that the cis and trans potential energy surfaces of the ultrafast isomerization of retinal in bacteriorhodopsin are mixed via the hydrogen out of plane (HOOP mode.

  20. Ruminant and industrially produced trans fatty acids

    DEFF Research Database (Denmark)

    Stender, Steen; Astrup, Arne; Dyerberg, Jørn

    2008-01-01

    Fatty acids of trans configuration in our food come from two different sources - industrially produced partially hydrogenated fat (IP-TFA) used in frying oils, margarines, spreads, and in bakery products, and ruminant fat in dairy and meat products (RP-TFA). The first source may contain up to 60......% of the fatty acids in trans form compared to the content in ruminant fat which generally does not exceed 6%. In Western Europe, including Scandinavia, the average daily intake of IP-TFA has decreased during the recent decade due to societal pressure and a legislative ban, whereas the intake of RP-TFA has...

  1. A High Molar Extinction Coefficient Bisterpyridyl Homoleptic Ru(II) Complex with trans-2-Methyl-2-butenoic Acid Functionality: Potential Dye for Dye-Sensitized Solar Cells

    Science.gov (United States)

    Adeloye, Adewale O.; Olomola, Temitope O.; Adebayo, Akinbulu I.; Ajibade, Peter A.

    2012-01-01

    In our continued efforts in the synthesis of ruthenium(II) polypyridine complexes as potential dyes for use in varied applications, such as the dye-sensitized solar cells (DSSCs), this work particularly describes the synthesis, absorption spectrum, redox behavior and luminescence properties of a new homoleptic ruthenium(II) complex bearing a simple trans-2-methyl-2-butenoic acid functionality as the anchoring ligand on terpyridine moiety. The functionalized terpyridine ligand: 4′-(trans-2-methyl-2-butenoic acid)-terpyridyl (L1) was synthesized by aryl bromide substitution on terpyridine in a basic reaction condition under palladium carbide catalysis. In particular, the photophysical and redox properties of the complex formulated as: bis-4′-(trans-2-methyl-2-butenoic acid)-terpyridyl ruthenium(II) bis-hexafluorophosphate [Ru(L1)2(PF6)2] are significantly better compared to those of [Ru(tpy)2]2+ and compare well with those of the best emitters of Ru(II) polypyridine family containing tridentate ligands. Reasons for the improved photophysical and redox properties of the complex may be attributed partly to the presence of a substituted α,β-unsaturated carboxylic acid moiety leading to increase in the length of π-conjugation bond thereby enhancing the MLCT-MC (Metal-to-ligand-charge transfer-metal centred) energy gap, and to the reduced difference between the minima of the excited and ground states potential energy surfaces. PMID:22489165

  2. A High Molar Extinction Coefficient Bisterpyridyl Homoleptic Ru(II Complex with trans-2-Methyl-2-butenoic Acid Functionality: Potential Dye for Dye-Sensitized Solar Cells

    Directory of Open Access Journals (Sweden)

    Peter A. Ajibade

    2012-03-01

    Full Text Available In our continued efforts in the synthesis of ruthenium(II polypyridine complexes as potential dyes for use in varied applications, such as the dye-sensitized solar cells (DSSCs, this work particularly describes the synthesis, absorption spectrum, redox behavior and luminescence properties of a new homoleptic ruthenium(II complex bearing a simple trans-2-methyl-2-butenoic acid functionality as the anchoring ligand on terpyridine moiety. The functionalized terpyridine ligand: 4’-(trans-2-methyl-2-butenoic acid-terpyridyl (L1 was synthesized by aryl bromide substitution on terpyridine in a basic reaction condition under palladium carbide catalysis. In particular, the photophysical and redox properties of the complex formulated as: bis-4’-(trans-2-methyl-2-butenoic acid-terpyridyl ruthenium(II bis-hexafluorophosphate [Ru(L12(PF62] are significantly better compared to those of [Ru(tpy2]2+ and compare well with those of the best emitters of Ru(II polypyridine family containing tridentate ligands. Reasons for the improved photophysical and redox properties of the complex may be attributed partly to the presence of a substituted α,β-unsaturated carboxylic acid moiety leading to increase in the length of π-conjugation bond thereby enhancing the MLCT-MC (Metal-to-ligand-charge transfer-metal centred energy gap, and to the reduced difference between the minima of the excited and ground states potential energy surfaces.

  3. Biotransformation of trans-1-chloro-3,3,3-trifluoropropene (trans-HCFO-1233zd).

    Science.gov (United States)

    Schmidt, Tobias; Bertermann, Rüdiger; Rusch, George M; Tveit, Ann; Dekant, Wolfgang

    2013-05-01

    trans-1-Chloro-3,3,3-trifluoropropene (trans-HCFO-1233zd) is a novel foam blowing and precision cleaning agent with a very low impact for global warming and ozone depletion. trans-HCFO-1233zd also has a low potential for toxicity in rodents and is negative in genotoxicity testing. The biotransformation of trans-HCFO-1233zd and kinetics of metabolite excretion with urine were assessed in vitro and in animals after inhalation exposures. For in vitro characterization, liver microsomes from rats, rabbits and humans were incubated with trans-HCFO-1233zd. Male Sprague Dawley rats and female New Zealand White rabbits were exposed to 2,000, 5,000 and 10,000ppm for 6h and urine was collected for 48h after the end of the exposure. Study specimens were analyzed for metabolites using (19)F NMR, LC-MS/MS and GC/MS. S-(3,3,3-trifluoro-trans-propenyl)-glutathione was identified as predominant metabolite of trans-HCFO-1233zd in all microsomal incubation experiments in the presence of glutathione. Products of the oxidative biotransformation of trans-HCFO-1233zd were only minor metabolites when glutathione was present. In rats, both 3,3,3-trifluorolactic acid and N-acetyl-(3,3,3-trifluoro-trans-propenyl)-l-cysteine were observed as major urinary metabolites. 3,3,3-Trifluorolactic acid was not detected in the urine of rabbits. Quantitation showed rapid excretion of both metabolites in both species (t1/2trans-HCFO-1233zd was determined as approximately 0.01% of received dose in rabbits and approximately 0.002% in rats. trans-HCFO-1233zd undergoes both oxidative biotransformation and glutathione conjugation at very low rates. The low extent of biotransformation and the rapid excretion of metabolites formed are consistent with the very low potential for toxicity of trans-HCFO-1233zd in mammals. Copyright © 2013 Elsevier Inc. All rights reserved.

  4. Glutamate receptor ligands

    DEFF Research Database (Denmark)

    Guldbrandt, Mette; Johansen, Tommy N; Frydenvang, Karla Andrea

    2002-01-01

    Homologation and substitution on the carbon backbone of (S)-glutamic acid [(S)-Glu, 1], as well as absolute stereochemistry, are structural parameters of key importance for the pharmacological profile of (S)-Glu receptor ligands. We describe a series of methyl-substituted 2-aminoadipic acid (AA...... or slightly lower potencies than (S)-AA [e.g., EC(50) = 76 microM for (2S,4S)-4-methyl-AA (5a) as compared to EC(50) = 35 microM for (S)-AA]. The position of the methyl substituent had a profound effect on the observed pharmacology, whereas the absolute stereochemistry at the methylated carbon atom had a very......) analogs, and the synthesis, stereochemistry, and enantiopharmacology of 3-methyl-AA (4a-d), 4-methyl-AA (5a-d), 5-methyl-AA (6a-d), and (E)-Delta(4)-5-methyl-AA (7a and 7b) are reported. The compounds were resolved using chiral HPLC and the configurational assignments of the enantiomers were based on X...

  5. Ideal CdSe/CdS Core/Shell Nanocrystals Enabled by Entropic Ligands and Their Core Size-, Shell Thickness-, and Ligand-Dependent Photoluminescence Properties.

    Science.gov (United States)

    Zhou, Jianhai; Zhu, Meiyi; Meng, Renyang; Qin, Haiyan; Peng, Xiaogang

    2017-11-22

    This work explored possibilities to obtain colloidal quantum dots (QDs) with ideal photoluminescence (PL) properties, i.e., monoexponential PL decay dynamics, unity PL quantum yield, ensemble PL spectrum identical to that at the single-dot level, single-dot PL nonblinking, and antibleaching. Using CdSe/CdS core/shell QDs as the model system, shell-epitaxy, ligand exchange, and shape conversion of the core/shell QDs were studied systematically to establish a strategy for reproducibly synthesizing QDs with the targeted properties. The key synthetic parameter during epitaxy was application of entropic ligands, i.e., mixed carboxylate ligands with different hydrocarbon chain length and/or structure. Well-controlled epitaxial shells with certain thickness (∼3-8 monolayers of the CdS shells) were found to be necessary to reach ideal photoluminescence properties, and the size of the core QDs was found to play a critical role in determining both photophysical and photochemical properties of the core/shell QDs. Effects of shape of the core QDs were unnoticeable, and shape of the core/shell QDs only affected photophysical properties quantitatively. Surface ligands, amines versus carboxylates, were important for photochemical properties (antiblinking and antibleaching) but barely affected photophysical properties as long as entropic ligands (mixed carboxylate ligands with distinguishable hydrocarbon chain lengths) were applied during epitaxy. Chemical environment (in polymer or in air), coupled with surface ligands, determined photochemical properties of the core/shell QDs with a given core size and shell thickness.

  6. The european Trans-Tools transport model

    NARCIS (Netherlands)

    Rooijen, T. van; Burgess, A.

    2008-01-01

    The paper presents the use of ArcGIS in the Transtools Transport Model, TRANS-TOOLS, created by an international consortium for the European Commission. The model describe passenger as well as freight transport in Europe with all medium and long distance modes (cars, vans, trucks, train, inland

  7. Vibronic interactions in s-trans butadiene

    NARCIS (Netherlands)

    Buma, W.J.; Zerbetto, F.

    1998-01-01

    Configuration interaction calculations are performed to investigate vibronic effects in s-trans-butadiene. Explicit calculations of vibronic coupling matrix elements find that their absolute value depends to a large extent on the level of theory used, a situation that differs markedly from that of

  8. TranSign Android Sign Translator

    OpenAIRE

    Monforte Batiste, Pol

    2013-01-01

    Projecte realitzat en el marc d’un programa de mobilitat amb l'Institute of Applied Informatics, FIIT STU in Bratislava TranSign goal is to translate words from signs (with black letters and white background) from one language to another.

  9. Steric and Electronic Effects of Bidentate Phosphine Ligands on Ruthenium(II)-Catalyzed Hydrogenation of Carbon Dioxide.

    Science.gov (United States)

    Zhang, Pan; Ni, Shao-Fei; Dang, Li

    2016-09-20

    The reactivity difference between the hydrogenation of CO2 catalyzed by various ruthenium bidentate phosphine complexes was explored by DFT. In addition to the ligand dmpe (Me2 PCH2 CH2 PMe2 ), which was studied experimentally previously, a more bulky diphosphine ligand, dmpp (Me2 PCH2 CH2 CH2 PMe2 ), together with a more electron-withdrawing diphosphine ligand, PN(Me) P (Me2 PCH2 N(Me) CH2 PMe2 ), have been studied theoretically to analyze the steric and electronic effects on these catalyzed reactions. Results show that all of the most favorable pathways for the hydrogenation of CO2 catalyzed by bidentate phosphine ruthenium dihydride complexes undergo three major steps: cis-trans isomerization of ruthenium dihydride complex, CO2 insertion into the Ru-H bond, and H2 insertion into the ruthenium formate ion. Of these steps, CO2 insertion into the Ru-H bond has the lowest barrier compared with the other two steps in each preferred pathway. For the hydrogenation of CO2 catalyzed by ruthenium complexes of dmpe and dmpp, cis-trans isomerization of ruthenium dihydride complex has a similar barrier to that of H2 insertion into the ruthenium formate ion. However, in the reaction catalyzed by the PN(Me) PRu complex, cis-trans isomerization of the ruthenium dihydride complex has a lower barrier than H2 insertion into the ruthenium formate ion. These results suggest that the steric effect caused by the change of the outer sphere of the diphosphine ligand on the reaction is not clear, although the electronic effect is significant to cis-trans isomerization and H2 insertion. This finding refreshes understanding of the mechanism and provides necessary insights for ligand design in transition-metal-catalyzed CO2 transformation. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Scope and limitations of chiral bis(oxazoline) ligands in the copper-catalysed asymmetric cyclopropanation of trisubstituted alkenes

    DEFF Research Database (Denmark)

    Østergaard, N.; Jensen, Jakob Feldthusen; Tanner, David Ackland

    2001-01-01

    A series of derivatives of 3-methyl-2-buten-1-ol has been used to test the scope and limitations of the copper-catalysed asymmetric cyclopropanation of trisubstituted alkenes by ethyl diazoacetate in the presence of C-2-symmetric bis(oxazoline) ligands. In the best case, a trans/cis ratio of 91......:9, with 92% ee for the major isomer, was obtained from the reaction of the p-methoxybenzoate derivative. The highest ee was 95%, for the trans isomer of a 80:20 diastereomer mixture (acetate derivative)....

  11. Mixing Ventilation

    DEFF Research Database (Denmark)

    Kandzia, Claudia; Kosonen, Risto; Melikov, Arsen Krikor

    In this guidebook most of the known and used in practice methods for achieving mixing air distribution are discussed. Mixing ventilation has been applied to many different spaces providing fresh air and thermal comfort to the occupants. Today, a design engineer can choose from large selection...

  12. Functionalization of Cadmium Selenide Quantum Dots with Poly(ethylene glycol): Ligand Exchange, Surface Coverage, and Dispersion Stability.

    Science.gov (United States)

    Wenger, Whitney Nowak; Bates, Frank S; Aydil, Eray S

    2017-08-22

    Semiconductor quantum dots synthesized using rapid mixing of precursors by injection into a hot solution of solvents and surfactants have surface ligands that sterically stabilize the dispersions in nonpolar solvents. Often, these ligands are exchanged to disperse the quantum dots in polar solvents, but quantitative studies of quantum dot surfaces before and after ligand exchange are scarce. We studied exchanging trioctylphosphine (TOP) and trioctylphosphine oxide (TOPO) ligands on as-synthesized CdSe quantum dots dispersed in hexane with a 2000 g/mol thiolated poly(ethylene glycol) (PEG) polymer. Using infrared spectroscopy we quantify the absolute surface concentration of TOP/TOPO and PEG ligands per unit area before and after ligand exchange. While 50-85% of the TOP/TOPO ligands are removed upon ligand exchange, only a few are replaced with PEG. Surprisingly, the remaining TOP/TOPO ligands outnumber the PEG ligands, but these few PEG ligands are sufficient to disperse the quantum dots in polar solvents such as chloroform, tetrahydrofuran, and water. Moreover, as-synthesized quantum dots once easily dispersed in hexane are no longer dispersible in nonpolar solvents after ligand exchange. A subtle coverage-dependent balance between attractive PEG-solvent interactions and repulsive TOP/TOPO-solvent interactions determines the dispersion stability.

  13. Mineralocorticoid Receptor (MR) trans-Activation of Inflammatory AP-1 Signaling

    Science.gov (United States)

    Dougherty, Edward J.; Elinoff, Jason M.; Ferreyra, Gabriela A.; Hou, Angela; Cai, Rongman; Sun, Junfeng; Blaine, Kevin P.; Wang, Shuibang; Danner, Robert L.

    2016-01-01

    Glucocorticoids are commonly used to treat inflammatory disorders. The glucocorticoid receptor (GR) can tether to inflammatory transcription factor complexes, such as NFκB and AP-1, and trans-repress the transcription of cytokines, chemokines, and adhesion molecules. In contrast, aldosterone and the mineralocorticoid receptor (MR) primarily promote cardiovascular inflammation by incompletely understood mechanisms. Although MR has been shown to weakly repress NFκB, its role in modulating AP-1 has not been established. Here, the effects of GR and MR on NFκB and AP-1 signaling were directly compared using a variety of ligands, two different AP-1 consensus sequences, GR and MR DNA-binding domain mutants, and siRNA knockdown or overexpression of core AP-1 family members. Both GR and MR repressed an NFκB reporter without influencing p65 or p50 binding to DNA. Likewise, neither GR nor MR affected AP-1 binding, but repression or activation of AP-1 reporters occurred in a ligand-, AP-1 consensus sequence-, and AP-1 family member-specific manner. Notably, aldosterone interactions with both GR and MR demonstrated a potential to activate AP-1. DNA-binding domain mutations that eliminated the ability of GR and MR to cis-activate a hormone response element-driven reporter variably affected the strength and polarity of these responses. Importantly, MR modulation of NFκB and AP-1 signaling was consistent with a trans-mechanism, and AP-1 effects were confirmed for specific gene targets in primary human cells. Steroid nuclear receptor trans-effects on inflammatory signaling are context-dependent and influenced by nuclear receptor conformation, DNA sequence, and the expression of heterologous binding partners. Aldosterone activation of AP-1 may contribute to its proinflammatory effects in the vasculature. PMID:27650495

  14. Technical aspects of trans reduction in modified fats

    Directory of Open Access Journals (Sweden)

    Van Duijn Gerrit

    2005-09-01

    Full Text Available Modification of the solid phase lines of naturally occurring oils and fats is required to produce optimal hardstocks for fat continuous products like margarines, spreads and shortenings. Trans-free hardstocks are produced by combination of the trans-free modification techniques: full hydrogenation, interesterification, and fractionation together with the choice of the feedstock. The introduction of trans-free hardstocks in domestic margarines since 1995 has drastically reduced the daily trans intake by European consumers.

  15. Implication of trans-11,trans-13 conjugated linoleic acid in the development of hepatic steatosis

    OpenAIRE

    Pachikian, Barbara D.; Druart, Céline; Catry, Emilie; Bindels, Laure B.; Neyrinck, Audrey M.; Larondelle, Yvan; Cani, Patrice D.; Delzenne, Nathalie M.

    2018-01-01

    Scope Conjugated linoleic acids are linoleic acid isomers found in the diet that can also be produced through bacterial metabolism of polyunsaturated fatty acids. Our objective was to evaluate the contribution of fatty acid metabolites produced from polyunsaturated fatty acids by the gut microbiota in vivo to regulation of hepatic lipid metabolism and steatosis. Methods and results In mice with depleted n-3 polyunsaturated fatty acids, we observed an accumulation of trans-11,trans-13 CLA and ...

  16. cis,trans-Dicarbonyldichlorido[2-(2-pyridyl-1,8-naphthyridine-κN1,N2]ruthenium(II

    Directory of Open Access Journals (Sweden)

    Takashi Hamada

    2008-03-01

    Full Text Available The asymmetric unit of the title compound, [RuCl2(C13H9N3(CO2], consists of four crystallographically independent RuII complexes. Each RuII atom is in a distorted octahedral environment coordinated by two carbonyl ligands, two Cl atoms and a chelating 2-(2-pyridyl-1,8-naphthyridine (pynp ligand. The carbonyl ligands are cis to each other, while the Cl atoms are trans. Relatively short interatomic distances (2.60–2.67 Å between the uncoordinated N atom of pynp and the C atom of the carbonyl imply a donor–acceptor interaction between the pynp and carbonyl ligands.

  17. Eco-friendly kinetic separation of trans-limonene and ...

    Indian Academy of Sciences (India)

    epoxides cleaved preferen- tially compared to trans-epoxides in the presence of. Lewis acids catalysts. In order to develop an efficient eco-friendly kinetic separation of cis-/trans-limonene oxide, and cis-/trans-carvomenthene oxide, we checked.

  18. Trans-Kullo jagatakse tükkideks / Kadrin Karner

    Index Scriptorium Estoniae

    Karner, Kadrin

    2008-01-01

    Primos OÜ omanik ja Trans-Kullo osanik Endel Siff ütles, et Trans-Kullo on aktsionäride erinevate ärihuvide tõttu läinud jagunemisele, mis võib lõppeda ettevõtte likvideerimisega. Lisa: Trans-Kullo

  19. Production of Methyl Ester (Biodiesel from Used Cooking Oils via Trans-esterification process

    Directory of Open Access Journals (Sweden)

    Sameer Mohammed Salman

    2016-06-01

    Full Text Available Used cooking oil was undergoing trans-esterification reaction to produce biodiesel fuel. Method of production consisted of pretreatment steps, trans-esterification, separation, washing and drying. Trans-esterification of treated oils was studied at different operation conditions, the methanol to oil mole ratio were 6:1, 8:1, 10:1, and 12:1, at different temperature 30, 40, 50, and 60 º C, reaction time 40, 60, 80, and 120 minutes, amount of catalyst 0.5, 1, 1.5, and 2 wt.% based on oil and mixing speed 400 rpm. The maximum yield of biodiesel was 91.68 wt.% for treated oils obtained by trans-esterification reaction with 10:1 methanol to oil mole ratio, 60 º C reaction temperature, 80 minute reaction time and 0.5 wt.% of NaOH catalyst. The physical properties such as specific gravity, kinematic viscosity, acid number, flash point, pour point, and water content, were measured and compared them with American Standard Test Methods (ASTM D6751. The results of these properties for biodiesel product at (6:1, 8:1, 10:1, and 12:1 of methanol to oil mole ratio were within the range of American Standard Test Methods (ASTM D6751.

  20. Ligand-guided receptor optimization.

    Science.gov (United States)

    Katritch, Vsevolod; Rueda, Manuel; Abagyan, Ruben

    2012-01-01

    Receptor models generated by homology or even obtained by crystallography often have their binding pockets suboptimal for ligand docking and virtual screening applications due to insufficient accuracy or induced fit bias. Knowledge of previously discovered receptor ligands provides key information that can be used for improving docking and screening performance of the receptor. Here, we present a comprehensive ligand-guided receptor optimization (LiBERO) algorithm that exploits ligand information for selecting the best performing protein models from an ensemble. The energetically feasible protein conformers are generated through normal mode analysis and Monte Carlo conformational sampling. The algorithm allows iteration of the conformer generation and selection steps until convergence of a specially developed fitness function which quantifies the conformer's ability to select known ligands from decoys in a small-scale virtual screening test. Because of the requirement for a large number of computationally intensive docking calculations, the automated algorithm has been implemented to use Linux clusters allowing easy parallel scaling. Here, we will discuss the setup of LiBERO calculations, selection of parameters, and a range of possible uses of the algorithm which has already proven itself in several practical applications to binding pocket optimization and prospective virtual ligand screening.

  1. Formation of fusarenone X, nivalenol, zearalenone, alpha-trans-zearalenol, beta-trans-zearalenol, and fusarin C by Fusarium crookwellense.

    Science.gov (United States)

    Golinski, P; Vesonder, R F; Latus-Zietkiewicz, D; Perkowski, J

    1988-08-01

    Fusarium crookwellense KF748 (NRRL A-28100) (isolated from dry rotted potato tubers in Central Poland) produced six mycotoxins on both rice and corn substrates at 25 degrees C. The metabolites detected were zearalenone, alpha-trans-zearalenol, beta-trans-zearalenol, fusarin C, and the trichothecenes fusarenone X and nivalenol. This is the first report of formation of alpha-trans-zearalenol, beta-trans-zearalenol, fusarenone X, and nivalenol by F. crookwellense.

  2. Formation of fusarenone X, nivalenol, zearalenone, alpha-trans-zearalenol, beta-trans-zearalenol, and fusarin C by Fusarium crookwellense.

    OpenAIRE

    Golinski, P; Vesonder, R F; Latus-Zietkiewicz, D; Perkowski, J

    1988-01-01

    Fusarium crookwellense KF748 (NRRL A-28100) (isolated from dry rotted potato tubers in Central Poland) produced six mycotoxins on both rice and corn substrates at 25 degrees C. The metabolites detected were zearalenone, alpha-trans-zearalenol, beta-trans-zearalenol, fusarin C, and the trichothecenes fusarenone X and nivalenol. This is the first report of formation of alpha-trans-zearalenol, beta-trans-zearalenol, fusarenone X, and nivalenol by F. crookwellense.

  3. Novel olfactory ligands via terpene synthases.

    Science.gov (United States)

    Touchet, Sabrina; Chamberlain, Keith; Woodcock, Christine M; Miller, David J; Birkett, Michael A; Pickett, John A; Allemann, Rudolf K

    2015-05-01

    A synthetic biology approach to the rational design of analogues of olfactory ligands by providing unnatural substrates for the enzyme synthesising (S)-germacrene D, an olfactory ligand acting as a plant derived insect repellent, to produce novel ligands is described as a viable alternative to largely unsuccessful ligand docking studies. (S)-14,15-Dimethylgermacrene D shows an unexpected reversal in behavioural activity.

  4. Dietary trans-Fatty Acid Induced NASH is Normalized Following Loss of trans-Fatty Acids from Hepatic Lipid Pools

    Science.gov (United States)

    Ford, David A.; Acharya, Sahaja; Gilkey, George; Basaranoglu, Metin; Tetri, Laura H.; Brunt, Elizabeth M.

    2012-01-01

    Previous experiments in mice showed that dietary trans-fats could play a role in non-alcoholic steatohepatitis (NASH) yet little is known about the accumulation trans-fats in hepatic lipid pools in relationship to liver injury. NASH is also associated with obesity yet improves with only modest weight loss. To distinguish the role of obesity versus sustained consumption of a trans-fat containing diet in causing NASH, mice with obesity and NASH induced by consuming a high trans-fat diet for 16 weeks were subsequently fed standard chow or maintained on trans-fat chow for another 8 weeks. The accumulation, partitioning and loss of trans-fats in the major hepatic lipid pools during and after trans-fat consumption were determined. Obese mice switched to standard chow remained obese but steatohepatitis improved. trans-fats were differentially incorporatedinto the majorhepatic lipid pools and the loss of trans-fats after crossover to control chow was greatest in the cholesteryl ester pool. In summary, dietary changes can improve the biochemical and histopathological changes of NASH despite persistent obesity in mice. Analysis of hepatic lipids confirmed that dietary trans-fats accumulate in the major lipid pools and are released differentially with diet normalization. The substantial loss of trans-fats from the cholesteryl ester pool in parallel with improvement in NASH suggests that this pool of trans-fats could play a role in the pathogenesis of NASH. PMID:22923371

  5. Mixed parentage

    DEFF Research Database (Denmark)

    Bang Appel, Helene; Singla, Rashmi

    2016-01-01

    Despite an increase in cross border intimate relationships and children of mixed parentage, there is little mention or scholarship about them in the area of childhood and migrancy in the Nordic countries. The international literature implies historical pathologisation, contestation and current...... complex paradigms regarding these children. This chapter explores how children of mixed parentage negotiate their identities in the Danish context, where statistically and socially there are no widely acceptable terms for categorizing them. To this purpose, an empirical qualitative in...

