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Water Molecules (water + molecule)
Kinds of Water Molecules Selected AbstractsCatalytic Action of a Single Water Molecule in a Proton-Migration Reaction,ANGEWANDTE CHEMIE, Issue 29 2010Yoshiyuki Matsuda Dr. Ein kleiner Schritt: Der Mechanismus der Protonenverschiebung in ionisiertem Aceton durch Wasser wurde IR-spektroskopisch untersucht. Im Anschluss an die Ionisation spaltet das Wassermolekül ein Proton von einer Methylgruppe des Acetonmoleküls ab und überträgt es auf die Carbonylgruppe (siehe Bild). [source] Infrared Spectroscopy of Water Cluster Anions, (H2O)n=3-24 - in the HOH Bending Region: Persistence of the Double H-Bond Acceptor (AA) Water Molecule in the Excess Electron Binding Site of the Class I Isomers.CHEMINFORM, Issue 35 2006Joseph R. Roscioli Abstract ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract, please click on HTML or PDF. [source] A Role for Internal Water Molecules in Proton Affinity Changes in the Schiff Base and Asp85 for One-way Proton Transfer in Bacteriorhodopsin,PHOTOCHEMISTRY & PHOTOBIOLOGY, Issue 4 2008Joel E. Morgan Light-induced proton pumping in bacteriorhodospin is carried out through five proton transfer steps. We propose that the proton transfer to Asp85 from the Schiff base in the L-to-M transition is accompanied by the relocation of a water cluster on the cytoplasmic side of the Schiff base from a site close to the Schiff base in L to the Phe219-Thr46 region in M. The water cluster present in L, formed at 170 K, is more rigid than that at room temperature. This may be responsible for blocking the conversion of L to M at 170 K. In the photocycle at room temperature, this water cluster returns to the site close to the Schiff base in N, with a rigid structure similar to that of L at 170 K. The increase in the proton affinity of Asp85, which is a prerequisite for the one-way proton transfer in the M-to-N transition, is suggested to be facilitated by a structural change which disrupts interactions between Asp212 and the Schiff base, and between Asp212 and Arg82. We propose that this liberation of Asp212 is accompanied by a rearrangement of the structure of water molecules between Asp85 and Asp212, stabilizing the protonated Asp85 in M. [source] ChemInform Abstract: Matrix-Isolation Infrared Spectroscopic and Density Functional Theory Studies on Reactions of Laser-Ablated Lead and Tin Atoms with Water Molecules.CHEMINFORM, Issue 3 2008Yun-Lei Teng Abstract ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a "Full Text" option. The original article is trackable via the "References" option. [source] Effect of Water Molecules on the Cycloaromatization of Non-Conjugated Aromatic Tetraynes.CHEMINFORM, Issue 41 2006Tomikazu Kawano Abstract ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract, please click on HTML or PDF. [source] Adsorption of Insulin Peptide on Charged Single-Walled Carbon Nanotubes: Significant Role of Ordered Water MoleculesCHEMPHYSCHEM, Issue 8 2009Jia-Wei Shen Abstract Ordered hydration shells: The more ordered hydration shells outside the charged CNT surfaces prevent more compact adsorption of the peptide in the charged CNT systems (see picture), but peptide binding strengths on the charged CNT surfaces are stronger due to the electrostatic interaction. Studies of adsorption dynamics and stability for peptides/proteins on single-walled carbon nanotubes (SWNTs) are of great importance for a better understanding of the properties and nature of nanotube-based biosystems. Herein, the dynamics and mechanism of the adsorption of the insulin chain B peptide on different charged SWNTs are investigated by explicit solvent molecular dynamics simulations. The results show that all types of surfaces effectively attract the model peptide. Water molecules play a significant role in peptide adsorption on the surfaces of charged carbon nanotubes (CNTs). Compared to peptide adsorption on neutral CNT surfaces, the more ordered hydration shells outside the tube prevent more compact adsorption of the peptide in charged CNT systems. This shield effect leads to a smaller conformational change and van der Waals interaction between the peptide and surfaces, but peptide binding strengths on charged CNT surfaces are stronger than those on the neutral CNT surface due to the strong electrostatic interaction. The result