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Metal Coordination (metal + coordination)

Distribution by Scientific Domains

Chemistry	100%

Distribution within Chemistry

General & Introductory Chemistry	53%
Crystallography	20%

Selected Abstracts

Metal Coordination Mediated Reversible Conversion between Linear and Cross-Linked Supramolecular Polymers,

ANGEWANDTE CHEMIE, Issue 6 2010
Feng Wang Dr.
Dynamisches Duo: Dynamische supramolekulare Polymere mit unterschiedlichen Topologien, z.,B. lineare und vernetzte Strukturen (siehe Schema), können reversibel ineinander umgewandelt werden. Als externe Auslöser dienen nichtkovalente Wirt-Gast- und Metall-Ligand-Erkennungsmotive. [source]

Multifunctional "Clickates" as Versatile Extended Heteroaromatic Building Blocks: Efficient Synthesis via Click Chemistry, Conformational Preferences, and Metal Coordination

CHEMISTRY - A EUROPEAN JOURNAL, Issue 35 2007
Robert
Abstract Click chemistry has been utilized to access 2,6-bis(1-aryl-1,2,3-triazol-4-yl)pyridines (BTPs) as versatile extended heteroaromatic building blocks for their exploitation in supramolecular chemistry, in particular foldamer and ligand design. In addition to their high-yielding synthesis using CuI -catalyzed Huisgen-type 1,3-dipolar cycloaddition reactions the formed triazole moieties constitute an integral part of the BTP framework and encode both its pronounced conformational preferences as well as its chelating ability. A diverse set of symmetrical and non-symmetrical BTPs carrying electron-donating and -withdrawing substituents at both terminal aryl and the central pyridine moieties has efficiently been synthesized and could furthermore readily be postfunctionalized with amphiphilic side chains and porphyrin chromophores. In both solution and solid state, the BTP scaffold adopts a highly conserved horseshoe-like anti,anti conformation. Upon protonation or metal coordination, the BTP scaffold switches to the chelating syn,syn conformation. Iron and europium complexes have been prepared, successfully characterized by single-crystal X-ray diffraction analysis, and investigated with regard to their spin state and luminescent properties. The extended heteroaromatic BTP scaffold should prove useful for the design of responsive foldamer backbones and the preparation of new magnetic and emissive materials. [source]

Disulfides, Imines, and Metal Coordination within a Single System: Interplay between Three Dynamic Equilibria

CHEMISTRY - A EUROPEAN JOURNAL, Issue 34 2007
Rupam
Abstract We report a system in which three distinct dynamic linkages, disulfide (SS), imine (CN), and coordinative (N,metal) bonds were shown to be capable of simultaneous reversible exchange. The "disulfide layer" of the system under study consists of two homo-disulfides, bis(4-aminophenyl) disulfide 1 and bis(4-methoxyphenyl) disulfide 2 that equilibrate in the presence of catalytic amount of triethylamine to favor the formation of a hetero-disulfide product, 4-aminophenyl-4,-methoxyphenyl disulfide 3. The addition of 2-formylpyridine and a metal salt strongly perturbed this 1+2,3 equilibrium through the formation of metal complexes incorporating disulfide 1 as a subcomponent. CuI perturbed the equilibrium by a factor of 3.3, and FeII by a factor of 179, in both cases in favor of the homo-disulfides. The disulfide equilibrium could be further modified, following metal-complex formation, by coordinative (transmetallation: substitution of FeII for CuI) or covalent (imine exchange: the substitution of one amine residue for another) exchange. Thus, although the three kinds of dynamic linkages were demonstrated to be mutually compatible, changes at one kind of linkage could be used to predictably perturb an equilibrium involving another. [source]

A Cyclam Core Dendrimer Containing Dansyl and Oligoethylene Glycol Chains in the Branches: Protonation and Metal Coordination