  6. Introduction to Trans Australia Airlines CRM training

    Science.gov (United States)

    Davidson, Jim

    1987-01-01

    Trans Australia believes that its excellent accident rate record is due to a number of factors. It has a good group of standard operating procedures, and its crews are pretty well self-disciplined and adhere to those procedures. But the other thing that it believes is a factor in its safety record is that perhaps it is also due to its preparedness to be innovative, to keep up with what is going on in the rest of the world and, if it looks to have value, then to be amongst the first to try it out. Trans Australia commenced a program similar to Line Oriented Flight Training (LOFT) fairly early in 1979--that being its first windshear program-- which leads to why they are doing a course of resource management training, which we have chosen to call Aircrew Team Management (ATM). This course is detailed in another presentation.

  7. Trans-sphenoidal excision of craniopharyngiomas.

    Directory of Open Access Journals (Sweden)

    Nagpal R

    1991-04-01

    Full Text Available Craniopharyngiomas have been by and large excised by the transcranial route. Since 1982, 11 patients have been operated by the traus-sphensidal route in the department. The clinical features with which they were presented, diagnostic investigations, details of surgical procedures and follow-up analysis is being presented here. A retrospective study of radiological investigation was done to determine the features that help decide the choice of surgical approach to these lesions. Only lesions that were primarily intrasellar, cystic and those that expanded the sella could be treated by the trans-sphenoidal route. Associated suprasellar extensions could also be removed. Predominantly calcified or firm, fleshy tumours lent themselves poorly to removal by the trans-sphenoidal route.

  8. Trans fat bans and human freedom.

    Science.gov (United States)

    Resnik, David

    2010-03-01

    A growing body of evidence has linked consumption of trans fatty acids to cardiovascular disease. To promote public health, numerous state and local governments in the United States have banned the use of artificial trans fats in restaurant foods, and additional bans may follow. Although these policies may have a positive impact on human health, they open the door to excessive government control over food, which could restrict dietary choices, interfere with cultural, ethnic, and religious traditions, and exacerbate socioeconomic inequalities. These slippery slope concerns cannot be dismissed as far-fetched, because the social and political pressures are place to induce additional food regulations. To protect human freedom and other values, policies that significantly restrict food choices, such as bans on types of food, should be adopted only when they are supported by substantial scientific evidence, and when policies that impose fewer restrictions on freedom, such as educational campaigns and product labeling, are likely to be ineffective.

  9. Trans Fat Bans and Human Freedom

    Science.gov (United States)

    Resnik, David

    2014-01-01

    A growing body of evidence has linked consumption of trans fatty acids to cardiovascular disease. To promote public health, numerous state and local governments in the United States have banned the use of artificial trans fats in restaurant foods, and additional bans may follow. Although these policies may have a positive impact on human health, they open the door to excessive government control over food, which could restrict dietary choices, interfere with cultural, ethnic, and religious traditions, and exacerbate socioeconomic inequalities. These slippery slope concerns cannot be dismissed as far-fetched, because the social and political pressures are place to induce additional food regulations. To protect human freedom and other values, policies that significantly restrict food choices, such as bans on types of food, should be adopted only when they are supported by substantial scientific evidence, and when policies that impose fewer restrictions on freedom, such as educational campaigns and product labeling, are likely to be ineffective. PMID:20229412

  10. The met axial ligand determines the redox potential in Cu-A sites

    DEFF Research Database (Denmark)

    Ledesma, G.N.; Murgida, D.H.; Ly, H.K.

    2007-01-01

    The replacement of the axial methionine ligand in a native Cu-A protein rendered a series of stable mutants with spectroscopic features of a mixed valence center. The mutations resulted in minor perturbations of the electronic structure of this site but led to significant changes in the redox...... potential. This suggests that the axial ligand plays a role in tuning the redox potential Of Cu-A, resembling the behavior observed in blue copper sites....

  11. Trans-triquetral Perilunate fracture dislocation

    OpenAIRE

    John-Henry Rhind; Abhinav Gulihar; Andrew Smith

    2018-01-01

    Perilunate dislocations and perilunate fracture dislocations are rare and serious injuries. Perilunate dislocations represent less than 10% of all carpal injuries of which 61% represent transcaphoid fractures. Because of their rarity, up to 25% of perilunate dislocations are initially missed on first assessment. We present the case of a 66-year-old-gentleman who sustained an isolated trans-triquetral perilunate fracture dislocation while walking his dog. This was diagnosed in the emergency de...

  12. trans-Dibromidobis(triphenylphosphaneplatinum(II chloroform monosolvate

    Directory of Open Access Journals (Sweden)

    Alexandra M. Z. Slawin

    2011-06-01

    Full Text Available Both the platininum complex and the solvent molecule of the title compound, [PtBr2(C18H15P2]·CHCl3, are located on a twofold rotation axis. The CH unit and the Cl atoms of the CHCl3 molecule are disordered over two equally occupied positions. The complex shows a trans square-planar geometry about the Pt atom.

  13. TransCanada Corporation 2004 annual report

    International Nuclear Information System (INIS)

    2005-01-01

    TransCanada is a leading North American energy company dealing with natural gas transmission, power generation and marketing opportunities. Financial information from TransCanada was presented in this annual report along with a review of its operations in 2004 and a summary of how the company performed in terms of providing natural gas transmission and power services in North America. In 2004, TransCanada increased earnings from continuing operations and maintained a strong cash flow and continued to strengthen its balance sheet. Achievements in 2004 included the acquisition of the Gas Transmission Northwest Pipeline System and the North Baja Pipeline System; the purchase of hydroelectric generation assets in New England with a total generating capacity of more than 500 MW; and the completed construction of two new gas-fired cogeneration plants, the 165 MW MacKay River facility in Alberta and the 90 MW Grandview facility in New Brunswick. The challenges in 2004 included the performance of the company's existing asset-based businesses and the new initiatives to produce another year of solid operating and financial results. This report summarized the company's energy resource activities and presented an operations review as well as consolidated financial statements and common share information. This included the utility's assets, liabilities, revenues, expenses and cash flows. Revenue and expenditure statements were summarized by source. tabs., figs

  14. TransAlta 2003 annual report

    International Nuclear Information System (INIS)

    2004-01-01

    This annual report presents financial information from TransAlta Corp., along with a review of its operations throughout 2003 and a summary of the how the electric utility has performed in terms of power generation, independent power producers, transmission and energy marketing. TransAlta is one of the largest non-regulated power generation and wholesale marketing companies in Canada. It's assets include coal-fired, gas-fired, hydro and renewable generation facilities in Canada, the United States, Mexico and Australia. Reported earnings in 2003 were $1.26 per share compared to $1.17 in 2002. The strong first quarter was followed by harsh market conditions, low water levels which affected hydro production, and pricing restrictions in Ontario that reduced contribution from the Sarnia plant. This report outlines the utility's progress in increasing revenue and producing more power. In 2003, unplanned outages were reduced by 7 per cent and injury frequency rate was reduced by 27 per cent. The installation of 114 wind turbines in Fort Macleod, Alberta, increased TransAlta's renewable energy capacity to 3.7 per cent in 2003. The wind farm produces 75 MW of electricity, enough to power more than 32,500 homes annually. This report summarized the company's energy resource activities and presented an operations review as well as consolidated financial statements and common share information. This included the utility's assets, liabilities, revenues, expenses and cash flows. Revenue and expenditure statements were summarized by source. refs., tabs., figs

  15. TransCanada Corporation 2003 annual report

    International Nuclear Information System (INIS)

    2004-01-01

    This annual report presents financial information from TransCanada Corp., along with a review of its operations throughout 2003 and a summary of the how the company performed in terms of providing natural gas transmission and power services in North America. In 2003, TransCanada increased earnings from continuing operations by 7 per cent. It maintained a strong cash flow and continued to strengthen its balance sheet. More than 1.2 billion was invested and dividends were increased by 7 per cent in January 2004, for a total return to shareholders of 27 per cent, including dividends. In 2003, TransCanada also increased its ownership interest in Foothills Pipe Lines Ltd. to 100 per cent from 50 per cent. It secured a position in the Mackenzie Gas Pipeline Project and progressed the development of multiple liquefied natural gas projects in the northeast United States and eastern Canada. The company acquired 31.6 per cent interest in Bruce Power, adding nearly 1,500 megawatts base load generation to its portfolio. Plans are underway for cogeneration plants in Quebec, New Brunswick and Alberta. This report summarized the company's energy resource activities and presented an operations review as well as consolidated financial statements and common share information. This included the utility's assets, liabilities, revenues, expenses and cash flows. Revenue and expenditure statements were summarized by source. tabs., figs

  16. Trans-Cultural, Trans-Language Practices: Potentialities for Rethinking Doctoral Education Pedagogies

    Directory of Open Access Journals (Sweden)

    Sarojni Choy

    2017-01-01

    Full Text Available Over the last decade, there has been a rapid increase in doctoral enrolments of Asian international students in Australian universities. While policies have been developed to meet the needs of these students, there seems to be some confusion around the terms internationalisation, globalisation, bi-cultural, inter-cultural, multi-cultural, and trans-cultural within these policies. In this paper, we define these terms and advocate for a policy position which orients to a futurist definition of culture. We then review the work of Michael Singh and his research team at Western Sydney University who have responded to this rapid increase in Asian international student doctoral enrolments in Australian universities by developing pedagogic principles around notions of trans-language and trans-cultural practices. In the final section of the paper, we then draw on our own experiences of doctoral supervision in Australian universities to reflect on our positioning within the pedagogic principles around trans-language and trans-cultural practices.

  17. Nitroxyl as a ligand in ruthenium tetraammine systems: a density functional theory study.

    Science.gov (United States)

    Da Silva, Augusto C H; Da Silva, Juarez L F; Franco, Douglas W

    2016-03-21

    The properties of the free nitroxyl molecule and the nitroxyl ligand in Ru(ii) tetraammines (trans-[Ru(NH3)4(nitroxyl)(n)(L)](2+n) (n = nitroxyl charge; L = NH3, py, P(OEt)3, H2O, Cl(-) and Br(-))) were studied using density functional theory. According to the calculated conformational energies, HNO complexes are more stable than their deprotonated analogues, and the singlet configuration (trans-(1)[Ru(NH3)4(L)HNO](2+)) is lower in energy than the corresponding triplet (trans-(3)[Ru(NH3)4(L)HNO](2+)). An evaluation of the σ and π components of the L-Ru-HNO bond suggest that the increased stability of these orbitals and the enhanced contributions from the HNO orbitals correlate to shorter Ru-N(H)O distances and higher νRu-HNO stretching frequencies. The stability of the Ru-HNO bond was also evaluated through a theoretical kinetic study of HNO dissociation from trans-(1)[Ru(NH3)4(L)HNO](2+). The order of the Ru-HNO bonding stability in trans-(1)[Ru(NH3)4(L)HNO](2+) as a function of L was found to be as follows: H2O > Cl(-)∼ Br(-) > NH3 > py > P(OEt)3. This order parallels the order of the trans-effect and trans-influence series experimentally measured for L in octahedral complexes. The same trend was also observed using an explicit solvent model, considering the presence of both HNO and H2O molecules in the transition state. For this series, the calculated bond dissociation enthalpies for the Ru-HNO bonds are in the range 23.8 to 45.7 kcal mol(-1). A good agreement was observed between the calculated ΔG(‡) values for the displacement of HNO by H2O in trans-(1)[Ru(NH3)4(P(OEt)3HNO](2+) (23.4 kcal mol(-1)) and the available experimental data for the substitution reactions of trans[Ru(NH3)4(POEt)3(Lx)](2+) (19.4 to 24.0 kcal mol(-1) for Lx = isn and P(OET)3, respectively).

  18. Mononuclear Nickel(II Complexes with Schiff Base Ligands: Synthesis, Characterization, and Catalytic Activity in Norbornene Polymerization

    Directory of Open Access Journals (Sweden)

    Yi-Mei Xu

    2017-03-01

    Full Text Available The nickel(II catalyst has manifested higher catalytic activity compared to that of other late transition metal catalysts for norbornene polymerization. Therefore, several structurally similar trans-nickel(II compounds of N,O-chelate bidentate ligands were synthesized and characterized. Both the electronic effect and the steric hindrance influence polymerization. The molecular structures of 2, 4 and 5 were further confirmed by single-crystal X-ray diffraction.

  19. Nutritional implications of trans fatty acids during perinatal period, in French pregnant women

    Directory of Open Access Journals (Sweden)

    Boue Carole

    2001-01-01

    Full Text Available Some studies have demonstrated the transfer of trans fatty acids (TFA across the human placenta. It was suggested that TFA might disturb the metabolism of essential fatty acids (EFA in fetus and consequently might affect intrauterine human growth more or less according to the TFA intake level of the mother. In this context, the objective of this study was to assess, for French pregnant women, possible impact of their TFA intake on parameters of their term infants: 1/ TFA composition of the umbilical cord (plasma lipids and parietal phospholipids, 2/ birth weight and head circumference. The TFA composition of maternal and umbilical plasma lipids, and parietal phospholipids of umbilical cord were determined by gas chromatography, associated with a thin-layer chromatography for the phospholipids. Because TFA content of adipose tissue is a reliable biochemical indicator of the usual TFA intake level, maternal adipose tissue was also analyzed. Trans fatty acid (TFA percentage was significantly higher (p = 0.001 in maternal (0.9% of total fatty acids than in umbilical plasma total lipids (0.6% thus confirming their placental passage. Moreover, trans isomer pattern of cord plasma lipids was different from the maternal’s one, especially regarding trans isomers of linoleic acid (9c,12c-18:2. Percentage values of 9c,13t + 9t,12t and 9t,12c isomers were respectively, 2 and 3 times higher (p < 0.001 in umbilical than in maternal plasma (Except trans 16:1 acids. All trans isomers observed in umbilical plasma lipids were detected in both parietal and vessel (vein and arteries phospholipids of umbilical cord. Nevertheless, 9c13t + 9t12t isomer mix level was significantly higher (p < 0.001 in artery than in vein TPL. Moreover, in artery TPL, percentage value of 9c13t+9t12t isomer mix was inversely correlated (r = - 0.703, p = 0.003 with arachidonic acid content. Nevertheless, for this French population, there was no relation between either weight or head

  20. Sexual desire in trans persons: associations with sex reassignment treatment.

    Science.gov (United States)

    Wierckx, Katrien; Elaut, Els; Van Hoorde, Birgit; Heylens, Gunter; De Cuypere, Griet; Monstrey, Stan; Weyers, Steven; Hoebeke, Piet; T'Sjoen, Guy

    2014-01-01

    Sex steroids and genital surgery are known to affect sexual desire, but little research has focused on the effects of cross-sex hormone therapy and sex reassignment surgery on sexual desire in trans persons. This study aims to explore associations between sex reassignment therapy (SRT) and sexual desire in a large cohort of trans persons. A cross-sectional single specialized center study including 214 trans women (male-to-female trans persons) and 138 trans men (female-to-male trans persons). Questionnaires assessing demographics, medical history, frequency of sexual desire, hypoactive sexual desire disorder (HSDD), and treatment satisfaction. In retrospect, 62.4% of trans women reported a decrease in sexual desire after SRT. Seventy-three percent of trans women never or rarely experienced spontaneous and responsive sexual desire. A third reported associated personal or relational distress resulting in a prevalence of HSDD of 22%. Respondents who had undergone vaginoplasty experienced more spontaneous sexual desire compared with those who planned this surgery but had not yet undergone it (P = 0.03). In retrospect, the majority of trans men (71.0%) reported an increase in sexual desire after SRT. Thirty percent of trans men never or rarely felt sexual desire; 39.7% from time to time, and 30.6% often or always. Five percent of trans men met the criteria for HSDD. Trans men who were less satisfied with the phalloplasty had a higher prevalence of HSDD (P = 0.02). Trans persons who were more satisfied with the hormonal therapy had a lower prevalence of HSDD (P = 0.02). HSDD was more prevalent in trans women compared with trans men. The majority of trans women reported a decrease in sexual desire after SRT, whereas the opposite was observed in trans men. Our results show a significant sexual impact of surgical interventions and both hormonal and surgical treatment satisfaction on the sexual desire in trans persons. © 2013 International Society for Sexual

  1. TransCanada PipeLines Limited 1998 annual report : TransCanada energy solutions

    International Nuclear Information System (INIS)

    1999-01-01

    Financial information from TransCanada PipeLines Limited and a review of the company's 1998 operations was made available for the benefit of shareholders. TransCanada's pipeline system transports natural gas and crude oil from Western Canada Sedimentary Basin to North America's major energy markets. Net earnings from continuing operations for 1998, before unusual charges, were $575 million ($ 355 million after unusual charges) compared to $522 million for 1997. Solid performances from the energy transmission and international business, when compared to 1997, were more than offset by a decreased contribution from energy processing. TransCanada recorded integration costs of $166 million, after tax, related to the merger with NOVA in 1998, which was the major operational accomplishment during the year, creating a seamless economic energy delivery, processing and marketing system from the wellhead to the market. tabs., figs

  2. Solid and solution NMR studies of the complexation of Ag + with the trans isomer of captopril: Biological activities of this high blood pressure drug along with its Ag + complex

    Science.gov (United States)

    Isab, Anvarhusein A.; Wazeer, Mohamed I. M.

    2006-09-01

    Complexation of Ag + with captopril, 1-[(2 S)-3-mercapto-2-methylpropionyl]- L-proline, has been studied by 1H and 13C-NMR spectroscopy. The equilibrium constants for the trans to cis isomers of captopril bound to Ag + were measured by 1H NMR spectroscopy. It is observed that the trans isomer of the drug binds more strongly to Ag + between pH 5 and 8, as shown by the broadening of the trans isomer's resonances in 13C NMR spectra on complexation. A monodentate complexation of the trans captopril with Ag + via the thiol site is proposed based on the solid-state NMR and IR data. A superior antimicrobial activity is exhibited by the Cap-Ag(I) complex compared to captopril ligand itself against Heterotrotropic Plate Counts (HPC), Pseudomonas aeruginosa and Fecal streptococcus bacteria.

  3. The construction of racial identity in infants of mixed parentage

    OpenAIRE

    Katz, Ilan Barry

    1994-01-01

    This thesis was submitted for the degree of Doctor of Philosophy and awarded by Brunel University. In recent years there has been much debate in this country around the issue of race, and specifically around the role of 'black' children placed trans-racially for adoption. Little attention has been focused on the situation of mixed-race infants in their natural families. This study aims to explore the origins of racial identity development in mixed-race infants; consider how family relat...

  4. Mixed Movements

    DEFF Research Database (Denmark)

    Brabrand, Helle

    2010-01-01

    levels than those related to building, and this exploration is a special challenge and competence implicit artistic development work. The project Mixed Movements generates drawing-material, not primary as representation, but as a performance-based media, making the body being-in-the-media felt and appear......Mixed Movements is a research project engaged in performance-based architectural drawing. Architectonic implementation questions relations between the human body and a body of architecture by the different ways we handle drawing materials. A drawing may explore architectonic problems at other...

  5. Chiral-at-Metal Phosphorescent Square-Planar Pt(II)-Complexes from an Achiral Organometallic Ligand.

    Science.gov (United States)

    Schulte, Thorben R; Holstein, Julian J; Krause, Lennard; Michel, Reent; Stalke, Dietmar; Sakuda, Eri; Umakoshi, Keisuke; Longhi, Giovanna; Abbate, Sergio; Clever, Guido H

    2017-05-24

    The synthesis and characterization of a new kind of cis- and trans-cyclometalated square-planar platinum(II) complexes is reported. Uncharged organometallic compounds carrying one or two of the C ∧ N-donor ligand L CN were prepared. Due to the heterobidentate coordination of the achiral chelate ligand, the formed [PtL CN Cl(SEt 2 )], cis- and trans-[PtL CN 2 ] complexes are chiral with the metal serving as the stereo center. The enantiomers of complex trans-[PtL CN 2 ] could be separated and their absolute configuration was determined by anomalous X-ray diffraction, in accordance with CD spectroscopic results and TD-DFT calculations. All compounds were fully characterized by NMR spectroscopy, mass spectrometry and X-ray structure determination. The photophysical properties of trans-[PtL CN 2 ] have been investigated showing phosphorescence in solution and in the solid state with a moderate quantum yield. For the enantiomers, strong circular dichroism (CD) and circularly polarized luminescence (CPL) effects were observed, rendering this new structural motif suitable for application in chiroptical and luminescent materials.

  6. Isomerization of vaccenic acid to cis and trans C18:1 isomers during biohydrogenation by rumen microbes.

    Science.gov (United States)

    Laverroux, S; Glasser, F; Gillet, M; Joly, C; Doreau, M

    2011-09-01

    In ruminants, cis and trans C18:1 isomers are intermediates of fatty acid transformations in the rumen and their relative amounts shape the nutritional quality of ruminant products. However, their exact synthetic pathways are unclear and their proportions change with the forage:concentrate ratio in ruminant diets. This study traced the metabolism of vaccenic acid, the main trans C18:1 isomer found in the rumen, through the incubation of labeled vaccenic acid with mixed ruminal microbes adapted to different diets. [1-(13)C]trans-11 C18:1 was added to in vitro cultures with ruminal fluids of sheep fed either a forage or a concentrate diet. (13)C enrichment in fatty acids was analyzed by gas-chromatography-mass spectrometry after 0, 5 and 24 h of incubation. (13)C enrichment was found in stearic acid and in all cis and trans C18:1 isomers. Amounts of (13)C found in fatty acids showed that 95% of vaccenic acid was saturated to stearic acid after 5 h of incubation with the concentrate diet, against 78% with the forage diet. We conclude that most vaccenic acid is saturated to stearic acid, but some is isomerized to all cis and trans C18:1 isomers, with probably more isomerization in sheep fed a forage diet.

  7. Ruthenium(II) carbonyl compounds with the 4'-chloro-2,2':6',2''-terpyridine ligand.

    Science.gov (United States)

    Tatikonda, Rajendhraprasad; Haukka, Matti

    2017-04-01

    Two ruthenium carbonyl complexes with the 4'-chloro-2,2':6',2''-terpyridine ligand (tpy-Cl, C 15 H 10 ClN 3 ), i.e. [RuCl(tpy-Cl)(CO) 2 ][RuCl 3 (CO) 3 ] (I) [systematic name: cis -di-carbonyl-chlorido(4'-chloro-2,2':6',2''-terpyridine-κ 3 N )ruthenium(II) fac -tricarbonyltri-chlorido-ruthenate(II)], and [RuCl 2 (tpy-Cl)(CO) 2 ] (II) [ cis -dicarbonyl- trans -di-chlorido(4'-chloro-2,2':6',2''-terpyridine-κ 2 N 1 , N 1' )ruthenium(II)], were synthesized and characterized by single-crystal X-ray diffraction. The Ru II atoms in both centrosymmetric structures (I) and (II) display similar, slightly distorted octa-hedral coordination spheres. The coordination sphere in the complex cation in compound (I) is defined by three N atoms of the tridentate tpy-Cl ligand, two carbonyl carbon atoms and one chlorido ligand; the charge is balanced by an octa-hedral [Ru(CO) 3 Cl 3 ] - counter-anion. In the neutral compound (II), the tpy-Cl ligand coordinates to the metal only through two of its N atoms. The coordination sphere of the Ru II atom is completed by two carbonyl and two chlorido ligands. In the crystal structures of both (I) and (II), weak C-H⋯Cl inter-actions are observed.

  8. Effects of ligand substitution on the excited state dynamics of the Ru(dcbpy)(CO){sub 2}I{sub 2} complex

    Energy Technology Data Exchange (ETDEWEB)

    Lehtovuori, Viivi; Kallioinen, Jani; Myllyperkioe, Pasi; Haukka, Matti; Korppi-Tommola, Jouko

    2003-11-15

    Spectroscopic evidence suggest [PCCP 3 (2001) 1992] that illumination with visible light of the [trans-I-Ru(dcbpy)(CO){sub 2}I{sub 2}] (dcbpy4,4{sup '}-dicarboxy-2,2{sup '}-bipyridine) complex in solution induces dissociation of a CO group followed by reorganization of the ligands and attachment of a solvent molecule. In the present study, we report results on excited state dynamics of this ruthenium complex and its photoproduct. Femtosecond transient absorption measurements reveal dominance of excited state absorption of the reactant and the photoproduct [cis-I-Ru(dcbpy)(CO)(Sol)I{sub 2}] (Sol=ethanol or acetonitrile) in the visible spectral region. The time-resolved measurements for the reactant at 77 K indicate interligand charge transfer from mixed Ru-I states to empty dcbpy orbitals. For the photoproduct, no such transfer was observed. In both complexes recovery from the lowest energy excited triplet state to the ground state occurs via two channels: radiative relaxation and a parallel barrier controlled non-radiative relaxation. The barrier is much higher in the reactant (about 850 cm{sup -1}) than in the product. A combination of DFT and ZINDO/CI calculations was used to estimate excited singlet and triplet spectra of the reactant and the product molecules. Calculated singlet-triplet difference spectra qualitatively match the observed transient spectra 500 fs after excitation supporting the idea that observed excited state relaxation occurs from the triplet states in both complexes.

  9. Synergistic extraction of manganese(II) with thenoyltrifluoroacetone and neutral unidentate and bidentate ligands

    International Nuclear Information System (INIS)

    Nakamura, S.; Imura, H.; Suzuki, N.