of these simulations implies the possibility of improving the binding strength of peptides/proteins on CNT surfaces, as well as keeping the integrity of the peptide/protein conformation in peptide/protein,CNT complexes by charging the CNTs. [source] How Does a Membrane Protein Achieve a Vectorial Proton Transfer Via Water Molecules?CHEMPHYSCHEM, Issue 18 2008Steffen Wolf Abstract We present a detailed mechanism for the proton transfer from a protein-bound protonated water cluster to the bulk water directed by protein side chains in the membrane protein bacteriorhodopsin. We use a combined approach of time-resolved Fourier transform infrared spectroscopy, molecular dynamics simulations, and X-ray structure analysis to elucidate the functional role of a hydrogen bond between Ser193 and Glu204. These two residues seal the internal protonated water cluster from the bulk water and the protein surface. During the photocycle of bacteriorhodopsin, a transient protonation of Glu204 leads to a breaking of this hydrogen bond. This breaking opens the gate to the extracellular bulk water, leading to a subsequent proton release from the protonated water cluster. We show in detail how the protein achieves vectorial proton transfer via protonated water clusters in contrast to random proton transfer in liquid water. [source] Energy Transfer in Single Hydrogen-Bonded Water MoleculesCHEMPHYSCHEM, Issue 6 2005Huib J. Bakker Prof. Abstract We study the structure and dynamics of hydrogen-bonded complexes of H2O/HDO and acetone dissolved in carbon tetrachloride by probing the response of the OH stretching vibrations with linear mid-infrared spectroscopy and femtosecond mid-infrared pump,probe spectroscopy. We find that the hydrogen bonds in these complexes break and reform with a characteristic time scale of ,1 ps. These hydrogen-bond dynamics are observed to play an important role in the equilibration of vibrational energy over the two OH groups of the H2O molecule. For both H2O and HDO, the OH stretching vibrational excitation relaxes with a time constant of 6.3±0.3 ps, and the molecular reorientation has a time constant of 6±1 ps. [source] Influence of relative gas humidity on the inactivation efficiency of a low temperature gas plasmaJOURNAL OF APPLIED MICROBIOLOGY, Issue 6 2008P. Muranyi Abstract Aims:, To investigate the effect of relative gas humidity on the inactivation efficiency of a cascaded dielectric barrier discharge (CDBD) in air against Aspergillus niger and Bacillus subtilis spores on PET foils. Methods and Results:, The inactivation kinetics as a function of treatment time were determined using synthetic air with different relative humidity as the process gas. Spores of A. niger and B. subtilis respectively were evenly sprayed on PET foils for use as bioindicators. In the case of A. niger, increased spore mortality was found at a high relative gas humidity of 70% (approx. 2 log10). This effect was more evident at prolonged treatment times. In contrast, B. subtilis showed slightly poorer inactivation at high gas humidity. Conclusions:, Water molecules in the process gas significantly affect the inactivation efficiency of CDBD in air. Significance and Impact of the Study:, Modifying simple process parameters such as the relative gas humidity can be used to optimize plasma treatment to improve inactivation of resistant micro-organisms such as conidiospores of A. niger. [source] Stability of the hydration layer of tropocollagen: A QM studyJOURNAL OF COMPUTATIONAL CHEMISTRY, Issue 4 2010K. Pálfi Abstract Collagen is a triple helical protein, highly hydrated in nature. Bella and Berman (J Mol Biol 1996, 264, 734) have reported the structure of the first hydration layer. Water molecules form bridges of different length around the POG repeats and self assemble into left-handed helical water threads. To explore the stability of these specifically hydrated places, we have designed suitable QM models: each comprises a triple helix formed by 18 residues surrounded by 8 to 12 explicit waters. Two sets of amino acids were used, one standing for the core structural subunit of tropocollagen (POG-model) and one for its natural enzyme recognition sites (AAG-model). We have determined the stability order of the water binding places, the strongest being ,8.1 kcal mol,1, while the weakest ,6.1 kcal mol,1 per hydrogen bond. In X-ray