CHEMISTRY - A EUROPEAN JOURNAL, Issue 35 2006
Barbara Branchi Dr.
Abstract We have synthesized a dendrimer (1) consisting of a 1,4,8,11-tetraazacyclotetradecane (cyclam) core, appended with four benzyl substituents that carry, in the 3- and 5-positions, a dansyl amide derivative (of type 2), in which the amide hydrogen is replaced by a benzyl unit that carries an oligoethylene glycol chain in the 3- and 5-positions. All together, the dendrimer contains 16 potentially luminescent moieties (eight dansyl- and eight dimethoxybenzene-type units) and three distinct types of multivalent sites that, in principle, can be protonated or coordinated to metal ions (the cyclam nitrogen atoms, the amine moieties of the eight dansyl units, and the 16 oligoethylene glycol chains). We have studied the absorption and luminescence properties of 1, 2, and 3 in acetonitrile and the changes taking place upon titration with acid and a variety of divalent (Co2+, Ni2+, Cu2+, Zn2+), and trivalent (Nd3+, Eu3+, Gd3+) metal ions as triflate and/or nitrate salts. The results obtained show that: 1) double protonation of the cyclam ring takes place before protonation of the dansyl units; 2) the oligoethylene glycol chains do not interfere with protonation of the cyclam core and the dansyl units in the ground state, but affect the luminescence of the protonated dansyl units; 3) the first equivalent of metal ion is coordinated by the cyclam core; 4) the interaction of the resulting cyclam complex with the appended dansyl units depends on the nature of the metal ion; 5) coordination of metal ions by the dansyl units follows at high metal-ion concentrations; 6) the effect of the metal ion depends on the nature of the counterion. This example demonstrates that dendrimers may exhibit complete functionality resulting from the integration of the specific properties of their component units. [source]

Pentadentate Ligands for the 1:1 Coordination of Lanthanide(III) Salts,

EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 20 2007
Markus Albrecht
Abstract Three hydrazone type ligands, namely 2 -H, 3, and 4, which were designed to form 1:1 complexes with lanthanoid(III) ions, are presented. Although the tetradentate ligand 2, leads to an interesting complex [(2)(2 -H)YCl2] with yttrium(III), a more general principle for the coordination of the metal ions by hydrazone-type ligands can be found with ligand 3, where 1:1 complexes are obtained with an effective coordination of the metal salts by the ligand. The stabledimer [{(3)Nd(CF3SO3)}2(,-CF3SO3)3]CF3SO3 was characterized by X-ray structure determination. Depending on the size of the metal ion, additional co-ligands can also be bound to the metal centers. This is observed in the molecular structures of [(3)Pr(NO3)2(MeOH)2](NO3), [(3)NdCl2(MeOH)(EtOH)]Cl, [(3)ErCl2(MeOH)]Cl, and [(3)LuCl2]Cl. The solid-state molecular structures of 4 and 4·HCl show the helicating ability of this ligand upon metal coordination. The corresponding lanthanide complexes of 4 are characterized by standard techniques such as NMR and CD spectroscopy and mass spectrometry.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007) [source]

Syntheses, Spectroscopic Studies, and Crystal Structures of Chiral [Rh(aminocarboxylato)(,4 -cod)] and Chiral [Rh(amino alcohol)(,4 -cod)](acetate) Complexes with an Example of a Spontaneous Resolution of a Racemic Mixture into Homochiral Helix-Enantiomers

EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 11 2006
Mohammed Enamullah
Abstract The dimeric complex acetato(,4 -cycloocta-1,5-diene)rhodium(I), [Rh(O2CMe)(,4 -cod)]2 (cod = cycloocta-1,5-diene), reacts with amino acids [HAA = L -alanine, (S)-2-amino-2-phenylacetic acid (L -phenylglycine), N -methylglycine, and N -phenylglycine] and with the amino alcohol (S)-2-amino-2-phenylethanol to afford the aminocarboxylato(,4 -cycloocta-1,5-diene)rhodium(I) complexes [Rh(AA)(,4 -cod)] (AA = deprotonated amino acid = aminocarboxylato ligand) and [(S)-2-amino-2-phenylethanol](,4 -cycloocta-1,5-diene)rhodium(I) acetate, [Rh{(S)-HOCH2,CH(Ph)-NH2}(,4 -cod)](O2CMe) (V). The complexes are characterized by IR, UV/Vis, 1H/13C NMR and mass spectroscopy. The achiral N -phenylglycine ligand gives a chiral N -phenylglycinato complex [Rh(O2C,CH2,NHPh)(,4 -cod)] (IV) with the amine nitrogen atom becoming the stereogenic center upon metal coordination. Complex IV crystallizes in the tetragonal, chiral space group P43 and the crystal structure reveals twofold spontaneous resolution of a racemic mixture into homochiral helix-enantiomers. The investigated crystal contained only one type of helix, namely (left-handed or M- ) 43 -helical chains. This is traced first to an intermolecular N,H···O hydrogen bonding from the stereogenic amino group to a neighboring unligated carboxyl oxygen atom that connects only molecules of the same (R)-configuration into (left-handed or M- ) 43 -helical chains. This intrachain homochirality is supplemented, secondly, by the interlocking of adjacent chains with their corrugated van der Waals surface to allow for an interchain transmission of the sense of helicity, building the single crystal from the same homochiral helix-enantiomer. The enantiomeric amino alcohol complex V crystallizes in the monoclinic, noncentrosymmetric (Sohncke) space group P21. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006) [source]