    1984-01-01

    Synergistic effect of neutral bidentate ligands, L, such as 1,10-phenanthroline(phen), 2,9-dimethyl-1,10-phenanthroline(dmp) and 2,2'-bipyridine(bpy) and of neutral unidentate ligands TBP and TOPO have been studied in the extraction of Mn(II) labelled with 54 Mn using 2-thenoyl-trifluoroacetone(HTTA) in various organic solvents. The following factors play important role in the synergistic extraction involving bidentate ligands: a two-phase partition of bidentate ligands, and their protonation and complex formation with Mn(II) in the aqueous phase. The mixed ligand complex, Mn(TTA) 2 L is formed in all bidentate ligand systems. The adduct formation constant (βsub(s,1)) decreases in the following order: phen (lg βsub(s,1)=12.64)>dmp(11.32)>.bpy(8.54) in the cyclohexane system. This order is ascribed to the bacisity and the steric effect of the bidentate ligands. Organic solvents influence both the adduct formation and the partition of the ligands, and βsub(s,1) decreases in the order cyclohexane > carbon tetrachloride > cholrobenzene approx.= benzene > chloroform. (author)

  10. Rosetta Ligand docking with flexible XML protocols.

    Science.gov (United States)

    Lemmon, Gordon; Meiler, Jens

    2012-01-01

    RosettaLigand is premiere software for predicting how a protein and a small molecule interact. Benchmark studies demonstrate that 70% of the top scoring RosettaLigand predicted interfaces are within 2Å RMSD from the crystal structure [1]. The latest release of Rosetta ligand software includes many new features, such as (1) docking of multiple ligands simultaneously, (2) representing ligands as fragments for greater flexibility, (3) redesign of the interface during docking, and (4) an XML script based interface that gives the user full control of the ligand docking protocol.

  11. Synthesis and Characterization of Divalent Manganese, Iron, and Cobalt Complexes in Tripodal Phenolate/N-Heterocyclic Carbene Ligand Environments

    DEFF Research Database (Denmark)

    Käß, Martina; Hohenberger, Johannes; Adelhardt, Mario

    2014-01-01

    of the ligands is evident. Particularly, the molecular structure of 1in which a pyridine molecule is situated next to the Mn–Cl bondand those of azide complexes 2, 4, and 6 demonstrate the flexibility of these mixed-ligand derivatives, which, in contrast to the corresponding symmetrical TIMENR ligands, allow......Two novel tripodal ligands, (BIMPNMes,Ad,Me)− and (MIMPNMes,Ad,Me)2–, combining two types of donor atoms, namely, NHC and phenolate donors, were synthesized to complete the series of N-anchored ligands, ranging from chelating species with tris(carbene) to tris(phenolate) chelating arms....... The complete ligand series offers a convenient way of tuning the electronic and steric environment around the metal center, thus, allowing for control of the complex’s reactivity. This series of divalent complexes of Mn, Fe, and Co was synthesized and characterized by 1H NMR, IR, and UV/vis spectroscopy...

  12. Mixed marriages

    Directory of Open Access Journals (Sweden)

    Crnić-Pejović Marija

    2005-01-01

    Full Text Available Until the II World War, the population of the Boka Kotorska Bay was a mixture of Orthodox and Catholic confessions: approximately two thirds of the population was Orthodox, while one third belonged to the Catholics. In spite of the religious affiliation, mixed marriages were relatively often between these two groups. Based on a research in archives, this paper deals with such mixed marriages, formed mostly in 18th and 19th century, in the area of Herceg Novi. The second half of 19th century witnessed 639 of marriages, or 12,78 marriages per year, out of which 72 were mixed or 8,87%. In this particular period, 64 Catholic males married Orthodox females, while only 8 Orthodox males married Catholic females. The Church influence on the society was significant, including issues related to marriage, which sometimes created troubles for mixed marriages; however, positive civil and church regulations supported mixed marriages. Marriages between people of a different religious confession thus created wider kinship affiliations, which in turn enhanced religious tolerance, intertwining of different cultures and customs, and acceptance of different political and social views. The tolerance therefore affected political and social turmoil especially in troubled times, which made many issues easier: troubled issues were solved more rationally, and there were not so many persecutions based on someone’s religious affiliation. We need a wider perspective and a broader research on the Boka Kotorska Bay in order to understand how marriages and kinship ties affected a way of life and intertwining of cultural models of the East and West.

  13. THERMODYNAMIC ASSESSMENT OF ANIONIC LIGANDS ...

    African Journals Online (AJOL)

    DJFLEX

    2010-06-30

    Jun 30, 2010 ... The presence of the ligands (ethylenediaminettraacetic acid, EDTA, enthylenediamine, en,and chloride ion, Cl-) generally improved the sorption capacity for the adsorbent, the best being. Cl- at optimum pH of 2.0 (for Co2+) and 5.0 (for Ni2+ and Cd2+). The thermodynamic studies reveal that the adsorption.

  14. In Search of Deeper Blues: Trans-N-Heterocyclic Carbene Platinum Phenylacetylide as a Dopant for Phosphorescent OLEDs.

    Science.gov (United States)

    Bullock, James D; Salehi, Amin; Zeman, Charles J; Abboud, Khalil A; So, Franky; Schanze, Kirk S

    2017-11-29

    A trans-N-heterocyclic carbene (NHC) platinum(II) acetylide complex bearing phenyl acetylene ligands (NPtPE1) has been synthesized via the Hagihara reaction in 64% yield. The complex features spectrally narrow deep blue emission with a phosphorescence quantum yield (0.30) and lifetime (∼10 μs) in the solid state. The modest quantum yield and lifetime make NPtPE1 a candidate for incorporation into an organic light emitting diode (OLED). Prototype devices exhibited a maximum EQE of 8% with CIE (0.20,0.20). To the best of our knowledge, this is the first example of a platinum(II) acetylide bearing NHC ligands to be incorporated into an OLED.

  15. New functionalized β-diketiminate ligands and f elements

    International Nuclear Information System (INIS)

    Dulong, Florian

    2013-01-01

    β-diketiminate ligands have received increased interest in coordination chemistry, especially for homogeneous catalysis. Their successful applications arise from an easy and fine tuning of the ligand electronic and geometric properties. However, these modifications are limited to the introduction of neutral donors (ethers or amines), on the nitrogen substituents of the β-diketiminate skeleton. The main focus of this research project is to overcome this limitation by synthesizing new β-diketiminate ligands functionalized by one or two anionic aryl-oxide groups, and to study their coordination chemistry with lanthanide and actinide ions. Access to these species relies on a fine understanding of the mechanism underlying their formation, and the sensitivity of the β-di-iminium skeleton towards nucleophiles (phenols) has been identified as the limiting side reaction in the synthetic route. Addition of reactants in well defined order allowed the formation of two new N-aryl-oxy-β-diketiminate dianions on a multi-gram scale. The two ligands differ by their steric bulk and exhibit different coordination behaviors towards lanthanides and actinide ions, which were rationalized on geometric considerations. The reactivity of three of these new complexes has been investigated. A Ce(III) N-aryl-oxy-β-diketiminate complex exhibits interesting reduction properties, due to the shift of its oxidation potential to negative values by its coordination environment. A Th(IV) complex presents a vacant coordination site, which has been probed with different Lewis bases, emphasizing two spatial arrangements ruled by inter-ligand repulsion. It has been compared to its U(IV) analogue, which can be oxidized to a rare terminal mono-oxo uranium(VI) species. The latter was reversibly reduced to its U(V) and U(IV) derivatives, creating the first series of terminal mono-oxo uranium complexes with three successive oxidation states. These compounds represent an opportunity to better understand

  16. Nuclear reactions: Science and trans-science

    International Nuclear Information System (INIS)

    Weinberg, A.M.

    1992-01-01

    This book is a collection of essays written by Weinberg over the span of his scientific and administrative career. A sound theorist, he was introduced to nuclear physics as part of the Manhattan project, and assumed administrative responsibilities during that project. His career has allowed him to make valuable contributions in a broad range of fields. These essays touch on topics of interest to him, concern to the country, and of profound import for society as it exists today. They are grouped into five sections: science and trans-science; scientific administration; strategic defense and arms control; time, energy and resources; nuclear energy

  17. Dietary trans-fatty acids and metabolic syndrome

    OpenAIRE

    Zdzisław Kochan; Joanna Karbowska; Ewa Babicz-Zielińska

    2010-01-01

    Trans-fatty acids (TFAs), products of partial hydrogenation of vegetable oils, have become more prevalent in our diet since the 1960s, when they replaced animal fats. TFAs also occur naturally in meat and dairy products from ruminants. There is growing evidence that dietary trans-fatty acids may increase the risk of metabolic syndrome. Several studies have demonstrated adverse effects of TFAs on plasma lipids and lipoproteins. In dietary trials, trans-fatty acids have been shown to raise the ...

  18. Trans-nationalisation Processes in the Ukrainian Economy

    OpenAIRE

    Bolharova Natalya K.; Panevnyk Tetyana M.

    2013-01-01

    The article considers main processes of trans-nationalisation of Ukrainian economy, identifies specific features of trans-national production and explains some theoretical aspects of these issues. It provides main stages of theoretical comprehension of activity of trans-national corporations (TNC), specific features of the theory of competitive advantages of TNC and specifies the basic ones of them. The article conducts analysis of flows of direct foreign investments into the Ukrainian econom...

  19. Tomato volatile components: enzymatic formation of trans-2-hexenal

    International Nuclear Information System (INIS)

    Sieso, Victor; Nicolas, Michel; Seck, Souleymane; Crouzet, Jean

    1976-01-01

    Evidence of the presence of trans-2-hexenol among tomato volatile components was shown using heavy solvent extraction and absorption-desorption techniques. The action of alcohol deshydrogenase isolated from tomato fruit on trans-2-hexenal shows that the pathway for the formation of trans-2-hexenol is enzymatic. The presence of hexanal and hexanol besides this alcohol indicate that the reduction of the double bonds by the enzymatic preparation is also possible. (Kako, I.)

  20. A trans European Union difference in the decline in trans fatty acids in popular foods

    DEFF Research Database (Denmark)

    Stender, Steen; Astrup, Arne; Dyerberg, Jørn

    2012-01-01

    To minimise the intake of industrial trans fatty acids (I-TFA) some countries have introduced labelling, while others have introduced legislative limits on the content of I-TFA in food. However, most countries still rely on food producers to voluntarily reduce the I-TFA content in food...

  1. Trans-nationalizing the African Public Sphere: What Role for Trans ...

    African Journals Online (AJOL)

    seriane.camara

    2011-03-09

    Mar 9, 2011 ... trans-border language spoken across several national boundaries in West. Africa – and assesses ways ... newspaper, radio, television or internet, which serves the purpose of framing public opinion. This paper .... Although written in French, his entire work is emblematic of a deep. Fulfulde cultural heritage ...

  2. Crystallization of protein–ligand complexes

    International Nuclear Information System (INIS)

    Hassell, Anne M.; An, Gang; Bledsoe, Randy K.; Bynum, Jane M.; Carter, H. Luke III; Deng, Su-Jun J.; Gampe, Robert T.; Grisard, Tamara E.; Madauss, Kevin P.; Nolte, Robert T.; Rocque, Warren J.; Wang, Liping; Weaver, Kurt L.; Williams, Shawn P.; Wisely, G. Bruce; Xu, Robert; Shewchuk, Lisa M.

    2007-01-01

    Methods presented for growing protein–ligand complexes fall into the categories of co-expression of the protein with the ligands of interest, use of the ligands during protein purification, cocrystallization and soaking the ligands into existing crystals. Obtaining diffraction-quality crystals has long been a bottleneck in solving the three-dimensional structures of proteins. Often proteins may be stabilized when they are complexed with a substrate, nucleic acid, cofactor or small molecule. These ligands, on the other hand, have the potential to induce significant conformational changes to the protein and ab initio screening may be required to find a new crystal form. This paper presents an overview of strategies in the following areas for obtaining crystals of protein–ligand complexes: (i) co-expression of the protein with the ligands of interest, (ii) use of the ligands during protein purification, (iii) cocrystallization and (iv) soaks

  3. Trans-NCI Pharmacogenomics and Pharmacoepidemiology Working Group (PPWG)

    Science.gov (United States)

    NCI established the Trans-NCI Pharmacogenomics and Pharmacoepidemiology Working Group to support development of a comprehensive and interdisciplinary pharmacoepidemiology and pharmacogenomics cancer research program.

  4. Attention modulates trans-saccadic integration.

    Science.gov (United States)

    Stewart, Emma E M; Schütz, Alexander C

    2018-01-01

    With every saccade, humans must reconcile the low resolution peripheral information available before a saccade, with the high resolution foveal information acquired after the saccade. While research has shown that we are able to integrate peripheral and foveal vision in a near-optimal manner, it is still unclear which mechanisms may underpin this important perceptual process. One potential mechanism that may moderate this integration process is visual attention. Pre-saccadic attention is a well documented phenomenon, whereby visual attention shifts to the location of an upcoming saccade before the saccade is executed. While it plays an important role in other peri-saccadic processes such as predictive remapping, the role of attention in the integration process is as yet unknown. This study aimed to determine whether the presentation of an attentional distractor during a saccade impaired trans-saccadic integration, and to measure the time-course of this impairment. Results showed that presenting an attentional distractor impaired integration performance both before saccade onset, and during the saccade, in selected subjects who showed integration in the absence of a distractor. This suggests that visual attention may be a mechanism that facilitates trans-saccadic integration. Copyright © 2017 The Author(s). Published by Elsevier Ltd.. All rights reserved.

  5. -Pincer Ligand Family through Ligand Post-Modification

    KAUST Repository

    Huang, Mei-Hui

    2017-10-02

    A series of air-stable nickel complexes containing triazine-based PN3P-pincer ligands were synthesized and fully characterized. Complex 3 contains a de-aromatized central triazine ring from the deprotonation of one of the N–H arms. With a post-modification strategy, the Me-PN3P*NiCl complex (3) could be converted into a new class of diimine–traizine PN3P-pincer nickel complexes.

  6. Homologous SV40 RNA trans-splicing: Special case or prime example of viral RNA trans-splicing?

    Directory of Open Access Journals (Sweden)

    Sushmita Poddar

    2014-06-01

    Full Text Available To date the Simian Virus 40 (SV40 is the only proven example of a virus that recruits the mechanism of RNA trans-splicing to diversify its sequences and gene products. Thereby, two identical viral transcripts are efficiently joined by homologous trans-splicing triggering the formation of a highly transforming 100 kDa super T antigen. Sequences of other viruses including HIV-1 and the human adenovirus type 5 were reported to be involved in heterologous trans-splicing towards cellular or viral sequences but the meaning of these events remains unclear. We computationally and experimentally investigated molecular features associated with viral RNA trans-splicing and identified a common pattern: Viral RNA trans-splicing occurs between strong cryptic or regular viral splice sites and strong regular or cryptic splice sites of the trans-splice partner sequences. The majority of these splice sites are supported by exonic splice enhancers. Splice sites that could compete with the trans-splicing sites for cis-splice reactions are weaker or inexistent. Finally, all but one of the trans-splice reactions seem to be facilitated by one or more complementary binding domains of 11 to 16 nucleotides in length which, however occur with a statistical probability close to one for the given length of the involved sequences. The chimeric RNAs generated via heterologous viral RNA trans-splicing either did not lead to fusion proteins or led to proteins of unknown function. Our data suggest that distinct viral RNAs are highly susceptible to trans-splicing and that heterologous viral trans-splicing, unlike homologous SV40 trans-splicing, represents a chance event.

  7. Chelating ligands for nanocrystals' surface functionalization

    NARCIS (Netherlands)

    Querner, Claudia; Reiss, Peter; Bleuse, Joël; Pron, Adam

    2004-01-01

    A new family of ligands for the surface functionalization of CdSe nanocrystals is proposed, namely alkyl or aryl derivatives of carbodithioic acids (R-C(S)SH). The main advantages of these new ligands are as follows: they nearly quantitatively exchange the initial surface ligands (TOPO) in very mild

  8. Crystallization behavior and texture of trans-containing and trans-free palm oil based confectionery fats.

    Science.gov (United States)

    De Graef, Veerle; Foubert, Imogen; Smith, Kevin W; Cain, Fred W; Dewettinck, Koen

    2007-12-12

    The objective of this study was to gain insight into the role of trans fatty acids in determining the crystallization behavior and texture of palm-based confectionery fats. Therefore, the isothermal crystallization behavior of two series, each of three fats, one trans-containing and one trans-free, was examined by pNMR, DSC, and rheology. Furthermore, the hardness of these samples was examined at three different storage times at 10 degrees C. All of the trans free samples showed a two-step crystallization at 10 degrees C which is hypothesized to be an alpha-mediated beta' crystallization for two of the samples and a fractionated crystallization in the beta' polymorph for the third, while the trans-containing fats crystallized in a single step, probably a direct beta' crystallization. The trans-containing fat series clearly crystallized faster than the trans-free fat series and also yielded higher hardness values at all storage times investigated. The presence of trans fatty acids seems to reduce the effect of compositional variations on the crystallization process. For the trans free fats, chemical composition was much more critical in determining the crystallization rate, the SFC, and the final hardness value.

  9. Structures of mono-unsaturated triacylglycerols. IV. The highest melting β'-2 polymorphs of trans-mono-unsaturated triacylglycerols and related saturated TAGs and their polymorphic stability

    NARCIS (Netherlands)

    van Mechelen, J.B.; Peschar, R.; Schenk, H.

    2008-01-01

    The β1'-2 crystal structures of a series of mixed-chain saturated and trans-mono-unsaturated triacylglycerols containing palmitoyl, stearoyl and elaidoyl acyl chains have been solved from high-resolution powder diffraction data, from synchrotron as well as laboratory X-ray sources. The structures

  10. A feasibility study of unconventional planar ligand spacers in chalcogenide nanocrystals.

    Science.gov (United States)

    Lukose, Binit; Clancy, Paulette

    2016-05-18

    The solar cell efficiency of chalcogenide nanocrystals (quantum dots) has been limited in the past by the insulation between neighboring quantum dots caused by intervening, often long-chain, aliphatic ligands. We have conducted a computationally based feasibility study to investigate the use of ultra-thin, planar, charge-conducting ligands as an alternative to traditional long passive ligands. Not only might these radically unconventional ligands decrease the mean distance between adjacent quantum dots, but, since they are charge-conducting, they have the potential to actively enhance charge migration. Our ab initio studies compare the binding energies, electronic energy gaps, and absorption characteristics for both conventional and unconventional ligands, such as phthalocyanines, porphyrins and coronene. This comparison identified these unconventional ligands with the exception of titanyl phthalocyanine, that bind to themselves more strongly than to the surface of the quantum dot, which is likely to be less desirable for enhancing charge transport. The distribution of finite energy levels of the bound system is sensitive to the ligand's binding site and the levels correspond to delocalized states. We also observed a trap state localized on a single Pb atom when a sulfur-containing phenyldithiocarbamate (PTC) ligand is attached to a slightly off-stoichiometric dot in a manner that the sulfur of the ligand completes stoichiometry of the bound system. Hence, this is indicative of the source of trap state when thio-based ligands are bound to chalcogenide nanocrystals. We also predict that titanyl phthalocyanine in a mix with chalcogenide dots of diameter ∼1.5 Å can form a donor-acceptor system.

  11. Alternative Affinity Ligands for Immunoglobulins.

    Science.gov (United States)

    Kruljec, Nika; Bratkovič, Tomaž

    2017-08-16

    The demand for recombinant therapeutic antibodies and Fc-fusion proteins is expected to increase in the years to come. Hence, extensive efforts are concentrated on improving the downstream processing. In particular, the development of better-affinity chromatography matrices, supporting robust time- and cost-effective antibody purification, is warranted. With the advances in molecular design and high-throughput screening approaches from chemical and biological combinatorial libraries, novel affinity ligands representing alternatives to bacterial immunoglobulin (Ig)-binding proteins have entered the scene. Here, we review the design, development, and properties of diverse classes of alternative antibody-binding ligands, ranging from engineered versions of Ig-binding proteins, to artificial binding proteins, peptides, aptamers, and synthetic small-molecular-weight compounds. We also provide examples of applications for the novel affinity matrices in chromatography and beyond.

  12. Ligand binding by PDZ domains

    DEFF Research Database (Denmark)

    Chi, Celestine N.; Bach, Anders; Strømgaard, Kristian

    2012-01-01

    The postsynaptic density protein-95/disks large/zonula occludens-1 (PDZ) protein domain family is one of the most common protein-protein interaction modules in mammalian cells, with paralogs present in several hundred human proteins. PDZ domains are found in most cell types, but neuronal proteins...... as pathological conditions have been reviewed recently. In this review, we focus on the molecular details of how PDZ domains bind their protein ligands and their potential as drug targets in this context....

  13. Bitopic Ligands and Metastable Binding Sites

    DEFF Research Database (Denmark)

    Fronik, Philipp; Gaiser, Birgit I; Sejer Pedersen, Daniel

    2017-01-01

    of orthosteric binding sites. Bitopic ligands have been employed to address the selectivity problem by combining (linking) an orthosteric ligand with an allosteric modulator, theoretically leading to high-affinity subtype selective ligands. However, it remains a challenge to identify suitable allosteric binding...... that have been reported to date, this type of bitopic ligands would be composed of two identical pharmacophores. Herein, we outline the concept of bitopic ligands, review metastable binding sites, and discuss their potential as a new source of allosteric binding sites....

  14. Mixed segmentation

    DEFF Research Database (Denmark)

    Hansen, Allan Grutt; Bonde, Anders; Aagaard, Morten

    This book is about using recent developments in the fields of data analytics and data visualization to frame new ways of identifying target groups in media communication. Based on a mixed-methods approach, the authors combine psychophysiological monitoring (galvanic skin response) with textual...... content analysis and audience segmentation in a single-source perspective. The aim is to explain and understand target groups in relation to, on the one hand, emotional response to commercials or other forms of audio-visual communication and, on the other hand, living preferences and personality traits...

  15. Tumor targeting via integrin ligands

    Directory of Open Access Journals (Sweden)

    Udaya Kiran eMarelli

    2013-08-01

    Full Text Available Selective and targeted delivery of drugs to tumors is a major challenge for an effective cancer therapy and also to overcome the side effects associated with current treatments. Overexpression of various receptors on tumor cells is a characteristic structural and biochemical aspect of tumors and distinguishes them from physiologically normal cells. This abnormal feature is therefore suitable for selectively directing anticancer molecules to tumors by using ligands that can preferentially recognize such receptors. Several subtypes of integrin receptors that are crucial for cell adhesion, cell signaling, cell viability and motility have been shown to have an upregulated expression on cancer cells. Thus, ligands that recognize specific integrin subtypes represent excellent candidates to be conjugated to drugs or drug carrier systems and be targeted to tumors. In this regard, integrins recognizing the RGD cell adhesive sequence have been extensively targeted for tumor specific drug delivery. Here we review key recent examples on the presentation of RGD-based integrin ligands by means of distinct drug delivery systems, and discuss the prospects of such therapies to specifically target tumor cells.

  16. Study of substitution reactions of ligands in VO2+ complexes in toluene solutions by ESR method

    International Nuclear Information System (INIS)

    Lundkvist, R.; Panfilov, A.T.; Kalinichenko, N.B.; Marov, I.N.; AN SSSR, Moscow. Inst. Geokhimii i Analiticheskoj Khimii)

    1976-01-01

    Kinetics and equilibrium of stepwise substitution of ligands have been investigated at different temperatures for the complexes of oxovanadium (4) with salicylaldoxime, 8-oxyquinoline, acetylacetone, benzoylacetone, and tenoyltrifluoroacetone. The relative complexability of these ligands in toluene has been studied. The parameters of spin-Hamiltonian of EPR spectra of the VO 2+ complexes have been determined. The equilibrium constants, the rate constants, and activation energy have been found for the substitution reactions of ligands in the complexes VOA 2 : VOA 2 +HB=VOAB+HA; VOAB+HB=VOB 2 +HA, where HA and HB are the ligands with different donor atoms. The mixed complexes have been detected of the general formula VOAB, where HA is salicylaldoxime or 8-oxyquinoline and HB is β-diketone

  17. Illela border market: origin and contributions to trans-border ...

    African Journals Online (AJOL)

    Illela border market: origin and contributions to trans-border relations between Nigeria and Niger republic. ... cordial relations between her and her immediate neighbours and thus stem the scourge of smuggling and other trans-border crimes which have negatively affected the Nigerian economy and her international image.

  18. Trans-sialidase-like gene from the bloodstream form of ...

    African Journals Online (AJOL)

    Trans-sialidase-like gene from the bloodstream form of Trypanosoma evansi conserves most of the active site residues and motifs found in Trypanosomal sialidases and trans-sialidases. ... Unique amino acids motifs found to occur in all African trypanosomes TS genes were identified in the TeTS gene. Catalytic site ...

  19. Shifting Paradigms: Moving beyond "Trans 101" in Sexuality Education

    Science.gov (United States)

    Green, Eli R.

    2010-01-01

    Trans-inclusive sexuality education can be complex, confusing, and outright intimidating for even the most seasoned sexuality educator to teach. Historically, standalone "Trans 101" sessions have successfully raised awareness about the highly marginalized transgender community. However, their potential success has been limited by being taught in…

  20. Trans-Z-source Neutral Point Clamped inverter

    DEFF Research Database (Denmark)

    Mo, W.; Loh, P. C.; Li, D.

    2012-01-01

    for buck-boost energy conversion with all the favourable advantages of multi-level switching retained. This paper presents three-level trans-Z-source Neutral Point Clamped (NPC) inverter topology, which achieves both the advantages of trans-Z-source and three-level NPC inverter configuration. With proper...

  1. Relative Stability of cis- and trans-Hydrindanones

    Directory of Open Access Journals (Sweden)

    Motoo Tori

    2015-01-01

    Full Text Available The relative stabilities of several cis- and trans-hydrindanones were compared using both isomerization experiments and MM2 calculations. The generally believed rule that cis-hydrindanones are more stable than trans-isomers is applicable, but is not always true. This review introduces examples, mainly from studies in our laboratory, to explain these facts.

