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Spectrophotometric Titrations (spectrophotometric + titration)
Selected AbstractsDual Luminescent Dinuclear Gold(I) Complexes of Terpyridyl-Functionalized Alkyne Ligands and Their Efficient Sensitization of EuIII and YbIII LuminescenceEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 22 2010Xiu-Ling Li Abstract Reaction of (tpyC6H4C,CAu)n {tpyC6H4C,CH = 4,-(4-ethynylphenyl)-2,2,:6,,2,-terpyridine} with diphosphane ligands Ph2P(CH2)xPPh2 (x = 2 dppe, 3 dppp, 4 dppb, 5 dpppen, 6 dpph) in CH2Cl2 afforded the corresponding dual luminescent binuclear gold(I) complexes [(tpyC6H4C,CAu)2(,-dppe)] (1), [(tpyC6H4C,CAu)2(, - dppp)] (2), [(tpyC6H4C,CAu)2(,-dppb)] (3), [(tpyC6H4C,CAu)2(,-dpppen)] (4), [(tpyC6H4C,CAu)2(,-dpph)] (5). Crystal structural analysis of complexes 1·2CH2Cl2 and 2·2CH2Cl2 show that the terpyridine moieties are free of coordination in these gold(I)-acetylide-phosphane complexes. Spectrophotometric titration between complex 1 and [Eu(tta)3] (Htta = 2-thenoyltrifluoroacetone) or [Yb(hfac)3(H2O)2] (Hhfac = hexafluoroacetylacetone) gave a 2:1 ratio between Ln(,-diketonate)3 (Ln = Eu, Yb) units and the complex 1 moiety, indicating the formation of Au2Ln2 complexes. Both the luminescence titrations and the luminescence quantum yields of Au2Ln2 (Ln = Eu, Yb) solutions show that the energy transfer occurs efficiently from the binuclear gold(I) antennas 1,5 to EuIII and YbIII centers, and all complexes 1,5 are good energy donors for sensitization of visible and NIR luminescence of EuIII and YbIII ions. [source] Characterization of a nif-regulated flavoprotein (FprA) from Rhodobacter capsulatusFEBS JOURNAL, Issue 3 20002S] ferredoxin, Redox properties, molecular interaction with a [2Fe A flavoprotein from Rhodobacter capsulatus was purified as a recombinant (His)6 -tag fusion from an Escherichia coli clone over-expressing the fprA structural gene. The FprA protein is a homodimer containing one molecule of FMN per 48-kDa monomer. Reduction of the flavoprotein by dithionite showed biphasic kinetics, starting with a fast step of semiquinone (SQ) formation, and followed by a slow reduction of the SQ. This SQ was in the anionic form as shown by EPR and optical spectroscopies. Spectrophotometric titration gave a midpoint redox potential for the oxidized/SQ couple of Em1 = +20 mV (pH 8.0), whereas the SQ/hydroquinone couple could not be titrated due to the thermodynamic instability of SQ associated with its slow reduction process. The inability to detect the intermediate form, SQ, upon oxidative titration confirmed this instability and led to an estimate of Em2 , Em1 of > 80 mV. The reduction of SQ by dithionite was significantly accelerated when the [2Fe,2S] ferredoxin FdIV was used as redox mediator. The midpoint redox potential of this ferredoxin was determined to be ,275 ± 2 mV at pH 7.5, consistent with FdIV serving as electron donor to FprA in vivo. FdIV and FprA were found to cross-react when incubated together with the 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide, giving a covalent complex with an Mr of , 60 000. Formation of this complex was unaffected by the redox states of the two proteins. Other [2Fe,2S] ferredoxins, including FdV and FdVI from R. capsulatus, were ineffective as electron carriers to FprA, and cross-reacted poorly with the flavoprotein. The possible function of FprA with regard to nitrogen fixation was investigated using an fprA -deleted mutant. Although nitrogenase activity was significantly reduced in the mutant compared with the wild-type strain, nitrogen fixation was apparently unaffected by the fprA deletion even under iron limitation or microaerobic conditions. [source] Toward an Allosteric Metallated ContainerEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 2 2009Helga Szelke Abstract Polytopic ligands L1 and L2 in which three 2,2,-bipyridine units are linked to a central tris(pyrid-2-yl)amine (L1) or tris(pyrid-2-yl)methanol (L2) moiety by alkyl spacers were prepared by multistep organic syntheses. The parent tris(pyrid-2-yl)-type ligands were shown to be modest-to-good chelators for Zn2+ and Cu2+ ions in solution, and bi- and tridentate N-coordination was confirmed by crystal structures of CuII and RuII complexes, respectively. FeII and RuII smoothly form stable, cage-like 1:1 complexes