Metal-Directed Self-Assembly: Two New Metal-Binicotinate Grid Polymeric Networks and Their Fluorescence Emission Tuned by Ligand Configuration

EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 13 2004
Benlai Wu
Abstract Two new 2-D metal-binicotinate coordination polymers, namely, [CdII(bpdc)]n (1) and {[ZnII8(bpdc)8(H2O)8](H2O)8}n (2) (H2bpdc = binicotinic acid) have been synthesized using hydrothermal and three-layer diffusion methods, respectively. Single-crystal X-ray analyses revealed that both are extended grid networks of the (4,4) topology. Their structures alter with the configuration and function of bpdc. The achiral, free H2bpdc has axial chirality induced by metal coordination in 1, and bpdc connects to four metal centers forming a 2-D (4,4) net with three kinds of apertures generated through self-assembly. In 2, however, bpdc connects to three metal centers, fabricating a microporous framework containing hydrophilic channels. Studies on the solid emission spectra of the free ligand, 1, and 2 confirmed, that the configuration of bpdc resulting from metal-directed coordination has a profound effect on the fluorescence emissions of 1 and 2. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004) [source]

Synthesis of Cyclic Peptides by Photochemical Decarboxylation of N -Phthaloyl Peptides in Aqueous Solution

HELVETICA CHIMICA ACTA, Issue 12 2002

The synthesis of a variety of cyclic peptides from N -phthaloyl-protected di-, tri-, tetra-, and pentapeptides with different aminocarboxylic acid tethers by photodecarboxylation , initiated by intramolecular electron transfer , has been explored in aqueous media. The progress and the chemoselectivity of the follow-up processes after CO2 extrusion were traced by the respective pH/time-profiles, as well as by the overall change in pH after completion of the reaction. The competition between cyclization and simple oxidative decarboxylation depends on spacer length and geometry, H-bonding interaction between the electron accepting phthalimide CO groups and amide H-atoms, as well as the geometric reorganization coupled with the radical combination step and the formation of the lactam rings. With progressing reaction, hydrolysis of the phthalimide chromophore becomes an increasingly important side reaction due to the constant increase in pH. The use of phosphate-buffered aqueous media consequently improved the cyclization yields. The ground-state interactions between amide groups and the terminal COO, group with the imide CO groups were studied for the model system [N -(phthaloyl)glycyl]sarcosine (1) by NMR spectroscopy where the amide (E/Z)-equilibrium depends on the presence of carboxylate vs. free carboxylic acid, demonstrating the role of H-bonding and metal coordination. [source]

Structural studies of human alkaline phosphatase in complex with strontium: Implication for its secondary effect in bones