  2. Survey of the trans-resveratrol and trans-piceid content of cocoa-containing and chocolate products.

    Science.gov (United States)

    Hurst, W Jeffrey; Glinski, Jan A; Miller, Kenneth B; Apgar, Joan; Davey, Matthew H; Stuart, David A

    2008-09-24

    Dietary resveratrol (3,4',5-trihydroxystilbene) has been implicated in the health benefits associated with grapes and red wine, more specifically with potential benefits for metabolic syndrome, energy use, and increased endurance. Levels of trans-resveratrol and its glucoside, trans-piceid, were determined in 19 top selling commercially available cocoa-containing and chocolate products from the U.S. market. Amounts of trans-resveratrol and trans-piceid were closely correlated with the amount of nonfat cocoa solids (NFCS) in the cocoa-containing products. Among these products, trans-resveratrol levels were highest in cocoa powders (1.85 +/- 0.43 microg/g), followed by unsweetened baking chocolates (1.24 +/- 0.22), semisweet chocolate baking chips (0.52 +/- 0.14), dark chocolates (0.35 +/- 0.08), milk chocolates (0.10 +/- 0.05), and chocolate syrups (0.09 +/- 0.02). These cocoa-containing and chocolate products have about 3-5 times more trans-piceid than trans-resveratrol. Levels of trans-piceid were highest in the cocoa powders (7.14 +/- 0.80 microg/g), followed by unsweetened baking chocolates (4.04 +/- 0.14), semisweet chocolate baking chips (2.01 +/- 0.18), dark chocolates (1.82 +/- 0.36), milk chocolates (0.44 +/- 0.06), and chocolate syrups (0.35 +/- 0.06). On an equal weight basis, cocoa powder had about half as much trans-resveratrol as the average California red wine. On a per serving basis, cocoa-containing and chocolate products had less trans-resveratrol than red wine and grape juice but more than roasted peanuts. Overall, these cocoa-containing and chocolate products rank second after red wines and grape juice in foods with the highest levels of total trans-resveratrol in the diet.

  3. Redox-induced spin-state switching and mixed valency in quinonoid-bridged dicobalt complexes

    Czech Academy of Sciences Publication Activity Database

    Schweinfurth, D.; Rechkemmer, Y.; Hohloch, S.; Deibel, N.; Peremykin, I.; Fiedler, Jan; Marx, R.; Neugebauer, P.; van Slageren, J.; Sarkar, B.

    2014-01-01

    Roč. 20, č. 12 (2014), s. 3475-3486 ISSN 0947-6539 R&D Projects: GA ČR GA203/09/0705 Institutional support: RVO:61388955 Keywords : bridging ligand s * mixed -valent compounds * non-innocent ligand s Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 5.731, year: 2014

  4. Collimated trans-axial tomographic scintillation camera

    International Nuclear Information System (INIS)

    1980-01-01

    The objects of this invention are first to reduce the time required to obtain statistically significant data in trans-axial tomographic radioisotope scanning using a scintillation camera. Secondly, to provide a scintillation camera system to increase the rate of acceptance of radioactive events to contribute to the positional information obtainable from a known radiation source without sacrificing spatial resolution. Thirdly to reduce the scanning time without loss of image clarity. The system described comprises a scintillation camera detector, means for moving this in orbit about a cranial-caudal axis relative to a patient and a collimator having septa defining apertures such that gamma rays perpendicular to the axis are admitted with high spatial resolution, parallel to the axis with low resolution. The septa may be made of strips of lead. Detailed descriptions are given. (U.K.)

  5. Collimated trans-axial tomographic scintillation camera

    International Nuclear Information System (INIS)

    1980-01-01

    The principal problem in trans-axial tomographic radioisotope scanning is the length of time required to obtain meaningful data. Patient movement and radioisotope migration during the scanning period can cause distortion of the image. The object of this invention is to reduce the scanning time without degrading the images obtained. A system is described in which a scintillation camera detector is moved to an orbit about the cranial-caudal axis relative to the patient. A collimator is used in which lead septa are arranged so as to admit gamma rays travelling perpendicular to this axis with high spatial resolution and those travelling in the direction of the axis with low spatial resolution, thus increasing the rate of acceptance of radioactive events to contribute to the positional information obtainable without sacrificing spatial resolution. (author)

  6. Cascaded Multicell Trans-Z-Source Inverters

    DEFF Research Database (Denmark)

    Li, Ding; Chiang Loh, Poh; Zhu, Miao

    2013-01-01

    Inverters with high-output voltage gain usually face the problem of high-input current flowing through their components. The problem might further be exaggerated if the inverters use high-frequency magnetic devices like transformers or coupled inductors. Leakage inductances of these devices must...... strictly be small to prevent overvoltages caused by switching of their winding currents. To avoid these related problems, cascaded trans-Z-source inverters are proposed. They use multiple magnetic cells in an alternately cascading pattern rather than a single magnetic cell with large turns ratio....... Simulation and experimental results have shown that the multicell inverters can produce the same high-voltage gain, while keeping currents and voltages of the components low. The inverters can also step down their output voltages like a traditional voltage-source inverter without compromising waveform...

  7. Becoming lesbian: Monique Wittig's queer-trans-feminism.

    Science.gov (United States)

    Henderson, Kevin

    2017-07-25

    Inspired by Lynne Huffer's queer feminist genealogy, this article explores queer-trans-feminism as a project that would bring together queer, feminist, and transgender theory and politics into a shared critical lineage. I suggest that Monique Wittig is a neglected thinker who could re-enliven connections and debates within queer, feminist, and trans theory and politics. Utilizing recent historiographies of queer and feminist theory, I imagine what it would mean to hold on to the figure of the lesbian as a figure for queer-trans-feminist politics rather than render the lesbian anachronistic. I then explore the implications of Wittig's notion that "lesbians are not women" for a queer-trans-feminism. I argue that Wittig's critique of the language of the social sciences offers queer-trans-feminist scholars a source for contemporary self-critique and coalition.

  8. Phosphatidylinositol 3-kinase is essential for kit ligand-mediated survival, whereas interleukin-3 and flt3 ligand induce expression of antiapoptotic Bcl-2 family genes

    DEFF Research Database (Denmark)

    Karlsson, Richard; Engström, Maria; Jönsson, Maria

    2003-01-01

    Cytokines such as interleukin 3 (IL-3), kit ligand (KL), and flt3 ligand (FL) promote survival of hematopoietic stem cells and myeloid progenitor cells. In many cell types, members of the Bcl-2 gene family are major regulators of survival, but the mediating mechanisms are not fully understood....... Using two myeloid progenitor cell lines, FDCP-mix and FDC-P1, as well as primary mouse bone marrow progenitors, we demonstrate that KL-mediated survival is dependent on the activation of phosphatidylinositol-3 (PI-3) kinase. The inhibitor LY294002 was able to completely abolish survival mediated by KL...

  9. Controlling with light the interaction between trans-tetrapyridyl ruthenium complexes and an oligonucleotide.

    Science.gov (United States)

    van Rixel, Vincent H S; Moolenaar, Geri F; Siegler, Maxime A; Messori, Luigi; Bonnet, Sylvestre

    2018-01-02

    Three new trans-ruthenium(ii) complexes coordinated to tetrapyridyl ligands, namely [Ru(bapbpy)(dmso)Cl]Cl ([2]Cl), [Ru(bapbpy)(Hmte) 2 ](PF 6 ) 2 ([3](PF 6 ) 2 ), and [Ru(biqbpy)(Hmte) 2 ](PF 6 ) 2 ([4](PF 6 ) 2 ), were prepared as analogues of [Ru(biqbpy)(dmso)Cl]Cl ([1]Cl), a recently described photoactivated chemotherapy agent. The new complexes were characterized, and their crystal structures showed the distorted coordination octahedron typical of this family of complexes. Their photoreactivity in solution was analyzed by spectrophotometry and mass spectrometry, which showed that the sulfur ligand was substituted upon blue light irradiation. The binding of the ruthenium complexes to a reference single-stranded oligonucleotide (s( 5' CTACGGTTTCAC 3' )) was explored both in the dark and under light irradiation by gel electrophoresis and high-resolution mass spectrometry. While adduct formation in the dark was negligible for the four complexes, light irradiation led to the formation of adducts with one or two ruthenium centers per oligonucleotide. The absence of interactions in the dark and the presence of complex-oligonucleotide adducts demonstrate that visible light controls the interaction of these ruthenium complexes with nucleic acids.

  10. Protonation of Ferrous Dinitrogen Complexes Containing a Diphosphine Ligand with a Pendant Amine

    Energy Technology Data Exchange (ETDEWEB)

    Heiden, Zachariah M.; Chen, Shentan; Mock, Michael T.; Dougherty, William G.; Kassel, W. S.; Rousseau, Roger J.; Bullock, R. Morris

    2013-04-01

    The addition of protons to pendant amine containing ferrous dinitrogen complexes, of the type [FeX(N2)(PEtNMePEt)(dmpm)]+ (X = H, Cl, or Br; PEtNMePEt = Et2PCH2N(Me)CH2PEt2 and dmpm = Me2PCH2PMe2), was found to protonate at the pendant amine as opposed to the dinitrogen ligand. This protonation increased the νN2 of the complex by about 25 cm-1, shifting the Fe(II/I) couple 330 mV to a more positive potential. A similar shift was observed in the case of [FeX(CO)(PEtNMePEt)(dmpm)]+ (X = H, Cl, or Br). Computational analysis verified these experimental results and showed the coordination of N2 to Fe(II) centers increases the basicity of N2 (vs. free N2) by 13 and 20 pKa units for the trans halides and hydrides, respectively. Although the iron center was found to increase the basicity of the bound N2 ligand, coordinated N2 is not sufficiently basic to be protonated. In the case of ferrous dinitrogen complexes containing a basic pendant methylamine, the amine site was determined to be the most basic site by 30 pKa units compared to protonation at the N2 ligand. To increase the basicity of the N2 ligand in order to promote proton transfer from the pendant amine to the N2 ligand, chemical reduction of these ferrous dinitrogen complexes was performed and found to result in oxidative addition of the methylene C-H bond of the PEtNMePEt ligand to Fe, preventing isolation of a reduced Fe(0) N2 complex. This work was supported as part of the Center for Molecular Electrocatalysis, an Energy Frontier Research Center funded by the U.S. Department of Energy Office of Science, Office of Basic Energy Sciences.

  11. Understanding the complexity of trans fatty acid reduction in the American diet: American Heart Association Trans Fat Conference 2006: report of the Trans Fat Conference Planning Group.

    Science.gov (United States)

    Eckel, Robert H; Borra, Susan; Lichtenstein, Alice H; Yin-Piazza, Shirley Y

    2007-04-24

    A 2-day forum was convened to discuss the current status and future implications of reducing trans fatty acids without increasing saturated fats in the food supply while maintaining functionality and consumer acceptance of packaged, processed, and prepared foods. Attendees represented the agriculture and oilseed industry and oil processing, food manufacturing, food service, government, food technology, and health and nutrition disciplines. Presentations included food science behind fatty acid technology, the health science of dietary fatty acids, alternatives to trans fatty acids, and the use of alternatives in food manufacturing and food service. The reduction of trans fatty acids in the food supply is a complex issue involving interdependent and interrelated stakeholders. Actions to reduce trans fatty acids need to carefully consider both intended and unintended consequences related to nutrition and public health. The unintended consequence of greatest concern is that fats and oils high in saturated fats, instead of the healthier unsaturated fats, might be used to replace fats and oils with trans fatty acids. Many different options of alternative oils and fats to replace trans fatty acids are available or in development. Decisions on the use of these alternatives need to consider availability, health effects, research and development investments, reformulated food quality and taste, supply-chain management, operational modifications, consumer acceptance, and cost. The conference demonstrated the value of collaboration between the food industry and health and nutrition professionals, and this conference model should be used to address other food development, processing, and/or technology issues.

  12. TNOs are Cool: A Survey of the Trans-Neptunian Region: Radiometric properties of Trans-Neptunian Objects

    NARCIS (Netherlands)

    Mommert, Michael; Müller, G.; Bühnhardt, Hermann; Lellouch, Emmanuel; Stansberry, John; Barucci, Antonella; Crovisier, Jacques; Delsanti, Audrey; Dores-Soundiram, Alain; Dotto, Elisabetta; Duffard, René; Fornasier, Sonia; Groussin, Olivier; Gutiérrez Buenestado, Pedro; Hainaut, Olivier; Harris, Alan; Hartogh, Paul; Henry, Florence; Hestroffer, Daniel; Horner, Jonathan; Jewitt, Dave; Kidger, Mark; Kiss, Csaba; Lacerda, Pedro; López, Luisa Lara; Lim, Tanya; Müller, Michael; Moreno, Raphael; Ortiz Moreno, Jose Luis; Protopapa, Silvia; Rengel, Miriam; Santos Sanz, Pablo; Swinyard, Bruce; Thomas, Nicolas; Thirouin, Audrey; Trilling, David

    2010-01-01

    The "TNOs are Cool: A Survey of the Trans-Neptunian Region" project is a Herschel Open Time Key Program awarded some 370 h of Herschel observing time. The observations include PACS and SPIRE point-source photometry on about 140 trans-Neptunian objects with known orbits. The goal is to characterize

  13. Assessment of biofuels supporting policies using the BioTrans model

    International Nuclear Information System (INIS)

    Lensink, Sander; Londo, Marc

    2010-01-01

    The introduction of advanced, 2nd generation biofuels is a difficult to forecast process. Policies may impact the timing of their introduction and the future biofuels mix. The least-cost optimization model BioTrans supports policy analyses on these issues. It includes costs for all parts of the supply chain, and endogenous learning for all biofuels technologies, including cost reductions through scale. BioTrans shows that there are significant lock-in effects favouring traditional biofuels, and that the optimal biofuels mix by 2030 is path dependent. The model captures important barriers for the introduction of emerging technologies, thereby providing valuable quantitative information that can be used in analyses of biofuels supporting policies. It is shown that biodiesel from oil crops will remain a cost effective way of producing biofuels in the medium term at moderate target levels. Aiming solely at least-cost biofuel production is in conflict with a longer term portfolio approach on biofuels, and the desire to come to biofuels with the lowest greenhouse gas emissions. Lowering the targets because of environmental constraints delays the development of 2nd generation biofuels, unless additional policy measures (such as specific sub targets for these fuels) are implemented.

  14. Atmospheric emissivity with clear sky computed by E-Trans/HITRAN

    Science.gov (United States)

    Mendoza, Víctor M.; Villanueva, Elba E.; Garduño, René; Sánchez-Meneses, Oscar

    2017-04-01

    The vertical profiles of temperature and pressure from the International Standard Atmosphere, together with the mixing ratio profiles of the main greenhouse effect gases (GG), namely water vapour, CO2 , CH4 , N2 O and stratospheric O3 , are used to determine the downward emissivity of long wave radiation by cloudless atmosphere, by means of the spectral calculator E-Trans with the HITRAN (high-resolution transmission) database. We make a review of emissivity parameterizations, reported by several authors, in terms of the surface vapour pressure and surface air temperature. We compute vertically weighted averages of temperature and pressure, also parameterize the CH4 , N2 O and O3 mixing ratio profiles, in order to adapt these variables as required by the E-Trans/HITRAN. Our results of emissivity for the corresponding vapour pressures agree well with those obtained by the reviewed authors. With this method, the emissivity can be computed at a regional scale and towards the future global warming, according to the IPCC temperature projections that will also increase the atmospheric humidity, from the emission scenarios of GG.

  15. Trans fatty acids in human milk are an indicator of different maternal dietary sources containing trans fatty acids.

    Science.gov (United States)

    Mueller, A; Thijs, C; Rist, L; Simões-Wüst, A P; Huber, M; Steinhart, H

    2010-03-01

    The trans fatty acid (TFA) patterns in the fats of ruminant meat and dairy products differ from those found in other (processed) fats. We have evaluated different TFA isomers in human breast milk as an indicator of dietary intake of ruminant and dairy fats of different origins. Breast milk samples were collected 1 month postpartum from 310 mothers participating in the KOALA Birth Cohort Study (The Netherlands). The study participants had different lifestyles and consumed different amounts of dairy products. Fatty acid methyl esters were determined by GC-FID and the data were evaluated by principal component analysis (PCA), ANOVA/Post Hoc test and linear regression analysis. The two major principal components were (1) 18:1 trans-isomers and (2) markers of dairy fat including 15:0, 17:0, 11(trans)18:1 and 9(cis),11(trans)18:2 (CLA). Despite similar total TFA values, the 9(trans)18:1/11(trans)18:1-ratio and the 10(trans)18:1/11(trans)18:1-ratio were significantly lower in milk from mothers with high dairy fat intake (40-76 g/day: 0.91 +/- 0.48, P fat intake (0-10 g/day: 1.59 +/- 0.48), and lower with strict organic meat and dairy use (>90% organic: 0.92 +/- 0.46, P trans)18:1/11(trans)18:1-ratio. We conclude that both ratios are indicators of different intake of TFA from ruminant and dairy origin relative to other (including industrial) sources.

  16. Molecular Determinants for Ligand Binding at Serotonin 5-HT2Aand 5-HT2CGPCRs: Experimental Affinity Results Analyzed by Molecular Modeling and Ligand Docking Studies.

    Science.gov (United States)

    Córdova-Sintjago, Tania; Sakhuja, Rajeev; Kondabolu, Krishnakanth; Canal, Clinton E; Booth, Raymond G

    2012-12-15

    Ligands that activate the serotonin 5-HT 2C G protein-coupled receptor (GPCR) may be therapeutic for psychoses, addiction, and other neuropsychiatric disorders. Ligands that are antagonists at the closely related 5-HT 2A GPCR also may treat neuropsychiatric disorders; in contrast, 5-HT 2A activation may cause hallucinations. 5-HT 2C -specific agonist drug design is challenging because 5-HT 2 GPCRs share 80% transmembrane (TM) homology, same second messenger signaling, and no crystal structures are reported. To help delineate molecular determinants underlying differential binding and activation of 5-HT 2 GPCRs, 5-HT 2A , and 5-HT 2C homology models were built from the β 2 -adrenergic GPCR crystal structure and equilibrated in a lipid phosphatidyl choline bilayer performing molecular dynamics simulations. Ligand docking studies at the 5-HT 2 receptor models were conducted with the (2 R , 4 S )- and (2 S , 4 R )-enantiomers of the novel 5-HT 2C agonist/5-HT 2A/2B antagonist trans -4-phenyl- N,N -dimethyl-2-aminotetralin (PAT) and its 4'-chlorophenyl congners. Results indicate PAT-5-HT 2 molecular interactions especially in TM domain V are important for the (2 R , 4 S ) enantiomer, whereas, TM domain VI and VII interactions are more important for the (2 S , 4 R ) enantiomer.

  17. Using inositol as a biocompatible ligand for efficient transgene expression

    Science.gov (United States)

    Zhang, Lei; Bellis, Susan L; Fan, Yiwen; Wu, Yunkun

    2015-01-01

    Transgene transfection techniques using cationic polymers such as polyethylenimines (PEIs) and PEI derivatives as gene vectors have shown efficacy, although they also have shortcomings. PEIs have decent DNA-binding capability and good cell internalization performance, but they cannot deliver gene payloads very efficiently to cell nuclei. In this study, three hyperbranched polyglycerol-polyethylenimine (PG6-PEI) polymers conjugated with myo-inositol (INO) molecules were developed. The three resulting PG6-PEI-INO polymers have an increased number of INO ligands per molecule. PG6-PEI-INO 1 had only 14 carboxymethyl INO (CMINO) units per molecule. PG6-PEI-INO 2 had approximately 130 CMINO units per molecule. PG6-PEI-INO 3 had as high as 415 CMINO units approximately. Mixing PG6-PEI-INO polymers with DNA produced compact nanocomposites. We then performed localization studies using fluorescent microscopy. As the number of conjugated inositol ligands increased in PG6-PEI-INO polymers, there was a corresponding increase in accumulation of the polymers within 293T cell nuclei. Transfection performed with spherical 293T cells yielded 82% of EGFP-positive cells when using PG6-PEI-INO 3 as the vehicle. Studies further revealed that extracellular adenosine triphosphate (eATP) can inhibit the transgene efficiency of PG6-PEI-INO polymers, as compared with PEI and PG6-PEI that were not conjugated with inositol. Our work unveiled the possibility of using inositol as an effective ligand for transgene expression. PMID:25926732

  18. Using inositol as a biocompatible ligand for efficient transgene expression.

    Science.gov (United States)

    Zhang, Lei; Bellis, Susan L; Fan, Yiwen; Wu, Yunkun

    2015-01-01

    Transgene transfection techniques using cationic polymers such as polyethylenimines (PEIs) and PEI derivatives as gene vectors have shown efficacy, although they also have shortcomings. PEIs have decent DNA-binding capability and good cell internalization performance, but they cannot deliver gene payloads very efficiently to cell nuclei. In this study, three hyperbranched polyglycerol-polyethylenimine (PG6-PEI) polymers conjugated with myo-inositol (INO) molecules were developed. The three resulting PG6-PEI-INO polymers have an increased number of INO ligands per molecule. PG6-PEI-INO 1 had only 14 carboxymethyl INO (CMINO) units per molecule. PG6-PEI-INO 2 had approximately 130 CMINO units per molecule. PG6-PEI-INO 3 had as high as 415 CMINO units approximately. Mixing PG6-PEI-INO polymers with DNA produced compact nanocomposites. We then performed localization studies using fluorescent microscopy. As the number of conjugated inositol ligands increased in PG6-PEI-INO polymers, there was a corresponding increase in accumulation of the polymers within 293T cell nuclei. Transfection performed with spherical 293T cells yielded 82% of EGFP-positive cells when using PG6-PEI-INO 3 as the vehicle. Studies further revealed that extracellular adenosine triphosphate (eATP) can inhibit the transgene efficiency of PG6-PEI-INO polymers, as compared with PEI and PG6-PEI that were not conjugated with inositol. Our work unveiled the possibility of using inositol as an effective ligand for transgene expression.

  19. Mixed cryoglobulinemia

    Directory of Open Access Journals (Sweden)

    Ferri Clodoveo

    2008-09-01

    Full Text Available Abstract Mixed cryoglobulinemia (MC, type II and type III, refers to the presence of circulating cryoprecipitable immune complexes in the serum and manifests clinically by a classical triad of purpura, weakness and arthralgias. It is considered to be a rare disorder, but its true prevalence remains unknown. The disease is more common in Southern Europe than in Northern Europe or Northern America. The prevalence of 'essential' MC is reported as approximately 1:100,000 (with a female-to-male ratio 3:1, but this term is now used to refer to a minority of MC patients only. MC is characterized by variable organ involvement including skin lesions (orthostatic purpura, ulcers, chronic hepatitis, membranoproliferative glomerulonephritis, peripheral neuropathy, diffuse vasculitis, and, less frequently, interstitial lung involvement and endocrine disorders. Some patients may develop lymphatic and hepatic malignancies, usually as a late complication. MC may be associated with numerous infectious or immunological diseases. When isolated, MC may represent a distinct disease, the so-called 'essential' MC. The etiopathogenesis of MC is not completely understood. Hepatitis C virus (HCV infection is suggested to play a causative role, with the contribution of genetic and/or environmental factors. Moreover, MC may be associated with other infectious agents or immunological disorders, such as human immunodeficiency virus (HIV infection or primary Sjögren's syndrome. Diagnosis is based on clinical and laboratory findings. Circulating mixed cryoglobulins, low C4 levels and orthostatic skin purpura are the hallmarks of the disease. Leukocytoclastic vasculitis involving medium- and, more often, small-sized blood vessels is the typical pathological finding, easily detectable by means of skin biopsy of recent vasculitic lesions. Differential diagnoses include a wide range of systemic, infectious and neoplastic disorders, mainly autoimmune hepatitis, Sjögren's syndrome

  20. Ligand photo-isomerization triggers conformational changes in iGluR2 ligand binding domain.

    Directory of Open Access Journals (Sweden)

    Tino Wolter

    Full Text Available Neurological glutamate receptors bind a variety of artificial ligands, both agonistic and antagonistic, in addition to glutamate. Studying their small molecule binding properties increases our understanding of the central nervous system and a variety of associated pathologies. The large, oligomeric multidomain membrane protein contains a large and flexible ligand binding domains which undergoes large conformational changes upon binding different ligands. A recent application of glutamate receptors is their activation or inhibition via photo-switchable ligands, making them key systems in the emerging field of optochemical genetics. In this work, we present a theoretical study on the binding mode and complex stability of a novel photo-switchable ligand, ATA-3, which reversibly binds to glutamate receptors ligand binding domains (LBDs. We propose two possible binding modes for this ligand based on flexible ligand docking calculations and show one of them to be analogues to the binding mode of a similar ligand, 2-BnTetAMPA. In long MD simulations, it was observed that transitions between both binding poses involve breaking and reforming the T686-E402 protein hydrogen bond. Simulating the ligand photo-isomerization process shows that the two possible configurations of the ligand azo-group have markedly different complex stabilities and equilibrium binding modes. A strong but slow protein response is observed after ligand configuration changes. This provides a microscopic foundation for the observed difference in ligand activity upon light-switching.