with L1 and L2, in which the metal ion is coordinated to the tris(bpy) site of the ligands. The vacant tris(pyrid-2-yl) site of these complexes is, however, a poor donor site for Zn2+ and Cu2+ ions. In addition, FeII modulates the coordination behaviour of the tris(pyrid-2-yl) site toward Zn2+: Whereas tris(5-methylpyrid-2-yl)amine forms a 2:1 complex with Zn2+ in CH2Cl2, [Fe(L1)]2+ forms a 1:1 Zn complex. Spectrophotometric titrations suggest that [Fe(L2)]2+ forms a polynuclear Zn2+ complex in CH2Cl2, possibly involving bridging coordination of the alcohol OH group, which contrasts the smooth formation of a 2:1 complex of the parent tris(pyrid-2-yl)-type ligand with Zn. FeII might therefore be considered as an allosteric effector, which modulates the metal binding properties of the second tris(pyrid-2-yl) site of L1 and L2. Contrary to expectation, Zn2+ and Cu2+ appear to associate weakly with donor atoms directed toward the exterior of the cage-like complexes [Fe(Ln)]2+ and [Ru(L1)]2+, rather than locating in the interior of the container by tripodal coordination to the tris(pyrid-2-yl) site.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009) [source] Receptor versus Counterion: Capability of N,N, -Bis(2-aminobenzyl)-diazacrowns for Giving Endo- and/or Exocyclic Coordination of ZnIIEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 13 2007Lea Vaiana Abstract The structure of ZnII complexes with receptors L1 and L2[L1 = N,N, -bis(2-aminobenzyl)-1,10-diaza-15-crown-5 and L2 = N,N, -bis(2-aminobenzyl)-4,13-diaza-18-crown-6] was studied both in the solid state and in acetonitrile solution. Both receptors form mononuclear ZnII complexes in this solvent, while no evidence for the formation of dinuclear complexes was obtained. This is in contrast with previous investigations that demonstrated the formation of dinuclear complexes of L2 with first-row transition metals such as NiII, CoII and CuII. Compounds of formula [Zn(L1)](ClO4)2 (1), [Zn(L1)](NO3)2·2CH3CN (2), [Zn(L2)](ClO4)2 (3) and [Zn(L2)(NO3)2] (4) were isolated and structurally characterised by X-ray diffraction analyses. L1 forms seven-coordinate ZnII complexes in the presence of both nitrate and perchlorate anions, as a consequence of the good fit between the macrocyclic cavity and the ionic radius of the metal ion. The ZnII ion is deeply buried into the receptor cavity and the anions are forced to remain out of the metal coordination sphere. The cation [Zn(L1)]2+ present in 1 and 2 is one of the very few examples of seven-coordinate Zn complexes. Receptor L2 provides a very rare example of a macrocyclic receptor allowing endocyclic and exocyclic coordination on the same guest cation, depending on the nature of the anion present. Thus, in 3 the ZnII ion is endocyclically coordinated, placed inside the crown hole coordinated to four donor atoms of the ligand in a distorted tetrahedral environment, whereas in 4, the presence of a strongly coordinating anion such as nitrate results in an exocyclic coordination of ZnII, which is directly bound only to the two primarily amine groups of L2 and two nitrate ligands. Spectrophotometric titrations of [Zn(L2)]2+ with tetrabutylammonium nitrate in acetonitrile solution demonstrate the stepwise formation of 1:1 and 1:2 adducts with this anion in acetonitrile solution. The [Zn(L1)]2+, [Zn(L2)]2+ and [Zn(L2)(NO3)2] systems were characterised by means of DFT calculations (B3LYP model). The calculated geometries show an excellent agreement with the experimental structures obtained from X-ray diffraction analyses. Calculated binding energies of the macrocyclic ligands to ZnII are also consistent with the experimental data.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007) [source] Enantioselective Recognition of Aliphatic Amino Acids by ,-Cyclodextrin Derivatives Bearing Aromatic Organoselenium Moieties on the Primary or Secondary SideEUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 8 2003Yu Liu Abstract Spectrophotometric titrations have been performed in order to determine the stability constants of inclusion complexation of some aliphatic amino acids with four structurally related organoselenium-modified ,-cyclodextrins: mono(6-phenylseleno-6-deoxy)-,-cyclodextrin (1a), mono[6-(p -methoxyphenylseleno)-6-deoxy]-,-cyclodextrin (1b), mono(2-phenylseleno-2-deoxy)-,-cyclodextrin (2a), and mono[2-(p -methoxyphenylseleno)-2-deoxy]-,-cyclodextrin (2b). Conformation analysis by circular dichroism and 2D NMR spectroscopic studies revealed that the aryl-substituted ,-cyclodextrins gave self-inclusion intramolecular complexes in aqueous solution, while the extent of penetration depended both on the positions and on the structures of substituents. Quantitative investigation on the binding ability of the hosts with amino acids showed that they were able to recognize the size and the shape of guests, affording supramolecular complexes with quite small stability constants ranging from 24 to 355 M,1. The molecular recognition abilities are discussed from the viewpoints of induced-fitting mechanisms, geometric complementary, and cooperative binding processes. Furthermore, these ,-cyclodextrin derivatives displayed considerable enantioselectivity towards L/D -amino acid isomers, giving the highest L -enantioselectivity (up to 8.4) for inclusion complexation between leucine and 2a. The binding modes of L/D -leucine with 1b were elucidated from NOESY studies and the chiral recognition phenomena were interpreted accordingly. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003) [source] 2-(2,4-Dinitrobenzyl)pyridine (DNBP): A Potential Light-Activated Proton ShuttleHELVETICA CHIMICA ACTA, Issue 10 2009Catrin Goeschen Abstract The well-known photochromic tautomerism of 2-(2,4-dinitrobenzyl)pyridine (1; CH; Scheme,1) was re-investigated by flash photolysis in aqueous solution in view of its potential application as a light-activated proton pump. Irradiation of 1 yields the enamine tautomer NH (,max=520,nm) that rapidly equilibrates with its conjugate base CNO, (,max=420,nm). The pH,rate profile for the first-order decay of NH and CNO, provides a direct determination of the acidity constant of NH, pK=5.94±0.12 (I=0.1M) and serves to clarify the mechanisms of proton transfer prevailing in aqueous solutions. The acidity constant of protonated 1 (CHNH+), pK=4.18±0.02, was determined by spectrophotometric titration. [source] Vesicles to Concentrate Iron in Low-Iron Media: An Attempt to Mimic Marine SiderophoresCHEMISTRY - A EUROPEAN JOURNAL, Issue 12 2008Lucie Bednarova Dr. Abstract Amphiphilic catechol-type iron chelators were studied with the aim of mimicking the properties of marine bacterial siderophores. The FeIII complexation constants and aqueous solution speciation of LS10, a sulfonated catechol unit that has a C10 lipophilic carbon chain connected by an amide linkage, were determined by spectrophotometric titration. The calculated value of pFe3+ is 18.1 at pH,7.4. Cryogenic transmission electron microscopy showed that the tris(catecholate) ferric complex formed at physiological pH initially assembles into micelles, in which the catecholate,iron units stay on the exterior of the micelle. The average diameter of these micelles was estimated to be 4.2,nm. The micelles then slowly rearrange into clusters of different sizes, which leads to the formation of unilamellar and bilamellar vesicles. The reorganization processes are comparable to those observed by Butler et al. for the marinobactin siderophores produced by marine bacteria, but in contrast to the marinobactins, vesicles of the Fe3+,LS10 complex form without an excess of iron relative to ligand concentration. The time-dependent micelle-to-vesicle transition is discussed herein. [source] Towards Selective Recognition of Sialic Acid Through Simultaneous Binding to Its cis -Diol and Carboxylate FunctionsEUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 17 2010Martín Regueiro-Figueroa Abstract A series of receptors containing phenylboronic acid and urea or thiourea units have been designed for simultaneous recognition of the cis -diol and carboxylate functions of sialic acids, which are known to be overexpressed on the surfaces of tumor cells. The interaction of the receptors with 5-acetylneuraminic acid (Neu5Ac) and 2-,- O -methyl Neu5Ac (MeNeu5Ac) in DMSO solution has been investigated bymeans of spectrophotometric titrations and 1H, 13C, and 11B NMR spectroscopy. Additionally, we have also investigated the binding of these receptors with competing monosaccharides such as D -(+)-glucose, D -fructose, methyl ,- D -galactoside, and methyl ,- D -mannoside. Our results show that 2-{[3-(4-nitrophenyl)thioureido]methyl}phenylboronic