PROTEIN SCIENCE, Issue 7 2006
Paola Llinas
Abstract Strontium is used in the treatment of osteoporosis as a ranelate compound, and in the treatment of painful scattered bone metastases as isotope. At very high doses and in certain conditions, it can lead to osteomalacia characterized by impairment of bone mineralization. The osteomalacia symptoms resemble those of hypophosphatasia, a rare inherited disorder associated with mutations in the gene encoding for tissue-nonspecific alkaline phosphatase (TNAP). Human alkaline phosphatases have four metal binding sites,two for zinc, one for magnesium, and one for calcium ion,that can be substituted by strontium. Here we present the crystal structure of strontium-substituted human placental alkaline phosphatase (PLAP), a related isozyme of TNAP, in which such replacement can have important physiological implications. The structure shows that strontium substitutes the calcium ion with concomitant modification of the metal coordination. The use of the flexible and polarizable force-field TCPEp (topological and classical polarization effects for proteins) predicts that calcium or strontium has similar interaction energies at the calcium-binding site of PLAP. Since calcium helps stabilize a large area that includes loops 210,228 and 250,297, its substitution by strontium could affect the stability of this region. Energy calculations suggest that only at high doses of strontium, comparable to those found for calcium, can strontium substitute for calcium. Since osteomalacia is observed after ingestion of high doses of strontium, alkaline phosphatase is likely to be one of the targets of strontium, and thus this enzyme might be involved in this disease. [source]

Molecular design and synthesis of artificial double helices

THE CHEMICAL RECORD, Issue 1 2007
Yoshio Furusho
Abstract This account describes novel artificial double helices recently developed by our group. We have designed and synthesized the double helices consisting of two complementary, m -terphenyl-based strands that are intertwined through chiral amidinium,carboxylate salt bridges. Due to the chiral substituents on the amidine groups, the double helices adopted an excess one-handed helical conformation in solution as well as in the solid state. By extending the modular strategy, we have synthesized double helices bearing Pt(II) linkers, which underwent the double helix-to-double helix transformations through the chemical reactions of the Pt(II) complex moieties. In addition, artificial double-stranded metallosupramolecular helical polymers were constructed by combining the salt bridges and metal coordination. In contrast to the design-oriented double helices based on salt bridges, we have serendipitously developed a spiroborate-based double helicate bearing oligophenol strands. The optical resolution of the helicate was successfully attained by a diastereomeric salt formation. We have also unexpectedly found that oligoresorcinols consisting of a very simple repeating unit self-assemble into double helices with the aid of aromatic interactions in water. Furthermore, a bias in the twist sense of the double helices can be achieved by incorporating chiral substituents at both ends of the strands. © 2007 The Japan Chemical Journal Forum and Wiley Periodicals, Inc. Chem Rec 7: 1,11; 2007: Published online in Wiley InterScience (www.interscience.wiley.com) DOI 10.1002/tcr.20097 [source]

Structural plasticity of peanut lectin: an X-ray analysis involving variation in pH, ligand binding and crystal structure

ACTA CRYSTALLOGRAPHICA SECTION D, Issue 2 2004
S. Kundhavai Natchiar
Until recently, it has only been possible to grow crystals of peanut lectin when complexed with sugar ligands. It is now shown that it is possible to grow peanut lectin crystals at acidic pH in the presence of oligopeptides corresponding to a loop in the lectin molecule. Crystals have also been prepared in the presence of these peptides as well as lactose. Low-pH crystal forms of the lectin,lactose complex similar to those obtained at neutral pH have also been grown. Thus, crystals of peanut lectin grown under different environmental conditions, at two pH values with and without sugar bound to the lectin, are now available. They have been used to explore the plasticity and hydration of the molecule. A detailed comparison between different structures shows that the lectin molecule is sturdy and that the effect of changes in pH, ligand binding and environment on it is small. The region involving the curved front ,-sheet and the loops around the second hydrophobic core is comparatively rigid. The back ,-sheet involved in quaternary association, which exhibits considerable variability, is substantially flexible, as is the sugar-binding region. The numbers of invariant water molecules in the hydration shell are small and they are mainly involved in metal coordination or in stabilizing unusual structural features. Small consistent movements occur in the combining site upon sugar binding, although the site is essentially preformed. [source]

Structures of three diphtheria toxin repressor (DtxR) variants with decreased repressor activity