  1. Study on the interactions of trans-resveratrol and curcumin with bovine α-lactalbumin by spectroscopic analysis and molecular docking

    Energy Technology Data Exchange (ETDEWEB)

    Mohammadi, Fakhrossadat, E-mail: fmohammadi@iasbs.ac.ir; Moeeni, Marzieh

    2015-05-01

    The ability of bovine α-lactalbumin (BLA) as a whey protein to carry curcumin and trans-resveratrol as two natural polyphenolic compounds was investigated by fluorescence quenching measurements and docking studies. Curcumin is the bioactive component of turmeric and trans-resveratrol is abundant in different types of fruits and vegetables. The binding parameters such as binding constants and the number of substantive binding sites have been estimated from the analysis of fluorescence quenching measurements. The differences in affinities of curcumin and trans-resveratrol for BLA were compared. The short Förster's distance (r) between donor (BLA) and acceptor (curcumin and trans-resveratrol) and also the binding constant values demonstrated the strong interaction between these two polyphenolic compounds and BLA. The thermodynamic parameters were obtained from the fluorescence quenching measurements in different temperatures. It can be concluded from the sign and magnitude of ∆H and ∆S that the final ligand–protein complexes were stabilized by hydrogen bonds. The considerable change in microregion of the Trp residues in BLA is observed upon the binding of the trans-resveratrol to BLA by synchronous fluorescence while this conformation alteration was not observed upon interaction with curcumin. It was indicated by docking studies that curcumin come closer to the Trp-118 than to other tryptophans and trans-resveratrol binds in the vicinity of Trp-60 and Trp-104. Docking studies indicated that these two compounds bind to BLA by two hydrogen bonds. The calculated distances between bound ligands and tryptophans obtained by docking studies were in agreement with fluorescence resonance energy transfer results. Therefore, the strong interaction of curcumin and trans-resveratrol with BLA was confirmed by theoretical and experimental studies. These achieved results may be applicable in the milk industry and drug formulation. - Highlights: • The binding parameters

  2. Study on the interactions of trans-resveratrol and curcumin with bovine α-lactalbumin by spectroscopic analysis and molecular docking

    International Nuclear Information System (INIS)

    Mohammadi, Fakhrossadat; Moeeni, Marzieh

    2015-01-01

    The ability of bovine α-lactalbumin (BLA) as a whey protein to carry curcumin and trans-resveratrol as two natural polyphenolic compounds was investigated by fluorescence quenching measurements and docking studies. Curcumin is the bioactive component of turmeric and trans-resveratrol is abundant in different types of fruits and vegetables. The binding parameters such as binding constants and the number of substantive binding sites have been estimated from the analysis of fluorescence quenching measurements. The differences in affinities of curcumin and trans-resveratrol for BLA were compared. The short Förster's distance (r) between donor (BLA) and acceptor (curcumin and trans-resveratrol) and also the binding constant values demonstrated the strong interaction between these two polyphenolic compounds and BLA. The thermodynamic parameters were obtained from the fluorescence quenching measurements in different temperatures. It can be concluded from the sign and magnitude of ∆H and ∆S that the final ligand–protein complexes were stabilized by hydrogen bonds. The considerable change in microregion of the Trp residues in BLA is observed upon the binding of the trans-resveratrol to BLA by synchronous fluorescence while this conformation alteration was not observed upon interaction with curcumin. It was indicated by docking studies that curcumin come closer to the Trp-118 than to other tryptophans and trans-resveratrol binds in the vicinity of Trp-60 and Trp-104. Docking studies indicated that these two compounds bind to BLA by two hydrogen bonds. The calculated distances between bound ligands and tryptophans obtained by docking studies were in agreement with fluorescence resonance energy transfer results. Therefore, the strong interaction of curcumin and trans-resveratrol with BLA was confirmed by theoretical and experimental studies. These achieved results may be applicable in the milk industry and drug formulation. - Highlights: • The binding parameters

  3. Synthesis and characterization of the Bis- Cyclometalating Ligand 3,3',5,5'-tetrakis[(dimethylamino)methyl]biphenyl and its use in the preparation of bimetallic M(II), M(IV) (M = Pt, Pd) and mixed-valence Pt(II)-Pt(IV) complexes via a dilithio-derivative. Crystal structure of the Pd dimer [ClPd{2,6-(Me2NCH2)2C6H2}]2,

    NARCIS (Netherlands)

    Koten, G. van; Lagunas, M.C.; Gossage, R.A.; Spek, A.L.

    1998-01-01

    The potentially bis-cyclometalating ligand 3,3',5,5'-tetrakis[(dimethylamino)methyl]biphenyl, was prepared from 3,5-(Me2NCH2)2C6H3Br in a one-pot synthesis involving lithium-halogen exchange, transmetalation, and reductive-elimination reactions. This ligand undergoes selective dilithiation in the 4

  4. Ruthenium Cumulenylidene Complexes Bearing Heteroscorpionate Ligands

    OpenAIRE

    Strinitz, Frank

    2014-01-01

    In previous work of the BURZLAFF group, the design of suitable N,N,O ligands for a wide variety of applications ranging from catalysis to bioinorganic model compounds has been extensively investigated. Especially the methyl substituted bis(3,5-dimethylpyrazol-1-yl) acetate (bdmpza) ligand has shown manifold chemistry, comparable to the anionic cyclopentadienyl (Cp) and hydridotris(pyrazol-1-yl)borato (Tp) ligand. In the first part of this thesis the new tricarbonylmanganese(I) complexes be...

  5. Synthesis and characterization of technetium(III) complexes containing 2,2'-bipyridine and 1,10-phenanthroline. X-ray crystal structures of cis (Cl),trans(P)-[TcCl2(P(CH3)2C6H5)2(bpy)]B(C6H5)4, cis (Cl),trans(P)-[TcCl2(P(CH3)2C6H5)2(phen)]B(C6H5)4, and cis (Cl),trans(P)-[TcCl2(P(CH3CH2)(C6H5)2)2(bpy)]SO3CF3

    International Nuclear Information System (INIS)

    Wilcox, B.E.; Ho, D.M.; Deutsch, E.

    1989-01-01

    Technetium(III) complexes of the general formula cis(Cl),trans(P)-[TcCl 2 (P) 2 L] + , where (P) is dimethylphenylphosphine (PMe 2 Ph) or ethyldiphenylphosphine (PEtPh 2 ) and L is 2,2'-bipyridine (bpy), 4,4'-dimethyl-2,2'-bipyridine (Me 2 bpy), or 1,10-phenanthroline (phen), have been synthesized and characterized. They are prepared by L substitution onto, with concomitant displacement of one chloride and one phosphine ligand from, the mer-TcCl 3 (P) 3 starting material in refluxing ethanol. Analysis of these complexes by fast atom bombardment mass spectrometry (in the positive ion mode) provides fingerprint mass spectra that exhibit peaks assigned to the molecular ion M + as well as peaks assigned to M + minus one or more monodentate ligands. Results of single-crystal x-ray structure determinations of cis(Cl),trans(P)-[TcCl 2 (PMe 2 Ph) 2 (bpy)]BPh 4 (A), cis(Cl),trans(P)-[TcCl 2- (PMe 2 Ph) 2 (phen)]BPh 4 (B), and cis(Cl),trans(P)-[TcCl 2 (PEtPh 2 ) 2 (bpy)]SO 3 CF 3 (C), with formula weights of 921.62, 945.64, and 903.65, respectively are reported. 26 refs., 5 figs., 5 tabs

  6. Two mixed-ligand lanthanide-hydrazone complexes: [Pr(NCS)3(pbh)2]·H2O and [Nd(NCS)(NO3)(pbh)2(H2O)]NO3·2.33H2O [pbh is N'-(pyridin-2-ylmethylidene)benzo-hydrazide, C13H11N3O].

    Science.gov (United States)

    Paschalidis, Damianos G; Harrison, William T A

    2016-02-01

    The gel-mediated syntheses and crystal structures of [N'-(pyridin-2-ylmethylidene-κN)benzohydrazide-κ(2) N',O]tris(thiocyanato-κN)praseodymium(III) mono-hydrate, [Pr(NCS)3(C13H11N3O)2]·H2O, (I), and aqua(nitrato-κ(2) O,O')[N'-(pyri-din-2-ylmethylidene-κN)benzohydrazide-κ(2) N',O](thiocyanato-κN)neo-dym-ium(III) nitrate 2.33-hydrate, [Nd(NCS)(NO3)(C13H11N3O)2(H2O)]NO3·2.33H2O, (II), are reported. The Pr(3+) ion in (I) is coordinated by two N,N,O-tridentate N'-(pyridin-2-ylmethylidene)benzohydrazide (pbh) ligands and three N-bonded thio-cyanate ions to generate an irregular PrN7O2 coordination polyhedron. The Nd(3+) ion in (II) is coordinated by two N,N,O-tridentate pbh ligands, an N-bonded thio-cyanate ion, a bidentate nitrate ion and a water mol-ecule to generate a distorted NdN5O5 bicapped square anti-prism. The crystal structures of (I) and (II) feature numerous hydrogen bonds, which lead to the formation of three-dimensional networks in each case.

  7. Two mixed-ligand lanthanide–hydrazone complexes: [Pr(NCS3(pbh2]·H2O and [Nd(NCS(NO3(pbh2(H2O]NO3·2.33H2O [pbh is N′-(pyridin-2-ylmethylidenebenzohydrazide, C13H11N3O

    Directory of Open Access Journals (Sweden)

    Damianos G. Paschalidis

    2016-02-01

    Full Text Available The gel-mediated syntheses and crystal structures of [N′-(pyridin-2-ylmethylidene-κNbenzohydrazide-κ2N′,O]tris(thiocyanato-κNpraseodymium(III monohydrate, [Pr(NCS3(C13H11N3O2]·H2O, (I, and aqua(nitrato-κ2O,O′[N′-(pyridin-2-ylmethylidene-κNbenzohydrazide-κ2N′,O](thiocyanato-κNneodymium(III nitrate 2.33-hydrate, [Nd(NCS(NO3(C13H11N3O2(H2O]NO3·2.33H2O, (II, are reported. The Pr3+ ion in (I is coordinated by two N,N,O-tridentate N′-(pyridin-2-ylmethylidenebenzohydrazide (pbh ligands and three N-bonded thiocyanate ions to generate an irregular PrN7O2 coordination polyhedron. The Nd3+ ion in (II is coordinated by two N,N,O-tridentate pbh ligands, an N-bonded thiocyanate ion, a bidentate nitrate ion and a water molecule to generate a distorted NdN5O5 bicapped square antiprism. The crystal structures of (I and (II feature numerous hydrogen bonds, which lead to the formation of three-dimensional networks in each case.

  8. Development of immobilized ligands for actinide separations

    International Nuclear Information System (INIS)

    Paine, R.T.

    1994-01-01

    Primary goals during this grant period were to (1) synthesize new bifunctional chelating ligands, (2) characterize the structural features of the Ln and An coordination complexes formed by these ligands, (3) use structural data to iteratively design new classes of multifunctional ligands, and (4) explore additional routes for attachment of key ligands to solid supports that could be useful for chromatographic separations. Some highlights of recently published work as well as a summary of submitted, unpublished and/or still in progress research are outlined

  9. Understanding ligand effects in gold clusters using mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Johnson, Grant E.; Laskin, Julia

    2016-01-01

    This review summarizes recent research on the influence of phosphine ligands on the size, stability, and reactivity of gold clusters synthesized in solution. Sub-nanometer clusters exhibit size- and composition-dependent properties that are unique from those of larger nanoparticles. The highly tunable properties of clusters and their high surface-to-volume ratio make them promising candidates for a variety of technological applications. However, because “each-atom-counts” toward defining cluster properties it is critically important to develop robust synthesis methods to efficiently prepare clusters of predetermined size. For decades phosphines have been known to direct the size-selected synthesis of gold clusters. Despite the preparation of numerous species it is still not understood how different functional groups at phosphine centers affect the size and properties of gold clusters. Using electrospray ionization mass spectrometry (ESI-MS) it is possible to characterize the effect of ligand substitution on the distribution of clusters formed in solution at defined reaction conditions. In addition, ligand exchange reactions on preformed clusters may be monitored using ESI-MS. Collision induced dissociation (CID) may also be employed to obtain qualitative insight into the fragmentation of mixed ligand clusters and the relative binding energies of differently substituted phosphines. Quantitative ligand binding energies and cluster stability may be determined employing surface induced dissociation (SID) in a custom-built Fourier transform ion cyclotron resonance mass spectrometer (FT-ICR-MS). Rice-Ramsperger-Kassel-Marcus (RRKM) based modeling of the SID data allows dissociation energies and entropy values to be extracted that may be compared with the results of high-level theoretical calculations. The charge reduction and reactivity of atomically precise gold clusters, including partially ligated species generated in the gas-phase by in source CID, on well

  10. Understanding ligand effects in gold clusters using mass spectrometry.

    Science.gov (United States)

    Johnson, Grant E; Laskin, Julia

    2016-06-21

    This review summarizes recent research on the influence of phosphine ligands on the size, stability, and reactivity of gold clusters synthesized in solution. Sub-nanometer clusters exhibit size- and composition-dependent properties that are unique from those of larger nanoparticles. The highly tunable properties of clusters and their high surface-to-volume ratio make them promising candidates for a variety of technological applications. However, because "each-atom-counts" toward defining cluster properties it is critically important to develop robust synthesis methods to efficiently prepare clusters of predetermined size. For decades phosphines have been known to direct the size-selected synthesis of gold clusters. Despite the preparation of numerous species it is still not understood how different functional groups at phosphine centers affect the size and properties of gold clusters. Using electrospray ionization mass spectrometry (ESI-MS) it is possible to characterize the effect of ligand substitution on the distribution of clusters formed in solution at defined reaction conditions. In addition, ligand exchange reactions on preformed clusters may be monitored using ESI-MS. Collision induced dissociation (CID) may also be employed to obtain qualitative insight into the fragmentation of mixed ligand clusters and the relative binding energies of differently substituted phosphines. Quantitative ligand binding energies and cluster stability may be determined employing surface induced dissociation (SID) in a custom-built Fourier transform ion cyclotron resonance mass spectrometer (FT-ICR-MS). Rice-Ramsperger-Kassel-Marcus (RRKM) based modeling of the SID data allows dissociation energies and entropy values to be extracted. The charge reduction and reactivity of atomically precise gold clusters, including partially ligated species generated in the gas-phase by in source CID, on well-defined surfaces may be explored using ion soft landing (SL) in a custom

  11. Synthesis, solvatochromism and crystal structure of trans-[Cu(Et2NCH2CH2NH2)2.H2O](NO3)2 complex: Experimental with DFT combination

    Science.gov (United States)

    Warad, Ismail; Musameh, Sharif; Badran, Ismail; Nassar, Nashaat N.; Brandao, Paula; Tavares, Carlos Jose; Barakat, Assem

    2017-11-01

    In this study, two dicationic asymmetrical diamine/copper(II) nitrate salt complexes of the general formula trans-[CuII(NN‧)2.H2O](NO3)2 were successfully synthesized using N,N-dimethylethylenediamine and N,N-diethylethylenediamine as asymmetrical diamine ligands. The structure of complex 2 was identified by X-ray single crystal diffraction analysis confirming that the bidentate ligand N,N-dimethylethylenediamine forms a penta-coordinated complex with an H2O molecule located around the copper(II) ion in a trans configuration. It was found that the metal centre is coordinated in a distorted square pyramidal fashion with a τ value of 0.274. The desired complexes were fully characterized using, MS, UV-Vis, CV, FTIR, TG/DTA, and Hirshfeld surface computational analysis. High level theoretical calculations were also performed in order to investigate the complexes structure, conformers, vibrational frequencies, and their excited states.

  12. EXPERIÊNCIAS ESCOLARES DE ESTUDANTES TRANS

    Directory of Open Access Journals (Sweden)

    Tania Mara Cruz

    2016-04-01

    Full Text Available Este estudo busca resgatar memórias, enquanto estudantes, de duas transexuais femininas, assim autodefinidas, de Tubarão – SC, no intuito de analisar suas experiências escolares durante o paulatino processo de feminilização. Trata-se de pesquisa qualitativa, construída com recortes de histórias de vida na Educação Básica em escolas públicas e nas licenciaturas de História e de Letras em universidades privadas. A pesquisa empírica se deu a partir de entrevistas com roteiro semiestruturado, sendo analisada a partir dos pressupostos dos estudos de gênero e de educação. O contraditório espaço escolar apresentou-se como lugar de discriminação heterossexista, vigilante contra quem não se enquadrasse nos padrões binários e hegemônicos de gênero e de sexualidade. No entanto, devido ao suporte de colegas e da resistência das estudantes trans, tal contexto não as impediu de seguir estudando.

  13. Trans-generational immune priming in honeybees.

    Science.gov (United States)

    Hernández López, Javier; Schuehly, Wolfgang; Crailsheim, Karl; Riessberger-Gallé, Ulrike

    2014-06-22

    Maternal immune experience acquired during pathogen exposure and passed on to progeny to enhance resistance to infection is called trans-generational immune priming (TgIP). In eusocial insects like honeybees, TgIP would result in a significant improvement of health at individual and colony level. Demonstrated in invertebrates other than honeybees, TgIP has not yet been fully elucidated in terms of intensity and molecular mechanisms underlying this response. Here, we immune-stimulated honeybee queens with Paenibacillus larvae (Pl), a spore-forming bacterium causing American Foulbrood, the most deadly bee brood disease worldwide. Subsequently, offspring of stimulated queens were exposed to spores of Pl and mortality rates were measured to evaluate maternal transfer of immunity. Our data substantiate the existence of TgIP effects in honeybees by direct evaluation of offspring resistance to bacterial infection. A further aspect of this study was to investigate a potential correlation between immune priming responses and prohaemocytes-haemocyte differentiation processes in larvae. The results point out that a priming effect triggers differentiation of prohaemocytes to haemocytes. However, the mechanisms underlying TgIP responses are still elusive and require future investigation.

  14. Integration of a semi-rigid proline ligand and 4,4'-bipyridine in the synthesis of homochiral metal-organic frameworks with helices.

    Science.gov (United States)

    Xu, Zhong-Xuan; Kang, Yao; Han, Min-Le; Li, Dong-Sheng; Zhang, Jian

    2015-06-28

    A pair of 3-D homochiral metal-organic frameworks (HMOFs) based on a mixed semi-rigid 5-(2-carboxypyrrolidine-1-carbonyl)isophthalate (PIA) ligand and rigid 4,4'-bipyridine (bipy), [Co3((R)-PIA)2(bipy)3]·6H2O (1-D) and [Co3((S)-PIA)2(bipy)3]·6H2O (1-L) are synthesized and structurally characterized. They are enantiomers and exhibit three-dimensional open frameworks. In each structure, the PIA ligands link the Co centers into homochiral frameworks with large open channels that are occupied by the bipy ligands. Interesting helical chains built from the connectivity between PIA ligands and Co centers are presented. Antiferromagnetic coupling is observed in 1-D. These results demonstrated that the mixed ligand approach is successful for the construction of HMOFs.

  15. Finding a Trans-Affirmative Provider: Challenges Faced by Trans and Gender Diverse Psychologists and Psychology Trainees.

    Science.gov (United States)

    Dickey, Lore M; Singh, Anneliese A

    2017-08-01

    This article explores some of the challenges faced by trans and gender diverse (TGD) individuals who not only are attempting to access trans-affirmative care, but who are also members of the very profession from which they are seeking services. The authors explore challenges related to finding supervision, accessing care for assessment services, and finding a provider for personal counseling. With each example, the authors unpack the challenges and also address the implications for training for all involved. Based on these challenges that TGD psychologists and trainees face in attempting to access care, the authors provide recommendations related to trans-affirmative training for psychologists. © 2017 Wiley Periodicals, Inc.

  16. DESENVOLVIMENTO, LIBERDADE E GÊNERO: EXPERIÊNCIAS TRANS / DEVELOPMENT, FREEDOM AND GENDER: TRANS EXPERIENCES

    Directory of Open Access Journals (Sweden)

    Tuanny Soeiro Sousa

    2017-04-01

    Full Text Available This essay seeks to make an examination on how the gender category influences in the development process, based on the concept of development as freedom by Amartya Sen. In view of this purpose, we analyze the main human rights violations suffered by travesties and transsexuals due to the female and male identity construction in contrast to social norms establishing hierarchical positions of men and women as constituents of male and female categories. In other words, conflicts made in the wake of gender relations. This study is the result of a literature review and analysis of data on homophobic violence against trans experience.

  17. Mapping Discrimination Experienced by Indonesian Trans* FtM Persons.

    Science.gov (United States)

    Gordon, Danny; Pratama, Mario Prajna

    2017-01-01

    This work sought to document how Indonesian trans* FtM persons experienced discrimination across the interlinked domains of social networks, religious and educational institutions, employment and the workplace, and health care institutions. Objectives were (1) to map the discrimination experienced by trans* FtM individuals in Indonesia, and (2) to establish the specific priorities of the Indonesian trans* FtM community. In-depth interviews, focus groups, and participant observation was used involving 14 respondents. Findings revealed that respondents experienced othering through rejection, misidentification, harassment, "correction," and bureaucratic discrimination across the five preestablished domains. Health care and a lack of information emerged as areas of particular concern for respondents. This work calls for health care that is sensitive to the needs of trans* FtM people coupled with high-quality information to alleviate the cycles through which discrimination is sustained.

  18. Trans-cis molecular photoswitching in interstellar Space*

    Science.gov (United States)

    Cuadrado, S.; Goicoechea, J. R.; Roncero, O.; Aguado, A.; Tercero, B.; Cernicharo, J.

    2016-01-01

    As many organic molecules, formic acid (HCOOH) has two conformers (trans and cis). The energy barrier to internal conversion from trans to cis is much higher than the thermal energy available in molecular clouds. Thus, only the most stable conformer (trans) is expected to exist in detectable amounts. We report the first interstellar detection of cis-HCOOH. Its presence in ultraviolet (UV) irradiated gas exclusively (the Orion Bar photodissociation region), with a low trans-to-cis abundance ratio of 2.8 ± 1.0, supports a photoswitching mechanism: a given conformer absorbs a stellar photon that radiatively excites the molecule to electronic states above the interconversion barrier. Subsequent fluorescent decay leaves the molecule in a different conformer form. This mechanism, which we specifically study with ab initio quantum calculations, was not considered in Space before but likely induces structural changes of a variety of interstellar molecules submitted to UV radiation. PMID:28003686

  19. Exoplanet: Trans-dimentional MCMC method for exoplanet discovery

    Science.gov (United States)

    Brewer, Brendon J.

    2015-01-01

    Exoplanet determines the posterior distribution of exoplanets by use of a trans-dimensional Markov Chain Monte Carlo method within Nested Sampling. This method finds the posterior distribution in a single run rather than requiring multiple runs with trial values.

  20. TRANS-NEPTUNIAN OBJECT LIGHTCURVES V1.1

    Data.gov (United States)

    National Aeronautics and Space Administration — This data set includes a collection of published lightcurves of trans-Neptunian objects published through December 2002. The collection includes lightcurves of 18...

  1. Crystal structure of trans-dichloridobis[N-(5,5-dimethyl-4,5-dihydro-3H-pyrrol-2-yl-κNacetamide]palladium(II dihydrate

    Directory of Open Access Journals (Sweden)

    Jamal Lasri

    2017-04-01

    Full Text Available The title complex, [PdCl2(C8H14N2O2]·2H2O, was obtained by N–O bond cleavage of the oxadiazoline rings of the trans-[dichlorido-bis(2,5,5-trimethyl-5,6,7,7a-tetrahydropyrrolo[1,2-b][1,2,4]oxadiazole-N1]palladium(II complex. The palladium(II atom exhibits an almost square-planar coordination provided by two trans-arranged chloride anions and a nitrogen atom from each of the two neutral organic ligands. In the crystal, N—H...O, O—H...O and O—H...Cl hydrogen bonds link complex molecules into double layers parallel to the bc plane.

  2. Multicomponent Ligand Interactions with Colloidal Gold and Silver Nanoparticles in Water

    Science.gov (United States)

    Siriwardana, W.-K.-Kumudu Dilhani

    Multicomponent ligand interactions are involved in essentially all nanoparticle (NP) applications. However, the ligand conformation and ligand binding mechanisms on NPs are highly controversial. The research reported here is focused on deepening the fundamental understanding of multicomponent ligand interactions with gold and silver nanoparticles (AuNPs and AgNPs) in water. We demonstrated that AuNPs passivated by saturated layer of poly(ethylene glycol) (PEG-SH) have large fractions of AuNP surface area available for ligand adsorption and exchange. The fraction of AuNP surface area passivated by PEG-SH with molecular weights of 2000, 5000, and 30000 g/mol was calculated to be 25%, 20%, and 9% using 2-mercaptobenzimidazole and adenine as model ligands. The effect of both reduced and oxidized protein cysteine residues on protein interactions with AgNPs was investigated. The model proteins included wild-type and mutated GB3 variants with 0, 1, or 2 reduced cysteine residues. Bovine serum albumin containing 34 oxidized (disulfide-linked) and 1 reduced cysteine residues was also included. Protein cysteine content that were found to have no detectable effect on kinetics of protein/AgNP binding. However, only proteins that contain reduced cysteine induced significant AgNP dissolution. We further demonstrated that organothiols can induce both AgNP disintegration and formation under ambient conditions by simply mixing organothiols with AgNPs or AgNO3, respectively. Surface plasmon- and fluorescence-active AgNPs formed by changing the concentration ratio between Ag+ and organothiol. Organothiols also induced AuNP formation by mixing HAuCl4 with organothiols, but no AuNP disintegration occured. Finally, we proposed that multicomponent ligand binding to AuNPs can be highly dependent on the sequence of ligand mixing with AuNPs. Quantitative studies revealed that competitive adenine and glutathione adsorption onto both as-synthesized and PEG-SH functionalized AuNPs is

  3. The importance of trans-generational effects in Lepidoptera

    OpenAIRE

    Woestmann, Luisa; Saastamoinen, Marjo

    2016-01-01

    The importance of trans-generational effects in shaping an individuals' phenotype and fitness, and consequently even impacting population dynamics is increasingly apparent. Most of the research on trans-generational effects still focuses on plants, mammals, and birds. In the past few years, however, increasing number of studies, especially on maternal effects, have highlighted their importance also in many insect systems. Lepidoptera, specifically butterflies, have been used as model systems ...

  4. Kinetics of the Acid Hydrolysis of Potassium Trans-dioxalatobis ...

    African Journals Online (AJOL)

    Kinetics of the Acid Hydrolysis of Potassium Trans-dioxalatobis(Ethylnicotinate) Chromium(iii). T.B.R. Yormah, D.V.A. Fode, M.K. Kormoh. Abstract. The kinetics of the aquation of trans-Cr(ox)2(py.3COOEt)2 - has been studied spectrophotometrically in aqueous HClO4-NaClO4 media. The results indicate a first-order ...