acid (3a) recognizes both Neu5Ac and MeNeu5Ac with good selectivity with regard to the remaining monosaccharides investigated. DFT calculations performed at the B3LYP/6-31G(d) level show that this selectivity is due to a cooperative two-site binding of Neu5Ac through 1) ester formation by interaction at the phenylboronic acid function of the receptor and 2) hydrogen-bond interaction between the thiourea moiety and the carboxylate group of Neu5Ac. Compound 3a can therefore be considered a promising synthon for the design of contrast agents for magnetic resonance imaging of tumors. In contrast, the analogue of 3a containing a urea moiety , compound 3b , displays strong binding to all monosaccharides investigated, due to two-site binding through interaction on the phenylboronic acid function of the receptor and a hydrogen-bond interaction between the urea moiety and the sugar hydroxy groups. [source] Zn2+ Complexes of Di- and Tri-nucleating Azacrown Ligands as Base-Moiety-Selective Cleaving Agents of RNA 3,,5,-Phosphodiester Bonds: Binding to Guanine BaseCHEMBIOCHEM, Issue 11 2008Qi Wang Dr. Abstract The ability of the dinuclear Zn2+ complex of 1,4-bis[(1,5,9-triazacyclododecan-3-yloxy)methyl]benzene (L1) to promote the cleavage of the phosphodiester bond of dinucleoside-3,,5,-monophosphates that contain a guanine base has been studied over a narrow pH range from pH 5.8 to 7.2 at 90,°C. Comparative measurements have been carried out by using the trinuclear Zn2+ complex of 1,3,5-tris[(1,5,9-triazacyclododecan-3-yloxy)methyl]benzene (L2) as a cleaving agent and guanylyl-3,,5,-guanosine (5,-GpG-3,) as a substrate. The strength of the interaction between the cleaving agent and the starting material has been elucidated by UV spectrophotometric titrations. The speciation and binding mode have been clarified by potentiometric titrations with hydrolytically stable 2,- O -methylguanylyl-3,,5,-guanosine and 1H NMR spectroscopic measurements with guanylyl-3,,5,-guanosine. The results show that the guanine base is able to serve as a site for anchoring for the Zn2+,azacrown moieties of the cleaving agents L1 and L2, analogously to uracil base. The interaction is, however, weaker than with the uracil base and, hence, only the 5,-GpG-3, site (in addition to 5,-GpU-3, and 5,-UpG-3, sites) is able to markedly modulate the phosphodiester cleavage by the Zn2+ complexes of di- and trinucleating azacrown ligands containing an ether oxygen as a potential H-bond-acceptor site. [source] Protonated Macrobicyclic Hosts Containing Pyridine Head Units for Anion RecognitionCHEMISTRY - A EUROPEAN JOURNAL, Issue 19 2008David Esteban-Gómez Dr. Abstract In this paper, we report two macrobicyclic receptors containing pyridine head units derived from 1,10-diaza-15-crown[5] (L1) or 4,13-diaza-18-crown[6] (L2) that can be protonated in MeCN and used for anion recognition. The interaction of these protonated lateral macrobicycles with different anions has been investigated by means of spectrophotometric titrations in MeCN. The association constants for the complexes of halide anions with the protonated macrobicycles follow the sequences Cl,>Br,>I,>F, (L1) and Cl,>F,>I,>Br, (L2), whereby an increase of more than two logarithmic units is observed from F, to Cl, for the binding constants of the receptor derived from L1. The association constants also indicate an important degree of selectivity of these macrobicyclic receptors for Cl, over Br, or I,. The X-ray crystal structure analyses of the chloride and bromide complexes confirms the formation of the envisaged supramolecular complexes. Moreover, the binding constants indicate that these receptors present a high sulfate-to-nitrate binding selectivity. The stability trend observed for the recognition of halide anions by the macrobicycles presented herein as well as the sulfate-to-nitrate binding selectivity have been rationalised by means of DFT calculations at the B3LYP/LanL2DZ level. These studies indicate that the especially high binding selectivity for Cl, is the result of the optimum fit between the protonated macrobicyclic cavity and the size of the anion, whereas the sulfate-to-nitrate selectivity results from shape complementarity between the hydrogen-binding acceptor sites on sulfate and the hydrogen-bond donors of the macrobicycle. [source] | ||||||||||