ACTA CRYSTALLOGRAPHICA SECTION D, Issue 5 2001
Ehmke Pohl
The diphtheria toxin repressor (DtxR) from Corynebacterium diphtheriae regulates the expression of the gene on corynebacteriophages that encodes diphtheria toxin (DT). Other genes regulated by DtxR include those that encode proteins involved in siderophore-mediated iron uptake. DtxR requires activation by divalent metals and holo-DtxR is a dimeric regulator with two distinct metal-binding sites per three-domain monomer. At site 1, three side chains and a sulfate or phosphate anion are involved in metal coordination. In the DtxR,DNA complex this anion is replaced by the side chain of Glu170 provided by the third domain of the repressor. At site 2 the metal ion is coordinated exclusively by constituents of the polypeptide chain. In this paper, five crystal structures of three DtxR variants focusing on residues Glu20, Arg80 and Cys102 are reported. The resolution of these structures ranges from 2.3 to 2.8,Å. The side chain of Glu20 provided by the DNA-binding domain forms a salt bridge to Arg80, which in turn interacts with the anion. Replacing either of the salt-bridge partners with an alanine reduces repressor activity substantially and it has been inferred that the salt bridge could possibly control the wedge angle between the DNA-binding domain and the dimerization domain, thereby modulating repressor activity. Cys102 is a key residue of metal site 2 and its substitution into a serine abolishes repressor activity. The crystal structures of Zn-Glu20Ala-DtxR, Zn-Arg80Ala-DtxR, Cd-Cys102Ser-DtxR and apo-Cys102Ser-DtxR in two related space groups reveal that none of these substitutions leads to dramatic rearrangements of the DtxR fold. However, the five crystal structures presented here show significant local changes and a considerable degree of flexibility of the DNA-binding domain with respect to the dimerization domain. Furthermore, all five structures deviate significantly from the structure in the DtxR,DNA complex with respect to overall domain orientation. These results confirm the importance of the hinge motion for repressor activity. Since the third domain has often been invisible in previous crystal structures of DtxR, it is also noteworthy that the SH3-like domain could be traced in four of the five crystal structures. [source]

Structure of TTHA1623, a novel metallo-,-lactamase superfamily protein from Thermus thermophilus HB8

ACTA CRYSTALLOGRAPHICA SECTION F (ELECTRONIC), Issue 5 2009
Akihiro Yamamura
TTHA1623 is a metallo-,-lactamase superfamily protein from the extremely thermophilic bacterium Thermus thermophilus HB8. Homologues of TTHA1623 exist in a wide range of bacteria and archaea and one eukaryote, Giardia lamblia, but their function remains unknown. To analyze the structural properties of TTHA1623, the crystal structures of its iron-bound and zinc-bound forms have been determined to 2.8 and 2.2,Å resolution, respectively. TTHA1623 possesses an ,,,,-fold similar to that of other metallo-,-lactamase superfamily proteins with glyoxalase II-type metal coordination. However, TTHA1623 exhibits a putative substrate-binding pocket with a unique shape. [source]

Anion,, Slides for Transmembrane Transport

CHEMISTRY - A EUROPEAN JOURNAL, Issue 1 2009
Jiri Mareda Dr.
Abstract The recognition and transport of anions is usually accomplished by hydrogen bonding, ion pairing, metal coordination, and anion,dipole interactions. Here, we elaborate on the concept to use anion,, interactions for this purpose. Different to the popular cation,, interactions, applications of the complementary ,-acidic surfaces do not exist. This is understandable because the inversion of the aromatic quadrupole moment to produce ,-acidity is a rare phenomenon. Here, we suggest that ,-acidic aromatics can be linked together to produce an unbendable scaffold with multiple binding sites for anions to move along across a lipid bilayer membrane. The alignment of multiple anion,, sites is needed to introduce a cooperative multi-ion hopping mechanism. Experimental support for the validity of the concept comes from preliminary results with oligonaphthalenediimide (O-NDI) rods. Predicted by strongly positive facial quadrupole moments, the cooperativity and chloride selectivity found for anion transport by O-NDI rods were consistent with the existence of anion,, slides. The proposed mechanism for anion transport is supported by DFT results for model systems, as well as MD simulations of rigid O-NDI rods. Applicability of anion,, slides to achieve electroneutral photosynthesis is elaborated with the readily colorizable oligoperylenediimide (O-PDI) rods. To clarify validity, scope and limitations of these concepts, a collaborative research effort will be needed to address by computer modeling and experimental observations the basic questions in simple model systems and to design advanced multifunctional anion,, architectures. [source]

Multifunctional "Clickates" as Versatile Extended Heteroaromatic Building Blocks: Efficient Synthesis via Click Chemistry, Conformational Preferences, and Metal Coordination