  5. Plasma phospholipid trans fatty acids and risk of heart failure.

    Science.gov (United States)

    Tokede, Oluwabunmi A; Petrone, Andrew B; Hanson, Naomi Q; Tsai, Michael Y; Weir, Natalie A; Glynn, Robert J; Gaziano, J Michael; Djoussé, Luc

    2013-04-01

    Although trans fatty acids (TFAs) may increase the risk of dyslipidemia and coronary artery disease (CAD), limited data are available on their association with heart failure (HF). Our goal was to assess associations of plasma and dietary TFAs with HF and CAD. We used a prospective, nested case-control design to select 788 incident HF cases and 788 matched controls from the Physicians' Health Study for biomarker analyses and a prospective cohort for the dietary analyses. Plasma fatty acids were assessed by using gas chromatography, and dietary intake was estimated by using a food-frequency questionnaire. Self-reported HF was ascertained by using annual follow-up questionnaires with validation in a subsample. We used conditional logistic (or Cox) regression to estimate multivariable-adjusted ORs (or HRs) for HF and CAD. Multivariable-adjusted ORs (95% CIs) for HF across consecutive quintiles of plasma trans 18:2 (linoleic acid) fatty acids were 1.0 (reference), 1.10 (0.79, 1.54), 0.88 (0.62, 1.25), 0.71 (0.49, 1.02), and 0.67 (0.45, 0.98) (P-trend = 0.01). Each SD of plasma trans 18:2 was associated with a 22% lower risk of HF (95% CI: 6%, 36%). Plasma trans 16:1 and 18:1 were not associated with risk of HF (P > 0.05). Dietary trans fats were not associated with incident HF or CAD. Our data are consistent with a lower risk of HF with higher concentrations of plasma trans 18:2 but not with trans 16:1 or trans 18:1 fatty acids in male physicians. Dietary TFAs were not related to incident HF or CAD.

  6. Naturally occurring and process-induced trans fatty acids and ...

    African Journals Online (AJOL)

    CHOKRI

    2013-05-22

    May 22, 2013 ... geometric and positional isomerization. As shown in. Figure 3, three individual isomers of trans linoleic acid were eluted before linoleic acid [18:2 n-6 (c9, c12)] in the following order: 18:2 (t9, t12), 18:2 (t9, c12) and 18:2 (c9, t12). The level of total trans linoleic acid isomers was. 1.84-fold higher in butter oil ...

  7. Regional Cooperation Towards Trans-country Natural Gas Market

    DEFF Research Database (Denmark)

    Shukla, P.R.; Dhar, Subash

    2009-01-01

    India began gas imports since 2004 through liquified natural gas (LNG) route. Imports through trans-country gas pipelines could help in bringing gas directly into the densely populated Northern part of India, which are far from domestic gas resources as well as coastal LNG terminals. The purpose...... of this paper is to report scenarios, which quantify the impacts for India of regional cooperation to materialize trans-country pipelines. The analysis covers time period from 2005 to 2030....

  8. Character, Audience Agency and Trans-Media Drama

    OpenAIRE

    Evans, Elizabeth

    2007-01-01

    Changes in the television industry with regards to the development of new media technologies are having a significant impact on audience engagement with television drama. This article explores how the internet is being used to extend audience engagement onto platforms other than the television set to the point where television drama should increasingly be reconsidered as trans-media drama. However audience engagement with the various elements of a trans-media drama text is complex. By explori...

  9. Eco-friendly kinetic separation of trans-limonene and ...

    Indian Academy of Sciences (India)

    Kinetic separation of trans-limonene oxide and trans-carvomenthene oxide was achieved in high yield by selective ring opening of their cis-epoxides in the presence of InCl3 catalyst in water. Catalytic activity of InCl3 was conserved up to 10 cycles. Nucleophilic addition of methanol in presence of InCl3 was also selective ...

  10. Letter to the editor: healthy alternatives to trans fats

    OpenAIRE

    Destaillats, Fr?d?ric; Moulin, Julie; Bezelgues, Jean-Baptiste

    2007-01-01

    Abstract Consumption of trans fats is associated with an increase of cardiovascular disease (CVD) risk. To comply with regulatory policies and public health authorities recommendations, trans fats should be replaced in food products. The study by Sundram et al. (Nutrition & Metabolism 2007, 4:3) reporting the effect on CVD risk factors of interesterified fat (IE) and partially hydrogenated soybean oil (PHSO) compared to palm olein (POL) has been critically analyzed. The study design and in pa...

  11. Insulin Mimetic Peroxo Complexes of Vanadium Containing Uracil or Cytosine as Ligand

    OpenAIRE

    Sarkar, Asit R.; Mandal, Shipra

    2000-01-01

    Mixed ligand oxo peroxo complexes of vanadium (V), M[VO(O2)L2].nH2O where M = K or NH4, HL = uracil or cytosine and n = 1 or 2, have been isolated from aqueous methanolic medium. The complexes were characterised by elemental analysis, conductance, TGA, UV-Visible, IR and NMR spectral studies. Both the peroxide and the other ligands acts as chelates coordinating through their oxygen at C (2) and nitrogen at N (3) and the presence of monomeric oxoperoxovanadium (V) species, have been establishe...

  12. Macrocyclic ligands for uranium complexation

    Energy Technology Data Exchange (ETDEWEB)

    Potts, K.T.

    1991-04-01

    A highly preorganized 24-macrocycle containing biuret, thiobiuret and pyridine subunits has been prepared by high dilution ring-closure procedures. Intermediate products to this macrocycle have been utilized to extend this synthetic route to include further representatives where solubility and stability will be influenced by substituent variation. A 1:1 complex has been formed from uranyl acetate and a quinquepyridine derivative, this representing a new type of ligand for the uranyl ion. A very convenient synthetic procedure that will allow the incorporation of these macrocycles into polymeric systems has been developed for the introduction of a vinyl substituent into the 4-position of the pyridine ring. Using triflate, vinyltributyltin and Pd{sup 0} chemistry, this procedure should make a variety of substituted 4-vinylpyridines available for the first time. 3 refs.

  13. Macrocyclic ligands for uranium complexation

    International Nuclear Information System (INIS)

    Potts, K.T.

    1991-04-01

    A highly preorganized 24-macrocycle containing biuret, thiobiuret and pyridine subunits has been prepared by high dilution ring-closure procedures. Intermediate products to this macrocycle have been utilized to extend this synthetic route to include further representatives where solubility and stability will be influenced by substituent variation. A 1:1 complex has been formed from uranyl acetate and a quinquepyridine derivative, this representing a new type of ligand for the uranyl ion. A very convenient synthetic procedure that will allow the incorporation of these macrocycles into polymeric systems has been developed for the introduction of a vinyl substituent into the 4-position of the pyridine ring. Using triflate, vinyltributyltin and Pd 0 chemistry, this procedure should make a variety of substituted 4-vinylpyridines available for the first time. 3 refs

  14. A Thousand Words Are Worth a Picture: A Snapshot of Trans* Postsecondary Educators in Higher Education

    Science.gov (United States)

    Simmons, Symone L.

    2017-01-01

    Trans* is becoming a buzzword and trans* celebrities have become increasingly visible. On college campuses, trans* students have also become more visible and advocacy for them continues to be extremely important. To support these claims, some literature has emerged regarding trans* college students' identity development and experiences on…

  15. 77 FR 22576 - Possible Revocation of Ocean Transportation Intermediary License No. 021899-Trans World Logistics...

    Science.gov (United States)

    2012-04-16

    ... information about its OTI business, Trans World Logistics has repeatedly failed to reply to such requests. The... Intermediary License No. 021899--Trans World Logistics Corporation; Order To Show Cause Trans World Logistics Corporation (Trans World Logistics) is an Indiana corporation, incorporated in October 2006. Records...

  16. DETERMINATION OF MIXED STABILITY CONSTANTS OF LEAD(II ...

    African Journals Online (AJOL)

    A method involving the use of paper ionophoresis is described for the study of equilibria in mixedligand complex systems in solution. The technique is based on the movement of a spot of metal ion under an electric field with the complexants added to the background electrolyte at pH 8.5. The stability constants of the ...

  17. Intervalence charge transfer transition in mixed valence complexes ...

    Indian Academy of Sciences (India)

    Keywords. Mixed valence complexes; intervalence charge transfer; rotaxane; inclusion complex; optical electron transfer; cyclodextrin. ... Further, inclusion of the bridging ligand with interrupted -electron system in a -CD cavity initiate an optical electron transfer from Fe(II) to Ru(III) which is otherwise not observed.

  18. Photo-induced chemical reaction of trans-resveratrol.

    Science.gov (United States)

    Zhao, Yue; Shi, Meng; Ye, Jian-Hui; Zheng, Xin-Qiang; Lu, Jian-Liang; Liang, Yue-Rong

    2015-03-15

    Photo-induced chemical reaction of trans-resveratrol has been studied. UV B, liquid state and sufficient exposure time are essential conditions to the photochemical change of trans-resveratrol. Three principal compounds, cis-resveratrol, 2,4,6-phenanthrenetriol and 2-(4-hydroxyphenyl)-5,6-benzofurandione, were successively generated in the reaction solution of trans-resveratrol (0.25 mM, 100% ethanol) under 100 μW cm(-2) UV B radiation for 4h. cis-Resveratrol, originated from isomerization of trans-resveratrol, resulted in 2,4,6-phenanthrenetriol through photocyclisation reaction meanwhile loss of 2 H. 2,4,6-Phenanthrenetriol played a role of photosensitizer producing singlet oxygen in the reaction pathway. The singlet oxygen triggered [4+2] cycloaddition reaction of trans-resveratrol, and then resulted in the generation of 2-(4-hydroxyphenyl)-5,6-benzofurandione through photorearrangement and oxidation reaction. The singlet oxygen reaction was closely related to the substrate concentration of trans-resveratrol in solution. Copyright © 2014 Elsevier Ltd. All rights reserved.

  19. A mixed-valent cyclodiphosphazane: Transition metal chemistry and ...

    Indian Academy of Sciences (India)

    The hydrolysis of cis-{ClP(-NBu)2P(NHBu)} (1) produced a mixed PIII/PV derivative of cyclodiphosphazane, cis-{(BuNH)P(-NBu)2P(O)H} (2). The treatment of 2 with elemental selenium resulted in the formation of the monoselenide, trans-{(BuNH)P(Se)(-NBu)2P(O)H} (3) in good yield. The reactions of two ...

  20. Insecticidal activity of basil oil, trans-anethole, estragole, and linalool to adult fruit flies of Ceratitis capitata, Bactrocera dorsalis, and Bactrocera cucurbitae.

    Science.gov (United States)

    Chang, Chiou Ling; Cho, Il Kyu; Li, Qing X

    2009-02-01

    Basil oil and its three major active constituents (trans-anethole, estragole, and linalool) obtained from basil (Oscimum basilicum L.) were tested on three tephritid fruit fly species [Ceratitis capitata (Wiedemann), Bactrocera dorsalis (Hendel), and Bactrocera cucurbitae (Coquillett)] for insecticidal activity. All test chemicals acted fast and showed a steep dose-response relationship. The lethal times for 90% mortality/knockdown (LT90) of the three fly species to 10% of the test chemicals were between 8 and 38 min. The toxic action of basil oil in C. capitata occurred significantly faster than in B. cucurbitae but slightly faster than in B. dorsalis. Estragole acted faster in B. dorsalis than in C. capitata and B. cucurbitae. Linalool action was faster in B. dorsalis and C. capitata than in B. cucurbitae. trans-Anethole action was similar to all three species. Methyl eugenol acted faster in C. capitata and B. cucurbitae than in B. dorsalis. When linalool was mixed with cuelure (attractant to B. cucurbitae male), its potency to the three fly species decreased as the concentration of cuelure increased. This was due to linalool hydrolysis catalyzed by acetic acid from cuelure degradation, which was confirmed by chemical analysis. When methyl eugenol (B. dorsalis male attractant) was mixed with basil oil, trans-anethole, estragole, or linalool, it did not affect the toxicity of basil oil and linalool to B. dorsalis, but it did significantly decrease the toxicity of trans-anethole and estragole. Structural similarity between methyl eugenol and trans-anethole and estragole suggests that methyl eugenol might act at a site similar to that of trans-anethole and estragole and serve as an antagonist if an action site exists. Methyl eugenol also may play a physiological role on the toxicity reduction.

  1. Ligand based pharmacophore modelling of anticancer histone ...

    African Journals Online (AJOL)

    USER

    2010-06-21

    Jun 21, 2010 ... HDAC ligands (Chen et al., 2008b). The knowledge of common properties of the binding group is essential for the determination of the type of inhibitor binding the target. Major goal of modern drug design is identification and development of new ligands with high affinity of binding toward a given protein.

  2. Organometallic chemistry of chiral diphosphazane ligands ...

    Indian Academy of Sciences (India)

    Unknown

    1. Introduction. Diphosphazanes constitute a class of versatile short-bite bidentate P-donor ligands that have given rise to a varied and extensive transition metal organometallic chemistry. The organometallic chemistry of diphosphazane ligands with almost every transition metal in the periodic table is well documented1–3.

  3. Cofactor-Controlled Chirality of Tropoisomeric Ligand

    NARCIS (Netherlands)

    Théveau, L.; Bellini, R.; Dydio, P.; Szabo, Z.; van der Werf, A.; Sander, R.A.; Reek, J.N.H.; Moberg, C.

    2016-01-01

    A new tropos ligand with an integrated anion receptor receptor site has been prepared. Chiral carboxylate and phosphate anions that bind in the anion receptor unit proved capable of stabilizing chiral conformations of the achiral flexible bidentate biaryl phosphite ligand, as shown by variable

  4. Ligand modification for mono- and biphasic oxosynthesis

    Energy Technology Data Exchange (ETDEWEB)

    Haerter, P.; Herrmann, W.A.; Baskakov, D. [Technische Univ. Muenchen (Germany). Dept. Chemie

    2006-07-01

    The use of aqueous/organic biphasic systems has attracted huge interest in catalytic reactions by transition metal complexes. [1,2,3] The biphasic systems have benefits in catalyst separation and recycling, and the reduction or elimination of organic solvents is also advantageous for the development of economical and environmentally friendly processes. The key for such biphasic catalysis is the use of water soluble phosphines as ligands. Since the launch of the commercial propylene hydroformylation process by Ruhrchemie/Rhone-Poulenc, sulfonated ligands such as TPPTS (1), and BINAS (2) have been widely used as ligands in hydroformylation, hydrogenation and related reactions catalyzed by transition metals. One of the draw backs of ligands 1 and 2 are corrosive production conditions and therefore unfavorable costs. With the synthesis of aminoacid based trishydroxymethylphosphine derivatives (THMP-aminoacid) we introduce to our knowledge a new group of water soluble and cheap to produce ligands [8]. The properties of catalysts based on these compounds in the hydroformylation reaction of propene are discussed in comparison to normally used catalyst systems. In a second part the performance of catalysts containing NHC-ligands in the hydroformylation of 1-octene is discussed [9]. These investigations show, that the activity can be influenced by the electron donating ability of the NHC ligand. Sterical variations on the NHC ligands have no effect on the selectivity performance of the the catalysts. (orig.)

  5. Organometallic chemistry of chiral diphosphazane ligands ...

    Indian Academy of Sciences (India)

    Unknown

    organometallic chemistry of diphosphazane ligands with almost every transition metal in the periodic table is well documented1–3. A very attractive feature of diphosphazane ligands is that 'chirality' can be incorporated at the phosphorus centres as well as at the substituents attached to the nitrogen and the two phosphorus ...

  6. Ligand sphere conversions in terminal carbide complexes

    DEFF Research Database (Denmark)

    Morsing, Thorbjørn Juul; Reinholdt, Anders; Sauer, Stephan P. A.

    2016-01-01

    Metathesis is introduced as a preparative route to terminal carbide complexes. The chloride ligands of the terminal carbide complex [RuC(Cl)2(PCy3)2] (RuC) can be exchanged, paving the way for a systematic variation of the ligand sphere. A series of substituted complexes, including the first exam...

  7. Dysprosium complexes with the tetraphenylporphyrin macrocyclic ligand

    International Nuclear Information System (INIS)

    Martinez M, V.; Padilla, J.; Ramirez, F.M.

    1992-04-01

    In this report, the results obtained on the synthesis, characterization and study of the chemical behavior of dysprosium complex with the acetylacetone chelating agent (Hacac) and the tetraphenylporphyrin macrocyclic ligand (H 2 TFP) are given. Based on the literature but according to our necessities and interest, the appropriate methodology settled down from the synthesis of prime matters until the obtaining and characterization of the products. The acetyl acetonate complex was obtained of mono hydrated dysprosium [Dy(acac) 3 . H 2 0] and trihydrated [Dy(acac) 3 .3 H 2 0], the mono tetra phenyl porphyrinate [Dy(TFP)(acac). 2 ac] the double sandwich of the dysprosium porphyrinate [Dy(TFP) 2 ] and the triple sandwich of the dysprosium porphyrinate [Dy(TFP) 3 . 2 TCB] (TCB = trichlorobenzene). Its were characterized by their melting points, solubility, IR, UV, TGA and DTA both first and besides the techniques already mentioned for NMR'H, RPE and Magnetic susceptibility the three last complexes. From the spectroscopic point of view, IR and RPE its suggested the existence of a complex of inverse mixed valence [Dy(TFP) 2- (TFP) 1- ] for the Dy(TFP) 2 as a result of the existence of the free radical (TFP' 1- and that it was not in none of the other porphyrin compounds. In the NMR'H spectra of the compounds were not observed signals in the region from 0 to 10 ppm that which shows that the dysprosium complexes in special those of the porphyrin type are highly paramagnetic and its could be used as displacement reagents, creators of images and contrast agents of great utility in these days in studies of NMR, technique today by today used in medical diagnoses. (Author)

  8. THE RESONANT TRANS-NEPTUNIAN POPULATIONS

    International Nuclear Information System (INIS)

    Gladman, B.; Lawler, S. M.; Van Laerhoven, C.; Petit, J.-M.; Rousselot, P.; Kavelaars, J.; Jones, R. L.; Parker, J. Wm.; Bieryla, A.; Nicholson, P.; Ashby, M. L. N.

    2012-01-01

    The trans-Neptunian objects (TNOs) trapped in mean-motion resonances with Neptune were likely emplaced there during planet migration late in the giant-planet formation process. We perform detailed modeling of the resonant objects detected in the Canada-France Ecliptic Plane Survey (CFEPS) in order to provide population estimates and, for some resonances, constrain the complex internal orbital element distribution. Detection biases play a critical role because phase relationships with Neptune make object discovery more likely at certain longitudes. This paper discusses the 3:2, 5:2, 2:1, 3:1, 5:1, 4:3, 5:3, 7:3, 5:4, and 7:4 mean-motion resonances, all of which had CFEPS detections, along with our upper limit on 1:1 Neptune Trojans (which is consistent with their small population estimated elsewhere). For the plutinos (TNOs in the 3:2 resonance) we refine the orbital element distribution given by Kavelaars et al. in 2009 and show that steep H-magnitude distributions (N(H)∝10 αH , with α = 0.8-0.9) are favored in the range H g = 8-9, and confirm that this resonance does not share the inclination distribution of the classical Kuiper Belt. We give the first population estimate for the 5:2 resonance and find that, to within the uncertainties, the population is equal to that of the 3:2 (≅13,000 TNOs with H g g 100 km) populations in the thousands. We compare our intrinsic population and orbital element distributions with several published models of resonant-TNO production; the most striking discrepancy is that resonances beyond the 2:1 are in reality more heavily populated than in published models.

  9. A directed approach for the identification of transcripts harbouring the spliced leader sequence and the effect of trans-splicing knockdown in Schistosoma mansoni.

    Science.gov (United States)

    Mourão, Marina de Moraes; Bitar, Mainá; Lobo, Francisco Pereira; Peconick, Ana Paula; Grynberg, Priscila; Prosdocimi, Francisco; Waisberg, Michael; Cerqueira, Gustavo Coutinho; Macedo, Andréa Mara; Machado, Carlos Renato; Yoshino, Timothy; Franco, Glória Regina

    2013-09-01

    Schistosomiasis is a major neglected tropical disease caused by trematodes from the genus Schistosoma. Because schistosomes exhibit a complex life cycle and numerous mechanisms for regulating gene expression, it is believed that spliced leader (SL) trans-splicing could play an important role in the biology of these parasites. The purpose of this study was to investigate the function of trans-splicing in Schistosoma mansoni through analysis of genes that may be regulated by this mechanism and via silencing SL-containing transcripts through RNA interference. Here, we report our analysis of SL transcript-enriched cDNA libraries from different S. mansoni life stages. Our results show that the trans-splicing mechanism is apparently not associated with specific genes, subcellular localisations or life stages. In cross-species comparisons, even though the sets of genes that are subject to SL trans-splicing regulation appear to differ between organisms, several commonly shared orthologues were observed. Knockdown of trans-spliced transcripts in sporocysts resulted in a systemic reduction of the expression levels of all tested trans-spliced transcripts; however, the only phenotypic effect observed was diminished larval size. Further studies involving the findings from this work will provide new insights into the role of trans-splicing in the biology of S. mansoni and other organisms. All Expressed Sequence Tags generated in this study were submitted to dbEST as five different libraries. The accessions for each library and for the individual sequences are as follows: (i) adult worms of mixed sexes (LIBEST_027999: JZ139310 - JZ139779), (ii) female adult worms (LIBEST_028000: JZ139780 - JZ140379), (iii) male adult worms (LIBEST_028001: JZ140380 - JZ141002), (iv) eggs (LIBEST_028002: JZ141003 - JZ141497) and (v) schistosomula (LIBEST_028003: JZ141498 - JZ141974).

  10. A directed approach for the identification of transcripts harbouring the spliced leader sequence and the effect of trans-splicing knockdown in Schistosoma mansoni

    Directory of Open Access Journals (Sweden)

    Marina de Moraes Mourao

    2013-09-01

    Full Text Available Schistosomiasis is a major neglected tropical disease caused by trematodes from the genus Schistosoma. Because schistosomes exhibit a complex life cycle and numerous mechanisms for regulating gene expression, it is believed that spliced leader (SL trans-splicing could play an important role in the biology of these parasites. The purpose of this study was to investigate the function of trans-splicing in Schistosoma mansoni through analysis of genes that may be regulated by this mechanism and via silencing SL-containing transcripts through RNA interference. Here, we report our analysis of SL transcript-enriched cDNA libraries from different S. mansoni life stages. Our results show that the trans-splicing mechanism is apparently not associated with specific genes, subcellular localisations or life stages. In cross-species comparisons, even though the sets of genes that are subject to SL trans-splicing regulation appear to differ between organisms, several commonly shared orthologues were observed. Knockdown of trans-spliced transcripts in sporocysts resulted in a systemic reduction of the expression levels of all tested trans-spliced transcripts; however, the only phenotypic effect observed was diminished larval size. Further studies involving the findings from this work will provide new insights into the role of trans-splicing in the biology of S. mansoni and other organisms. All Expressed Sequence Tags generated in this study were submitted to dbEST as five different libraries. The accessions for each library and for the individual sequences are as follows: (i adult worms of mixed sexes (LIBEST_027999: JZ139310 - JZ139779, (ii female adult worms (LIBEST_028000: JZ139780 - JZ140379, (iii male adult worms (LIBEST_028001: JZ140380 - JZ141002, (iv eggs (LIBEST_028002: JZ141003 - JZ141497 and (v schistosomula (LIBEST_028003: JZ141498 - JZ141974.

  11. Biomimetic affinity ligands for protein purification.

    Science.gov (United States)

    Sousa, Isabel T; Taipa, M Angela

    2014-01-01

    The development of sophisticated molecular modeling software and new bioinformatic tools, as well as the emergence of data banks containing detailed information about a huge number of proteins, enabled the de novo intelligent design of synthetic affinity ligands. Such synthetic compounds can be tailored to mimic natural biological recognition motifs or to interact with key surface-exposed residues on target proteins and are designated as "biomimetic ligands." A well-established methodology for generating biomimetic or synthetic affinity ligands integrates rational design with combinatorial solid-phase synthesis and screening, using the triazine scaffold and analogues of amino acids side chains to create molecular diversity.Triazine-based synthetic ligands are nontoxic, low-cost, highly stable compounds that can replace advantageously natural biological ligands in the purification of proteins by affinity-based methodologies.

  12. Biscoitos recheados: quanto mais baratos maior teor de gordura trans? = Filled cookies: the cheaper the higher trans fat content?

    Directory of Open Access Journals (Sweden)

    Galdino, Tatiana Pizzato

    2010-01-01

    Conclusões: quanto maior a quantidade de gorduras trans, menor a quantidade de gordura saturada e menor preço. Sugere-se uma revisão na legislação quanto à inserção da quantidade exata de gorduras trans no rótulo, uma vez que o consumo elevado dessas gorduras está associado a dislipidemias, um fator de risco para doença cardiovascular

  13. PUTAS Y TRANS. ¿ESTÁN LAS MUJERES TRANS EN LAS NARRATIVAS SOBRE LA PROSTITUCIÓN?

    Directory of Open Access Journals (Sweden)

    Liza García Reyes

    2015-06-01

    Full Text Available Este artículo evidencia los principales resultados de la investigación cualitativa titulada: Putas y trans. Narrativas sobre mujeres trans en España –desarrollada en 2010–, la cual estudió su presencia en textos académicos sobre prostitución en España, producidos entre los años 2000-2009. El análisis de contenido de 34 narrativas evidenció que las referencias a mujeres trans resulta escasa en ellas, aun siendo ellas quienes tienen mayor presencia en la prostitución, en proporción con las mujeres biológicas. Solo nueve textos mencionan la experiencia trans al interior de la prostitución y, entre estos, el asunto solo aparece asertivamente descrito cuando son las propias mujeres trans quienes escriben. AbstractThis paper shows the results of a qualitative research entitled: Hookers and Trans Women: Narratives about trans women in Spain. This study was developed in 2010 and it is based on presence of trans women in the academic texts of prostitution in Spain produced between 2000 and 2009. The content analysis of thirty four narratives showed that the references to in transsexual women in these texts were few, although they have more presence into prostitution, in relation to the biological women. Only nine texts show an experience of prostitution and among these, transexperience only is described assertively when transsexual women write the texts themselves.

  14. Reasons for decision in the matter of Trans Mountain Pipeline Inc. (formerly Terasen Pipelines (Trans Mountain) Inc.) : tariffs

    International Nuclear Information System (INIS)

    2007-01-01

    In 2006 and 2007 Terasen Pipelines (Trans Mountain) Inc. (now Trans Mountain Pipeline Inc.) submitted a series of applications to the National Energy Board for revisions to the Trans Mountain Tariffs. They were filed in response to apportionment concerns on the Trans Mountain pipeline. Four of the applications involved pronounced and contentious changes to the capacity allocation procedures on the pipeline system. For ease of reference, the Board amalgamated its 4 decisions on these applications into a single document. A map of the Trans Mountain pipeline system as a whole was presented along with a detailed map indicating the delivery locations served by the system in the lower mainland of British Columbia and the state of Washington. The issues considered by the Board in each of these decisions included capacity allocation for Westridge Dock; capacity allocations to export destinations; common carriage requirements; and the need for creating a new barge subcategory. Relevant sections of the National Energy Board Act referred to in the decisions were highlighted. This document also listed the Trans Mountain Tariffs that have introduced notable revisions to the capacity allocation procedures on the system since September 2003. 16 refs., 2 figs., 3 appendices

  15. Overview of infrared methodologies for trans fat determination.

    Science.gov (United States)

    Mossoba, Magdi M; Yurawecz, Martin P; Delmonte, Pierluigi; Kramer, John K G

    2004-01-01

    trans Fatty acids are present in a variety of foods like dairy products, but the major sources are products that contain commercially hydrogenated fats. Some studies have shown that trans fatty acids elevate levels of serum low-density lipoprotein (LDL)-cholesterol and lower high-density lipoprotein (HDL)-cholesterol. The quantitation and identification of trans fatty acid isomers is difficult because of the wide range of positional monoene, diene, and triene fatty acid isomers present in hydrogenated oils. This is complicated by the cis positional isomers that are also present, as well as the lack of commercial chromatographic standards for many fatty acid isomers. In this review, infrared methodologies for the determination of total trans fat are presented. Using an attenuated total reflection (ATR) infrared cell, a novel Fourier transform infrared (FTIR) spectroscopic method that was developed for the rapid (5 min) quantitation of the total trans fatty acid levels in neat (without solvent) fats and oils measured as triacylglycerols (TAG) is discussed. TAG required no derivatization, but had to be melted prior to measurement. The lower limit of trans quantitation was 5% of total fat. The precision of this ATR method was found to be superior to that of transmission infrared official methods. Accuracy was enhanced by generating a symmetric absorption trans infrared band at 966 cm(-1) on a horizontal background. This was achieved by "ratioing" the single-beam spectrum of the trans-containing fat or oil against that of a reference oil or standard having only cis double bonds. Attempts to apply this ATR-FTIR method to food matrixes with low trans fat and/or low total fat content were not satisfactory due to interfering infrared absorptions in the trans region. To overcome this interference, the method was modified by applying the standard addition technique to the ATR-FTIR determination. The modified procedure required more time, but eliminated any adverse impact on

  16. High Trans Kinetic Selectivity in Ruthenium-Based Olefin Cross-Metathesis through Stereoretention.

    Science.gov (United States)

    Johns, Adam M; Ahmed, Tonia S; Jackson, Bradford W; Grubbs, Robert H; Pederson, Richard L

    2016-02-19

    The first kinetically controlled, highly trans-selective (>98%) olefin cross-metathesis reaction is demonstrated using Ru-based catalysts. Reactions with either trans or cis olefins afford products with highly trans or cis stereochemistry, respectively. This E-selective olefin cross-metathesis is shown to occur between two trans olefins and between a trans olefin and a terminal olefin. Additionally, new stereoretentive catalysts have been synthesized for improved reactivity.

  17. Mechanistic Insights into Solvent and Ligand Dependency in Cu(I)-Catalyzed Allylic Alkylation with gem-Diborylalkanes.

    Science.gov (United States)

    Zhang, Qi; Wang, Bing; Liu, Jia-Qin; Fu, Yao; Wu, Yu-Cheng

    2018-01-19

    The recent Cu-catalyzed allylic substitution reaction between gem-diboryalkane and allyl electrophiles shows intriguing solvent and ligand-controlled regioselectivity. The α-alkylation product was obtained in DMF solvent, while γ-alkylation product was obtained in dioxane solvent and the dioxane and NHC ligand situation. In the present study, density functional theory calculations have been used to investigate the reaction mechanism and origin of the regioselectivity. For both dioxane and DMF, γ-alkylation undergoes successive oxidative addition (CH 2 Bpin trans to leaving group) and direct Cγ-C reductive elimination. The α-alkylation is found to undergo oxidative addition (CH 2 Bpin trans to leaving group), isomerization, and Cα-C reductive elimination rather than the previously proposed oxidative addition (-CH 2 Bpin cis to the leaving group) and Cα-C reductive elimination. The γ-alkylation and α-alkylation is, respectively, favorable for dioxane and DMF solvent, which is consistent with the γ- and α-selectivity in experiment. The solvent interferes the isomerization step, thereby affects the relative facility of the α- and γ-alkylation. Further investigation shows that η 1 -intermediate formation promoted by solvent is the rate-determining step of the isomerization. The stronger electron-donating ability of DMF than dioxane facilitates the η 1 -intermediate formation and finally results in the easier isomerization in DMF. For dioxane and NHC situation, in the presence of neutral NHC ligand, the -PO 4 Et 2 group tightly coordinates with the Cu center after the oxidative addition, preventing the isomerization process. The regioselectivity is determined by the relative facility of the oxidative addition step. Therefore, the favorable oxidative addition (in which -CH 2 Bpin trans to the leaving group) results in the facility of γ-alkylation.

  18. Origin of trans-bent geometries in maximally bonded transition metal and main group molecules.

    Science.gov (United States)

    Landis, Clark R; Weinhold, Frank

    2006-06-07

    Recent crystallographic data unambiguously demonstrate that neither Ar'GeGeAr' nor Ar'CrCrAr' molecules adopt the expected linear (VSEPR-like) geometries. Does the adoption of trans-bent geometries indicate that Ar'MMAr' molecules are not "maximally bonded" (i.e., bond order of three for M = Ge and five for M = Cr)? We employ theoretical hybrid density functional (B3LYP/6-311++G) computations and natural bond orbital-based analysis to quantify molecular bond orders and to elucidate the electronic origin of such unintuitive structures. Resonance structures based on quintuple M-M bonding dominate for the transition metal compounds, especially for molybdenum and tungsten. For the main group, M-M bonding consists of three shared electron pairs, except for M = Pb. For both d- and p-block compounds, the M-M bond orders are reflected in torsional barriers, bond-antibond splittings, and heats of hydrogenation in a qualitatively intuitive way. Trans-bent structures arise primarily from hybridization tendencies that yield the strongest sigma-bonds. For transition metals, the strong tendency toward sd-hybridization in making covalent bonds naturally results in bent ligand arrangements about the metal. In the p-block, hybridization tendencies favor high p-character, with increasing avidity as one moves down the Group 14 column, and nonlinear structures result. In both the p-block and the d-block, bonding schemes have easily identifiable Lewis-like character but adopt somewhat unconventional orbital interactions. For more common metal-metal multiply bonded compounds such as [Re2Cl8]2-, the core Lewis-like fragment [Re2Cl4]2+ is modified by four hypervalent three-center/four-electron additions.

  19. Sub-20 nm Stable Micelles Based on a Mixture of Coiled-Coils: A Platform for Controlled Ligand Presentation.

    Science.gov (United States)

    Ang, JooChuan; Ma, Dan; Jung, Benson T; Keten, Sinan; Xu, Ting

    2017-11-13

    Ligand-functionalized, multivalent nanoparticles have been extensively studied for biomedical applications from imaging agents to drug delivery vehicles. However, the ligand cluster size is usually heterogeneous and the local valency is ill-defined. Here, we present a mixed micelle platform hierarchically self-assembled from a mixture of two amphiphilic 3-helix and 4-helix peptide-polyethylene glycol (PEG)-lipid hybrid conjugates. We demonstrate that the local multivalent ligand cluster size on the micelle surface can be controlled based on the coiled-coil oligomeric state. The oligomeric states of mixed peptide bundles were found to be in their individual native states. Similarly, mixed micelles indicate the orthogonal self-association of coiled-coil amphiphiles. Using differential scanning calorimetry, fluorescence recovery spectroscopy, and coarse-grained molecular dynamics simulation, we studied the distribution of coiled-coil bundles within the mixed micelles and observed migration of coiled-coils into nanodomains within the sub-20 nm mixed micelle. This report provides important insights into the assembly and formation of nanophase-separated micelles with precise control over the local multivalent state of ligands on the micelle surface.

  20. 'Homens trans': novos matizes na aquarela das masculinidades? 'Trans men': new colours in the masculinities picture?

    Directory of Open Access Journals (Sweden)

    Guilherme Almeida

    2012-08-01

    Full Text Available O artigo discute de forma exploratória a emergência de uma nova categoria identitária no Brasil, a de 'homem trans'. Essa se constrói diferenciando-se da identidade lésbica e, também, de expressões de gênero de outros grupos que tiveram seus corpos assignados como femininos ao nascimento, mas que contestam essa assignação sem, contudo, se afirmarem 'homens' de forma constante. Afirma-se que a emergência dos 'homens trans' tem sido potencializada pelo estabelecimento do processo transexualizador no SUS. Discutem-se o uso do termo "homem trans" e algumas características comuns a tais sujeitos. Problematizam-se a complexidade de seus processos de autorreconhecimento e construção de masculinidades, sua rápida capacidade de indiferenciação a partir de modificações corporais e, alguns dos efeitos políticos e subjetivos, da visibilidade e da indiferenciação.The article discusses in an exploratory form the emergence of a new identity category in Brazil, namely "transmen". This identity is constructed as a differentiation from the lesbian identity and also from gender expressions of other groups that had their bodies assigned as female upon birth, but that later refuted this assignment without, however, affirming themselves as "men" on a permanent way. The article claims that the emergence of "transmen" has been made possible by the establishment of the transexualization process in the Public Health Care System. Furthermore, the article discusses the use of the term "transman" and some common characteristics related to those persons. The author critiques their complex processes of self-knowledge and construction of masculinities, as well as their quick capacity for non-differentiation from the stand-point of bodily modifications. Finally, the author discusses the political and subjective consequences of their visibility and non-differentiation.

  1. Direct synthesis of cis-dihalido-bis(NHC) complex of nickel(II) and catalytic application in olefin addition polymerization: effect of halogen co-ligands and density functional theory study.

    Science.gov (United States)

    Zhang, Dao; Zhou, Sen; Li, Zhiming; Wang, Quanrui; Weng, Linhong

    2013-09-07

    Two novel amine-containing N-heterocyclic carbene ligand precursors [H(1a-b)]Br have been prepared in good yield and fully characterized. Direct syntheses of cis- and trans-dihalido-bis(NHC) nickel complexes [Ni(NHC)2X2] (X = Cl, Br) are reported. The solid structures of trans-[Ni(1a-b)2Br2] (2a-b) and cis-[Ni(1a)2Cl2] (3) were determined by single-crystal X-ray analysis and 3 was found to be the first example of cis-configuration coordination of monodentate NHC ligands to a metal center for dihalido-bis(NHC) nickel complexes. DFT calculations were conducted to determine the energy difference between cis- and trans-isomers of complexes 2a and 3 bearing bromide and chloride co-ligands. The cis-[Ni(1a)2Cl2] (cis-3) is 1.77-1.55 kcal mol(-1) lower in energy than its trans-isomer in polar solvents including CH2Cl2 and THF, while the trans-[Ni(1a)2Br2] (trans-2a) is more stable than the cis-isomer similarly in the gas phase. The cis nickel complex 3 with two coordinated monodentate NHCs was tested for olefin addition polymerization at standard conditions. It was found that cis-3 was inactive in ethylene polymerization but showed moderate catalytic activities (0.5-3.0 × 10(6) g of PNB (mol of Ni)(-1) h(-1)) in the addition polymerization of norbornene in the presence of methylaluminoxane (MAO) as cocatalyst.

  2. Correcting ligands, metabolites, and pathways

    Directory of Open Access Journals (Sweden)

    Vriend Gert

    2006-11-01

    Full Text Available Abstract Background A wide range of research areas in bioinformatics, molecular biology and medicinal chemistry require precise chemical structure information about molecules and reactions, e.g. drug design, ligand docking, metabolic network reconstruction, and systems biology. Most available databases, however, treat chemical structures more as illustrations than as a datafield in its own right. Lack of chemical accuracy impedes progress in the areas mentioned above. We present a database of metabolites called BioMeta that augments the existing pathway databases by explicitly assessing the validity, correctness, and completeness of chemical structure and reaction information. Description The main bulk of the data in BioMeta were obtained from the KEGG Ligand database. We developed a tool for chemical structure validation which assesses the chemical validity and stereochemical completeness of a molecule description. The validation tool was used to examine the compounds in BioMeta, showing that a relatively small number of compounds had an incorrect constitution (connectivity only, not considering stereochemistry and that a considerable number (about one third had incomplete or even incorrect stereochemistry. We made a large effort to correct the errors and to complete the structural descriptions. A total of 1468 structures were corrected and/or completed. We also established the reaction balance of the reactions in BioMeta and corrected 55% of the unbalanced (stoichiometrically incorrect reactions in an automatic procedure. The BioMeta database was implemented in PostgreSQL and provided with a web-based interface. Conclusion We demonstrate that the validation of metabolite structures and reactions is a feasible and worthwhile undertaking, and that the validation results can be used to trigger corrections and improvements to BioMeta, our metabolite database. BioMeta provides some tools for rational drug design, reaction searches, and

  3. Metabolism of trans, trans-muconaldehyde, a cytotoxic metabolite of benzene, in mouse liver by alcohol dehydrogenase Adh1 and aldehyde reductase AKR1A4

    International Nuclear Information System (INIS)

    Short, Duncan M.; Lyon, Robert; Watson, David G.; Barski, Oleg A.; McGarvie, Gail; Ellis, Elizabeth M.

    2006-01-01

    The reductive metabolism of trans, trans-muconaldehyde, a cytotoxic metabolite of benzene, was studied in mouse liver. Using an HPLC-based stopped assay, the primary reduced metabolite was identified as 6-hydroxy-trans, trans-2,4-hexadienal (OH/CHO) and the secondary metabolite as 1,6-dihydroxy-trans, trans-2,4-hexadiene (OH/OH). The main enzymes responsible for the highest levels of reductase activity towards trans, trans-muconaldehyde were purified from mouse liver soluble fraction first by Q-sepharose chromatography followed by either blue or red dye affinity chromatography. In mouse liver, trans, trans-muconaldehyde is predominantly reduced by an NADH-dependent enzyme, which was identified as alcohol dehydrogenase (Adh1). Kinetic constants obtained for trans, trans-muconaldehyde with the native Adh1 enzyme showed a V max of 2141 ± 500 nmol/min/mg and a K m of 11 ± 4 μM. This enzyme was inhibited by pyrazole with a K I of 3.1 ± 0.57 μM. Other fractions were found to contain muconaldehyde reductase activity independent of Adh1, and one enzyme was identified as the NADPH-dependent aldehyde reductase AKR1A4. This showed a V max of 115 nmol/min/mg and a K m of 15 ± 2 μM and was not inhibited by pyrazole

  4. trans-Diaquabis[2,5-bis(pyridin-2-yl-1,3,4-thiadiazole]cobalt(II bis(tetrafluoridoborate

    Directory of Open Access Journals (Sweden)

    Fouad Bentiss

    2011-07-01

    Full Text Available The bidentate 1,3,4-thiadiazole ligand substituted by two 2-pyridyl rings (denoted L has been found to produce the new monomeric title complex, [Co(C12H8N4S2(H2O2](BF42. The thiadiazole and pyridyl rings surrounding the Co atom are almost coplanar [dihedral angle = 4.35 (7°]. The mean plane defined by these heterocyclic moieties makes a dihedral angle of 18.72 (6° with the non-coordinated pyridyl ring. The Co2+ cation, located at a crystallographic center of symmetry, is bonded to two ligands and two water molecules in a trans configuration in an octahedral environment. The tetrafluoridoborate ions can be regarded as free anions in the crystal lattice. Nevertheless, they are involved in an infinite two-dimensional network along the [010] and [101] directions of O—H...F hydrogen bonds.

  5. Autocrine signal transmission with extracellular ligand degradation

    International Nuclear Information System (INIS)

    Muratov, C B; Posta, F; Shvartsman, S Y

    2009-01-01

    Traveling waves of cell signaling in epithelial layers orchestrate a number of important processes in developing and adult tissues. These waves can be mediated by positive feedback autocrine loops, a mode of cell signaling where binding of a diffusible extracellular ligand to a cell surface receptor can lead to further ligand release. We formulate and analyze a biophysical model that accounts for ligand-induced ligand release, extracellular ligand diffusion and ligand–receptor interaction. We focus on the case when the main mode for ligand degradation is extracellular and analyze the problem with the sharp threshold positive feedback nonlinearity. We derive expressions that link the speed of propagation and other characteristics of traveling waves to the parameters of the biophysical processes, such as diffusion rates, receptor expression level, etc. Analyzing the derived expressions we found that traveling waves in such systems can exhibit a number of unusual properties, e.g. non-monotonic dependence of the speed of propagation on ligand diffusivity. Our results for the fully developed traveling fronts can be used to analyze wave initiation from localized perturbations, a scenario that frequently arises in the in vitro models of epithelial wound healing, and guide future modeling studies of cell communication in epithelial layers

  6. Chemistry of marine ligands and siderophores.

    Science.gov (United States)

    Vraspir, Julia M; Butler, Alison

    2009-01-01

    Marine microorganisms are presented with unique challenges to obtain essential metal ions required to survive and thrive in the ocean. The production of organic ligands to complex transition metal ions is one strategy to both facilitate uptake of specific metals, such as iron, and to mitigate the potential toxic effects of other metal ions, such as copper. A number of important trace metal ions are complexed by organic ligands in seawater, including iron, cobalt, nickel, copper, zinc, and cadmium, thus defining the speciation of these metal ions in the ocean. In the case of iron, siderophores have been identified and structurally characterized. Siderophores are low molecular weight iron-binding ligands produced by marine bacteria. Although progress has been made toward the identity of in situ iron-binding ligands, few compounds have been identified that coordinate the other trace metals. Deciphering the chemical structures and production stimuli of naturally produced organic ligands and the organisms they come from is fundamental to understanding metal speciation and bioavailability. The current evidence for marine ligands, with an emphasis on siderophores, and discussion of the importance and implications of metal-binding ligands in controlling metal speciation and cycling within the world's oceans are presented.

  7. Radiation induced ligand loss from cobalt complexes

    International Nuclear Information System (INIS)

    Funston, A. M.; McFadyen, W.D.; Tregloan, P.A.

    2000-01-01

    Full text: Due to the rapid nature of ligand dissociation from cobalt(II) complexes the study of the rate of ligand dissociation necessitates the use of a technique such as pulse radiolysis. This allows the rapid reduction of the corresponding cobalt(III) complex by a reducing radical, such as the aquated electron, to form the cobalt(II) complex. However, to date, no systematic study of either the mechanism of reduction or the influence of the electronic structure on the rate of ligand dissociation has been carried out. In order to understand these processes more fully the mechanism of reduction of a range of related cobalt(III) complexes by the aquated electron and the subsequent rate of ligand dissociation from the resulting cobalt(II) complexes is being investigated. It has been found that a number of processes are observed following the initial rapid reaction of the cobalt(III) complex with the aquated electron. Ultimately ligand loss is observed. Depending upon the complex, the initial processes observed may include the formation of coordinated radicals and electron transfer within the complex. For complexes containing aromatic ligands such as 2,2'-bipyridine, 1,10-phenanthroline and dipyrido[3,2-a:2',3'-c]phenazine the formation of a coordinated radical is observed as the initial reduction step. The kinetics of ligand dissociation of these complexes has been determined. The loss of monodentate ligands is fast and has been indistinguishable from the reduction processes when aromatic ligands are also present in the complex. However, for diamine chelates and diimine chelates spectra of the transient species can be resolved

  8. Linking of Antitumor trans NHC-Pt(II) Complexes to G-Quadruplex DNA Ligand for Telomeric Targeting.

    Science.gov (United States)

    Betzer, Jean-François; Nuter, Frédérick; Chtchigrovsky, Mélanie; Hamon, Florian; Kellermann, Guillaume; Ali, Samar; Calméjane, Marie-Ange; Roque, Sylvain; Poupon, Joël; Cresteil, Thierry; Teulade-Fichou, Marie-Paule; Marinetti, Angela; Bombard, Sophie

    2016-06-15

    G-quadruplex structures (G4) are promising anticancerous targets. A great number of small molecules targeting these structures have already been identified through biophysical methods. In cellulo, some of them are able to target either telomeric DNA and/or some sequences involved in oncogene promotors, both resulting in cancer cell death. However, only a few of them are able to bind to these structures G4 irreversibly. Here we combine within the same molecule the G4-binding agent PDC (pyridodicarboxamide) with a N-heterocyclic carbene-platinum complex NHC-Pt already identified for its antitumor properties. The resulting conjugate platinum complex NHC-Pt-PDC stabilizes strongly G-quadruplex structures in vitro, with affinity slightly affected as compared to PDC. In addition, we show that the new conjugate binds preferentially and irreversibly the quadruplex form of the human telomeric sequence with a profile in a way different from that of NHC-Pt thereby indicating that the platination reaction is oriented by stacking of the PDC moiety onto the G4-structure. In cellulo, NHC-Pt-PDC induces a significant loss of TRF2 from telomeres that is considerably more important than the effect of its two components alone, PDC and NHC-Pt, respectively.

  9. Mixed plastics recycling technology

    CERN Document Server

    Hegberg, Bruce

    1995-01-01

    Presents an overview of mixed plastics recycling technology. In addition, it characterizes mixed plastics wastes and describes collection methods, costs, and markets for reprocessed plastics products.

  10. Reference values of urinary trans,trans-muconic acid: Italian Multicentric Study.

    Science.gov (United States)

    Aprea, C; Sciarra, G; Bozzi, N; Pagliantini, M; Perico, A; Bavazzano, P; Leandri, A; Carrieri, M; Scapellato, M L; Bettinelli, M; Bartolucci, G B

    2008-08-01

    This article reports the results of a study, conducted in the framework of the scientific activities of the Italian Society for Reference Values, aimed at defining reference values of urinary trans,trans-muconic acid (t,t-MA) in the general population not occupationally exposed to benzene. t,t-MA concentrations detected in 376 subjects of the resident population in three areas of Italy, two in central (Florence and southern Tuscany) and one in northern Italy (Padua), by three laboratories, compared by repeated interlaboratory controls, showed an interval of 14.4-225.0 microg/L (5th-95th percentile) and a geometric mean of 52.5 microg/L. The concentrations measured were influenced by tobacco smoking in a statistically significant way: Geometric mean concentrations were 44.8 microg/L and 76.1 microg/Ll in nonsmokers (264 subjects) and smokers (112 subjects), respectively. In the nonsmoking population, a significant influence of gender was found when concentrations were corrected for urinary creatinine, geometric mean concentrations being 36.7 microg/g creatinine in males (128 subjects) and 44.7 microg/g creatinine in females (136 subjects). The place of residence of subjects did not seem to influence urinary excretion of the metabolite, although personal inhalation exposure to benzene over a 24-h period showed slightly higher concentrations in Padua and Florence (geometric means of 6.5 microg/m(3) and 6.6 microg/m(3), respectively) than in southern Tuscany (geometric mean of 3.9 microg/m(3)). Concentration of t,t-MA in urine samples collected at the end of personal air sampling showed little relationship to personal inhalation exposure to benzene, confirming the importance of other factors in determining excretion of t,t-MA when concentrations in personal air samples are very low.

  11. Stabilization of enzyme by using hydrophobic ligands

    Energy Technology Data Exchange (ETDEWEB)

    Ota, H.; Yamahara, K.; Kuboi, R. [Osaka University, Osaka (Japan)

    1998-02-01

    The protection (stabilization) effect of various hydrophobic ligands on the denaturation and aggregation of carbonic anhydrase from bovine (CAB) has been quantitatively investigated under various heat stress conditions. In a limited temperature range (40-60degC), where the protein was only partially denatured and the local hydrophobicities (LH) of CAB were positive effective stabilization of the protein is achieved by the addition of various ligands. The importance of balance between hydrophobic head and hydrophilic tail of the ligands is hypothesized. 18 refs., 5 figs.

  12. A versatile dinucleating ligand containing sulfonamide groups

    DEFF Research Database (Denmark)

    Sundberg, Jonas; Witt, Hannes; Cameron, Lisa

    2014-01-01

    ligand can be prepared in aqueous solutions using only divalent metal ions. Two of the copper(II) complexes, [Cu2(psmp)(OH)] and [Cu2(psmp)(OAc)2]-, demonstrate the anticipated 1:2 ligand/metal stoichiometry and show that the dimetallic binding site created for exogenous ligands possesses high inherent...... of antiferromagnetic coupling. This is corroborated computationally by broken-symmetry density functional theory, which for isotropic modeling of the coupling predicts an antiferromagnetic coupling strength of J = 70.5 cm-1....

  13. Influence of pyridine versus piperidine ligands on the chemical, DNA binding and cytotoxic properties of light activated trans,trans,trans-[Pt(N3)2(OH)2(NH3)(L)

    Czech Academy of Sciences Publication Activity Database

    Westendorf, A.F.; Zerzánková, Lenka; Salassa, L.; Sadler, P.J.; Brabec, Viktor; Bednarski, P.J.

    2011-01-01

    Roč. 105, č. 5 (2011), s. 652-662 ISSN 0162-0134 R&D Projects: GA AV ČR(CZ) IAA400040803; GA ČR(CZ) GD301/09/H004; GA ČR(CZ) GAP301/10/0598 Institutional research plan: CEZ:AV0Z50040507; CEZ:AV0Z50040702 Keywords : platinum azides * cisplatin * photoactivation Subject RIV: BO - Biophysics Impact factor: 3.354, year: 2011

  14. The importance of trans-generational effects in Lepidoptera.

    Science.gov (United States)

    Woestmann, Luisa; Saastamoinen, Marjo

    2016-10-01

    The importance of trans-generational effects in shaping an individuals' phenotype and fitness, and consequently even impacting population dynamics is increasingly apparent. Most of the research on trans-generational effects still focuses on plants, mammals, and birds. In the past few years, however, increasing number of studies, especially on maternal effects, have highlighted their importance also in many insect systems. Lepidoptera, specifically butterflies, have been used as model systems for studying the role of phenotypic plasticity within generations. As ectotherms, they are highly sensitive to environmental variation, and indeed many butterflies show adaptive phenotypic plasticity in response to environmental conditions. Here, we synthesize what is known about trans-generational effects in Lepidoptera, compile evidence for different environmental cues that are important drivers of trans-generational effects, and point out which offspring traits are mainly impacted. Finally, we emphasize directions for future research that are needed for better understanding of the adaptive nature of trans-generational effects in Lepidoptera in particular, but potentially also in other organisms.

  15. Trans-inactivation: Repression in a wrong place.

    Science.gov (United States)

    Shatskikh, Aleksei S; Abramov, Yuriy A; Lavrov, Sergey A

    2017-04-03

    Trans-inactivation is the repression of genes on a normal chromosome under the influence of a rearranged homologous chromosome demonstrating the position effect variegation (PEV). This phenomenon was studied in detail on the example of brown Dominant allele causing the repression of wild-type brown gene on the opposite chromosome. We have investigated another trans-inactivation-inducing chromosome rearrangement, In(2)A4 inversion. In both cases, brown Dominant and In(2)A4, the repression seems to be the result of dragging of the euchromatic region of the normal chromosome into the heterochromatic environment. It was found that cis-inactivation (classical PEV) and trans-inactivation show different patterns of distribution along the chromosome and respond differently to PEV modifying genes. It appears that the causative mechanism of trans-inactivation is de novo heterochromatin assembly on euchromatic sequences dragged into the heterochromatic nuclear compartment. Trans-inactivation turns out to be the result of a combination of heterochromatin-induced position effect and the somatic interphase chromosome pairing that is widespread in Diptera.

  16. A simplified study of trans-mitral Doppler patterns

    Directory of Open Access Journals (Sweden)

    Thomas George

    2008-11-01

    Full Text Available Abstract Background Trans-mitral Doppler produces complex patterns with a great deal of variability. There are several confusing numerical measures and indices to study these patterns. However trans-mitral Doppler produces readymade data visualization by pattern generation which could be interpreted by pattern analysis. By following a systematic approach we could create an order and use this tool to study cardiac function. Presentation of the hypothesis In this new approach we eliminate the variables and apply pattern recognition as the main criterion of study. Proper terminologies are also devised to avoid confusion. In this way we can get some meaningful information. Testing the hypothesis Trans-mitral Doppler should be seen as patterns rather than the amplitude. The hypothesis can be proven by logical deduction, extrapolation and elimination of variables. Trans-mitral flow is also analyzed vis-à-vis the Starling's Law applied to the left atrium. Implications of the hypothesis Trans-mitral Doppler patterns are not just useful for evaluating diastolic function. They are also useful to evaluate systolic function. By following this schema we could get useful diagnostic information and therapeutic options using simple pattern recognition with minimal measurements. This simplified but practical approach will be useful in day to day clinical practice and help in understanding cardiac function better. This will also standardize research and improve communication.

  17. A simplified study of trans-mitral Doppler patterns.

    Science.gov (United States)

    Thomas, George

    2008-11-28

    Trans-mitral Doppler produces complex patterns with a great deal of variability. There are several confusing numerical measures and indices to study these patterns. However trans-mitral Doppler produces readymade data visualization by pattern generation which could be interpreted by pattern analysis. By following a systematic approach we could create an order and use this tool to study cardiac function. In this new approach we eliminate the variables and apply pattern recognition as the main criterion of study. Proper terminologies are also devised to avoid confusion. In this way we can get some meaningful information. Trans-mitral Doppler should be seen as patterns rather than the amplitude. The hypothesis can be proven by logical deduction, extrapolation and elimination of variables. Trans-mitral flow is also analyzed vis-à-vis the Starling's Law applied to the left atrium. Trans-mitral Doppler patterns are not just useful for evaluating diastolic function. They are also useful to evaluate systolic function. By following this schema we could get useful diagnostic information and therapeutic options using simple pattern recognition with minimal measurements. This simplified but practical approach will be useful in day to day clinical practice and help in understanding cardiac function better. This will also standardize research and improve communication.

  18. Trans-nationalisation Processes in the Ukrainian Economy

    Directory of Open Access Journals (Sweden)

    Bolharova Natalya K.

    2013-12-01

    Full Text Available The article considers main processes of trans-nationalisation of Ukrainian economy, identifies specific features of trans-national production and explains some theoretical aspects of these issues. It provides main stages of theoretical comprehension of activity of trans-national corporations (TNC, specific features of the theory of competitive advantages of TNC and specifies the basic ones of them. The article conducts analysis of flows of direct foreign investments into the Ukrainian economy. It shows distribution of direct foreign investments into Ukraine by main countries-investors, regions-recipients and types of economic activity. It conducts review and analysis of the modern state of trans-national corporations of foreign origin in the Ukrainian market. It considers functioning of domestic TNC in Ukraine and main tendencies of entering of Ukrainian companies into the world environment and also identifies directions of further development of these phenomena. Prospects of further studies in this direction are identification of the degree of trans-nationalisation processes in the Ukrainian economy and identification of the positive effect, in particular, synergy from integration and globalisation.

  19. A double salt of iodobismuthate: cis-aquaiodidobis(1,10-phenanthrolinecobalt(II tris(1,10-phenanthrolinecobalt(II trans-hexa-μ2-iodido-hexaiodidotribismuthate(III

    Directory of Open Access Journals (Sweden)

    Jiongke Chen

    2011-09-01

    Full Text Available In the title complex, [Co(C12H8N23][CoI(C12H8N22(H2O][Bi3I12], conventionally abbreviated [Co(phen3][CoI(phen2(H2O][Bi3I12], where phen is 1,10-phenanthroline, the CoII atom in one cation is coordinated by six N atoms from three phen ligands in an octahedral coordination while the CoII atom in the other cation is coordinated octahedrally by four N atoms from two phen ligands, one water O atom and one I atom. In the anion, three BiIII ions adopt an octahedral coordination constructed by six I− ligands. The three BiI6 octahedra are fused together through trans face-sharing.

  20. Asymmetrically doped one-dimensional trans-polymers

    International Nuclear Information System (INIS)

    Caldas, Heron

    2009-01-01

    More than 30 years ago [H. Shirakawa, E.J. Louis, A.G. MacDiarmid, C.K. Chiang, A.J. Heeger, J. Chem. Soc. Chem. Comm. 578 (1977); S. Etemad, A.J. Heeger, Ann. Rev. Phys. Chem. 33 (1982) 443] it was discovered that doped trans-polyacetylene (CH) x , a one-dimensional (1D) conjugated polymer, exhibits electrical conductivity. In this work we show that an asymmetrically doped 1D trans-polymer has non-conventional properties, as compared to symmetrically doped systems. Depending on the level of asymmetry between the chemical potentials of the two involved fermionic species, the polymer can be in a partially or fully spin polarized state. Some possible experimental consequences of doped 1D trans-polymers used as 1D organic polarized conductors are discussed.

  1. Letter to the editor: healthy alternatives to trans fats

    Directory of Open Access Journals (Sweden)

    Moulin Julie

    2007-04-01

    Full Text Available Abstract Consumption of trans fats is associated with an increase of cardiovascular disease (CVD risk. To comply with regulatory policies and public health authorities recommendations, trans fats should be replaced in food products. The study by Sundram et al. (Nutrition & Metabolism 2007, 4:3 reporting the effect on CVD risk factors of interesterified fat (IE and partially hydrogenated soybean oil (PHSO compared to palm olein (POL has been critically analyzed. The study design and in particular the composition of the tested fats was not suitable to properly answer the question raised regarding the effect of alternative ingredients to trans fats on plasma lipids. The observed effects are divergent with predicted data derived from the literature model consolidated using the individual results of 60 randomized clinical trials. The results of the study published by Sundram and co-workers have to be considered with awareness.

  2. Mechanically induced cis to trans reisomerization of azobenzene

    Science.gov (United States)

    Turansky, Robert; Konopka, Martin; Stich, Ivan; Marx, Dominik

    2007-03-01

    Using density functional techniques we study mechanochemistry of the azobenzene molecule. Azobenzene is an optically switchable molecule. Laser light is normally used to achieve molecular switching between the cis and trans isomers. We use mechanochemistry to achieve the switching. Thiolate-gold bond can used to exert mechanical energy on the molecule bonded between two gold electrodes in static AFM apparatus. Our model consists of two realistic gold electrodes bridged by dithioazobenzene. We find that pulling the transisomer leads just to formation of gold nanowires and mechanical breakage of the electrodes. However, mechanochemistry with modest applied forces leads to cis trans reisomerization via rotation mechanism. Contrary, use of simple constraints instead of realistic gold electrodes, leads to cis trans reisomerization, albeit with significantly larger applied forces and via inversion mechanism. Important experimental and theoretical ramifications of these simulations will be discussed.

  3. In Search of a Trans-national Climate Change Law

    International Nuclear Information System (INIS)

    Lassus Saint-Genies, Geraud de

    2016-01-01

    Private entities engagement in the battle against climate change is a well-established fact, and a source of intense and diversified normative activity. A certain type of climate rules has thus arisen, with a private origin and an international scope, as they transcend the borders of existing territories. In this context, one could wonder about the possible existence of a trans-national climate change law, as a relatively autonomous body of law, which would exist at the margins of international and national climate change law. Building on the discussions that have been conducted about the trans-national law in other areas of regulations, this study intends to provide answers about the possible existence of a trans-national climate change law

  4. Controlling Signal Transduction with Synthetic Ligands

    Science.gov (United States)

    Spencer, David M.; Wandless, Thomas J.; Schreiber, Stuart L.; Crabtree, Gerald R.

    1993-11-01

    Dimerization and oligomerization are general biological control mechanisms contributing to the activation of cell membrane receptors, transcription factors, vesicle fusion proteins, and other classes of intra- and extracellular proteins. Cell permeable, synthetic ligands were devised that can be used to control the intracellular oligomerization of specific proteins. To demonstrate their utility, these ligands were used to reduce intracellular oligomerization of cell surface receptors that lacked their transmembrane and extracellular regions but contained intracellular signaling domains. Addition of these ligands to cells in culture resulted in signal transmission and specific target gene activation. Monomeric forms of the ligands blocked the pathway. This method of ligandregulated activation and termination of signaling pathways has the potential to be applied wherever precise control of a signal transduction pathway is desired.

  5. Allyl functionalized phosphinite and phosphonite ligands: Synthesis ...

    Indian Academy of Sciences (India)

    Allyl functionalized phosphinite and phosphonite ligands: Synthesis, transition metal chemistry and orthopalladation reactions. SINGAPPAGUDEM GOVINDARAJUa, GUDDEKOPPA S ANANTHNAGa, SUSMITA NAIKa,. SHAIKH M MOBINb and MARAVANJI S BALAKRISHNAa,∗. aPhosphorus Laboratory, Department of ...

  6. Organometallic chemistry of chiral diphosphazane ligands ...

    Indian Academy of Sciences (India)

    Home; Journals; Journal of Chemical Sciences; Volume 114; Issue 4. Organometallic chemistry of chiral diphosphazane ligands: Synthesis and structural characterisation. Kannan Raghuraman Swadhin K Mandal T S Venkatakrishnan Setharampattu S Krishnamurthy Munirathinam Nethaji. Volume 114 Issue 4 August 2002 ...

  7. EGFR Activation by Spatially Restricted Ligands

    National Research Council Canada - National Science Library

    Clouse, Katherine N; Goodrich, Jennifer S

    2006-01-01

    ...) activity has been associated with an increased prognosis of breast cancer. During cogenesis in Drosophila melanogaster local Egfr activation by the spatially-restricted TGFalpha-like ligand Gurken (Grk...

  8. EGFR Activation by Spatially Restricted Ligands

    National Research Council Canada - National Science Library

    Goodrich, Jennifer S

    2005-01-01

    ...) activity has been associated with an increased prognosis of breast cancer. During oogenesis in Drosophila melanogaster, local EGFR activation by the spatially restricted TGF alpha-like ligand, Gurken (Grk...

  9. High-pressure phase equilibrium data for systems with carbon dioxide, {alpha}-humulene and trans-caryophyllene

    Energy Technology Data Exchange (ETDEWEB)

    Michielin, Eliane M.Z.; Rosso, Sibele R. [EQA/UFSC, Chemical and Food Engineering Department, Federal University of Santa Catarina, C.P. 476, CEP 88040-900, Florianopolis, SC (Brazil); Franceschi, Elton; Borges, Gustavo R.; Corazza, Marcos L.; Oliveira, J. Vladimir [Department of Food Engineering, URI - Campus de Erechim, Av. Sete de Setembro, 1621, Erechim, RS, 99700-000 (Brazil); Ferreira, Sandra R.S. [EQA/UFSC, Chemical and Food Engineering Department, Federal University of Santa Catarina, C.P. 476, CEP 88040-900, Florianopolis, SC (Brazil)], E-mail: sandra@enq.ufsc.br

    2009-01-15

    The aim of this work is to report phase equilibrium data for the binary systems (CO{sub 2} + {alpha}-humulene) and (CO{sub 2} + trans-caryophyllene), and for the ternary system (CO{sub 2} + {alpha}-humulene + trans-caryophyllene). Results from literature show that {alpha}-humulene and trans-caryophyllene are the main compounds responsible for the anti-inflammatory and anti-allergic characteristics attributed to the medicinal plant Cordia verbenacea D.C., hence giving importance to the phase behaviour investigation performed in this work. Phase equilibrium experiments were performed in a high-pressure, variable-volume view cell over the temperature range of T = (303 to 343) K and pressures up to 20 MPa. (Liquid + liquid) and (vapour + liquid + liquid) equilibrium were observed at T = 303 K, while (vapour + liquid) phase transitions were verified to occur from T = (313 to 343) K, for all systems studied. Thermodynamic modelling was performed using the Peng-Robinson equation of state and the classical quadratic mixing rules, with a satisfactory agreement between experimental and calculated values.

  10. Complexation of biological ligands with lanthanides(III) for MRI: Structure, thermodynamic and methods; Complexation des cations lanthanides trivalents par des ligands d'origine biologique pour l'IRM: Structure, thermodynamique et methodes

    Energy Technology Data Exchange (ETDEWEB)

    Bonnet, C

    2006-07-15

    New cyclic ligands derived from sugars and amino-acids form a scaffold carrying a coordination sphere of oxygen atoms suitable to complex Ln(III) ions. In spite of their rather low molecular weights, the complexes display surprisingly high relaxivity values, especially at high field. The ACX and BCX ligands, which are acidic derivatives of modified and cyclo-dextrins, form mono and bimetallic complexes with Ln(III). The LnACX and LnBCX complexes show affinities towards Ln(III) similar to those of tri-acidic ligands. In the bimetallic Lu2ACX complex, the cations are deeply embedded in the cavity of the ligand, as shown by the X-ray structure. In aqueous solution, the number of water molecules coordinated to the cation in the LnACX complex depends on the nature and concentration of the alkali ions of the supporting electrolyte, as shown by luminescence and relaxometric measurements. There is only one water molecule coordinated in the LnBCX complex, which enables us to highlight an important second sphere contribution to relaxivity. The NMR study of the RAFT peptidic ligand shows the complexation of Ln(III), with an affinity similar to those of natural ligands derived from calmodulin. The relaxometric study also shows an important second sphere contribution to relaxivity. To better understand the intricate molecular factors affecting relaxivity, we developed new relaxometric methods based on probe solutes. These methods allow us to determine the charge of the complex, weak affinity constants, trans-metallation constants, and the electronic relaxation rate. (author)

  11. Chemistry of Marine Ligands and Siderophores

    OpenAIRE

    Vraspir, Julia M.; Butler, Alison

    2009-01-01

    Marine microorganisms are presented with unique challenges to obtain essential metal ions required to survive and thrive in the ocean. The production of organic ligands to complex transition metal ions is one strategy to both facilitate uptake of specific metals, such as iron, and to mitigate the potential toxic effects of other metal ions, such as copper. A number of important trace metal ions are complexed by organic ligands in seawater, including iron, cobalt, nickel, copper, zinc, and cad...

  12. Evolution of cichlid vision via trans-regulatory divergence

    Directory of Open Access Journals (Sweden)

    O’Quin Kelly E

    2012-12-01

    Full Text Available Abstract Background Phenotypic evolution may occur through mutations that affect either the structure or expression of protein-coding genes. Although the evolution of color vision has historically been attributed to structural mutations within the opsin genes, recent research has shown that opsin regulatory mutations can also tune photoreceptor sensitivity and color vision. Visual sensitivity in African cichlid fishes varies as a result of the differential expression of seven opsin genes. We crossed cichlid species that express different opsin gene sets and scanned their genome for expression Quantitative Trait Loci (eQTL responsible for these differences. Our results shed light on the role that different structural, cis-, and trans-regulatory mutations play in the evolution of color vision. Results We identified 11 eQTL that contribute to the divergent expression of five opsin genes. On three linkage groups, several eQTL formed regulatory “hotspots” associated with the expression of multiple opsins. Importantly, however, the majority of the eQTL we identified (8/11 or 73% occur on linkage groups located trans to the opsin genes, suggesting that cichlid color vision has evolved primarily via trans-regulatory divergence. By modeling the impact of just two of these trans-regulatory eQTL, we show that opsin regulatory mutations can alter cichlid photoreceptor sensitivity and color vision at least as much as opsin structural mutations can. Conclusions Combined with previous work, we demonstrate that the evolution of cichlid color vision results from the interplay of structural, cis-, and especially trans-regulatory loci. Although there are numerous examples of structural and cis-regulatory mutations that contribute to phenotypic evolution, our results suggest that trans-regulatory mutations could contribute to phenotypic divergence more commonly than previously expected, especially in systems like color vision, where compensatory changes in the

  13. Denmark's Policy on Artificial Trans Fat and Cardiovascular Disease.

    Science.gov (United States)

    Restrepo, Brandon J; Rieger, Matthias

    2016-01-01

    The consumption of trans fat is associated with cardiovascular disease (CVD). In January 2004, Denmark became the first country in the world to regulate the content of artificial trans fat in certain ingredients in food products, which nearly eliminated artificial trans fat from the Danish food supply. The goal of this study was to assess whether Denmark's trans fat policy reduced deaths caused by CVD. Annual mortality rates in Organisation for Economic Co-operation and Development (OECD) countries from 1990 to 2012 were used to estimate the effect of Denmark's food policy on CVD mortality rates. Synthetic control methods were employed to simulate the CVD mortality trajectory that Denmark would have witnessed in the absence of the policy and to measure the policy's impact on CVD mortality rates. Analyses were conducted in 2015. Before the trans fat policy was implemented, CVD mortality rates in Denmark closely tracked those of a weighted average of other OECD countries (i.e., the synthetic control group). In the years before the policy, the annual mean was 441.5 deaths per 100,000 people in Denmark and 442.7 in the synthetic control group. In the 3 years after the policy was implemented, mortality attributable to CVD decreased on average by about 14.2 deaths per 100,000 people per year in Denmark relative to the synthetic control group. Denmark's food policy, which restricted the content of artificial trans fat in certain ingredients in its food supply, has been followed by a decrease in CVD mortality rates. Published by Elsevier Inc.

  14. Continuous mixing of solids

    NARCIS (Netherlands)

    Raouf, M.S.

    1963-01-01

    The most important literature on theoretical aspects of mixing solids was reviewed.

    Only when the mixed materials showed no segregation it was possible to analyse the mixing process quantitatively. In this case the mixture could be described by the 'χ' Square test. Longitudinal mixing could be

  15. Trans- and cis-2-phenylindole platinum(II) complexes as cytotoxic agents against human breast adenocarcinoma cell lines

    Science.gov (United States)

    Tomé, Maria; López, Concepción; González, Asensio; Ozay, Bahadir; Quirante, Josefina; Font-Bardía, Mercè; Calvet, Teresa; Calvis, Carme; Messeguer, Ramon; Baldomá, Laura; Badía, Josefa

    2013-09-01

    The synthesis and characterization of the new 2-phenylindole derivative: C8H3N-2-C6H5-3NOMe-5OMe (3c) and the trans- and cis-isomers of [Pt(3c)Cl2(DMSO)] complexes (4c and 5c, respectively) are described. The crystal structures of 4c·CH2Cl2 and 5c confirm: (a) the existence of a Pt-Nindole bond, (b) the relative arrangement of the Cl- ligands [trans- (in 4c) or cis- (in 5c)] and (c) the anti-(E) configuration of the oxime. The cytotoxic assessment of C8H3N-2-(C6H4-4‧R1)-3NOMe-5R2 [with R1 = R2 = H (3a); R1 = Cl, R2 = H (3b) and R1 = H, R2 = OMe (3c)] and the geometrical isomers of [Pt(L)Cl2(DMSO)] with L = 3a-3c [trans- (4a-4c) and cis- (5a-5c), respectively] against human breast adenocarcinoma cell lines (MDA-MB231 and MCF-7) is also reported and reveals that all the platinum(II) complexes (except 4a) are more cytotoxic than cisplatin in front of the MCF7 cell line. Electrophoretic DNA migration studies of the synthesized compounds in the absence and in the presence of topoisomerase-I have been performed, in order to get further insights into their mechanism of action.

  16. Trans-Himalayan water contributions to river discharge

    Science.gov (United States)

    Andermann, Christoff; Stieglitz, Thomas; Schuessler, Jan A.; Parajouli, Binod

    2017-04-01

    Hydrological processes in high mountains are not well understood. Groundwater is commonly considered to be of little importance in the mountain water balance, while direct runoff, snow and ice melt are thought to be the principal hydrological buffer. We present new insights into hydrological fluxes between major reservoirs in a trans-Himalayan catchment. The study area is the Kali Gandaki catchment, rising in the dry Tibetan interior, carving through the high Himalayas and draining the full width of the foothills to the Ganges foreland. The catchment has a well-defined monsoon climate, with pronounced annual wet and dry seasons and a clear separation of wind- and leeward regions. We have sampled the main river and its tributaries as well as several springs during the four hydrological seasons (winter, pre-monsoon, monsoon, post-monsoon). We have measured major element abundances as well as 222Rn in situ, as a tracer for groundwater contribution. These measurements are placed in a context of topographic analyses as well as continuous discharge and precipitation measurements. Furthermore, we have equipped two sites with continuous water samplers, sampling over > 4 monsoon seasons, allowing us to resolve the seasonal hydrological dynamic range on a very high temporal resolution. Chemical fluxes vary spatially over several orders of magnitude, showing a systematic downstream dilution trend for most major elements during all hydrological seasons. High initial concentrations derive from evaporite deposits in the uppermost part of the catchment, constituting a large scale, natural salt tracer experiment. The well-defined decline of solute concentrations along the main river, paired with constraints on the composition of lateral water inputs downstream allow the calculation of the spatial distribution of additional hydrological fluxes, by applying end member mixing modeling. Continuous river stage and bulk dissolved load (electrical conductivity) monitoring depict well

  17. and Tetradentate N,O-donor Ligands

    African Journals Online (AJOL)

    NICO

    )], derived from the oxidation reactions (by O2) of trans-[ReCl3(MeCN)(PPh3)2] with the tridentate N2O-donor chelate 2-[((2-pyridinylmethyl)amino)methyl]phenol (Hham) and the N2O2-donor N,N-bis(2-hydroxybenzyl)-aminomethyl- pyridine ...

  18. Designer TGFβ superfamily ligands with diversified functionality.

    Directory of Open Access Journals (Sweden)

    George P Allendorph

    Full Text Available Transforming Growth Factor--beta (TGFβ superfamily ligands, including Activins, Growth and Differentiation Factors (GDFs, and Bone Morphogenetic Proteins (BMPs, are excellent targets for protein-based therapeutics because of their pervasiveness in numerous developmental and cellular processes. We developed a strategy termed RASCH (Random Assembly of Segmental Chimera and Heteromer, to engineer chemically-refoldable TGFβ superfamily ligands with unique signaling properties. One of these engineered ligands, AB208, created from Activin-βA and BMP-2 sequences, exhibits the refolding characteristics of BMP-2 while possessing Activin-like signaling attributes. Further, we find several additional ligands, AB204, AB211, and AB215, which initiate the intracellular Smad1-mediated signaling pathways more strongly than BMP-2 but show no sensitivity to the natural BMP antagonist Noggin unlike natural BMP-2. In another design, incorporation of a short N-terminal segment from BMP-2 was sufficient to enable chemical refolding of BMP-9, without which was never produced nor refolded. Our studies show that the RASCH strategy enables us to expand the functional repertoire of TGFβ superfamily ligands through development of novel chimeric TGFβ ligands with diverse biological and clinical values.

  19. Exploiting ligand-protein conjugates to monitor ligand-receptor interactions.

    Directory of Open Access Journals (Sweden)

    Hirohito Haruki

    Full Text Available We introduce three assays for analyzing ligand-receptor interactions based on the specific conjugation of ligands to SNAP-tag fusion proteins. Conjugation of ligands to different SNAP-tag fusions permits the validation of suspected interactions in cell extracts and fixed cells as well as the establishment of high-throughput assays. The different assays allow the analysis of strong and weak interactions. Conversion of ligands into SNAP-tag substrates thus provides access to a powerful toolbox for the analysis of their interactions with proteins.

  20. Li+-ligand binding energies and the effect of ligand fluorination on the binding energies

    Science.gov (United States)

    Bauschlicher, Charles W.

    2018-02-01

    The Li+-ligand binding energies are computed for seven ligands and their perfluoro analogs using Density Functional Theory. The bonding is mostly electrostatic in origin. Thus the size of the binding energy tends to correlate with the ligand dipole moment, however, the charge-induced dipole contribution can be sufficiently large to affect the dipole-binding energy correlation. The perfluoro species are significantly less strongly bound than their parents, because the electron withdrawing power of the fluorine reduces the ligand dipole moment.