structures, each triplet of tropocollagen is shielded by six to nine water molecules. Beside the mandatory six, the "surplus" three water molecules further strengthen the binding of all the others. However, the displacement of selected water molecules turns out to be energy neutral. These water binding places on the surface of the triple helix can provide explanation on how an almost liquid-like hydration environment exists between the closely packed tropocollagens (Henkelman et al., Magn Reson Med 1994, 32, 592). It seems that these water reservoirs or buffers can provide space for "hole conduction" of water molecules and thus contribute to the elasticity of collagen. © 2009 Wiley Periodicals, Inc. J Comput Chem, 2010 [source] WATGEN: An algorithm for modeling water networks at protein,protein interfacesJOURNAL OF COMPUTATIONAL CHEMISTRY, Issue 14 2007Huynh-Hoa Bui Abstract Water molecules at protein,protein interfaces contribute to the close packing of atoms and ensure complementarity between the protein surfaces, as well as mediating polar interactions. Therefore, modeling of interface water is of importance in understanding the structural basis of biomolecular association. We present an algorithm, WATGEN, which predicts locations for water molecules at a protein,protein or protein,peptide interface, given the atomic coordinates of the protein and peptide. A key element of the WATGEN algorithm is the prediction of water sites that can form multiple hydrogen bonds that bridge the binding interface. Trial calculations were performed on water networks predicted by WATGEN at 126 protein,peptide interfaces (X-ray resolutions , 2.0 Å), using different criteria for water placement. The energies of the predicted water networks were evaluated in AMBER8 and used in the choice of parameters for WATGEN. The 126 interfaces include 1264 experimentally determined bridging water sites, and the WATGEN algorithm predicts 72 and 88% of these sites within 1.5 and 2.0 Å, respectively. The predicted number of water molecules at each interface was much higher than the number of water molecules identified experimentally. Therefore, random placement of the same number of water molecules as that predicted at each interface was performed as a control, and resulted in only 22 and 40% of water sites placed within 1.5 and 2.0 Å of experimental sites, respectively. Based on these data, we conclude that WATGEN can accurately predict the location of water molecules at a protein,peptide interface, and this may be of value for understanding the energetics and specificity of biomolecular association. © 2007 Wiley Periodicals, Inc. J Comput Chem, 2007 [source] A tetrazol-5-yl analogue of glycine, 5-ammoniomethyl-1H -tetrazolide, and its copper(II) complexACTA CRYSTALLOGRAPHICA SECTION C, Issue 2 2010Alexander S. Lyakhov A nonclassical tetrazole isostere of glycine, viz. zwitterionic 5-ammoniomethyl-1H -tetrazolide, C2H5N5, (I), crystallizes in the chiral P31 space group, similar to ,-glycine. The crystal packing of (I) is determined by a set of classical hydrogen bonds, forming a three-dimensional network that is practically the same as that in ,-glycine. The CuII complex of (I), poly[[bis(,2 -5-aminomethyl-1H -tetrazolido-,3N1,N5:N4)copper(II)] dihydrate], {[Cu(C2H4N5)2]·2H2O}n, (II), is a layered coordination polymer formed as a result of tetrazole ring bridges. The CuII cations lie on inversion centres, are surrounded by four anions and adopt elongated octahedral coordination. Water molecules are located in the interlayer space and connect the layers into a three-dimensional network via a system of hydrogen bonds. [source] Hydrogen-bonded supramolecule of N,N,-bis(4-pyridylmethyl)oxalamide and a zigzag chain structure of catena -poly[[[dichloridocobalt(II)]-,- N,N,-bis(4-pyridylmethyl)oxalamide-,2N4:N4,] hemihydrate]ACTA CRYSTALLOGRAPHICA SECTION C, Issue 5 2007Gene-Hsiang Lee N,N,-Bis(4-pyridylmethyl)oxalamide, C14H14N4O2, exists as a dimer which is extended into a two-dimensional network with other dimers through pyridine,amide hydrogen bonds. The crystal structure of the title coordination polymer, {[CoCl2(C14H14N4O2)]·0.5H2O}n, features a one-dimensional zigzag chain, in which the cobalt ion sits at a twofold symmetry position and adopts a tetrahedral geometry, and the bridging ligand lies on an inversion center and connects to CoII ions in a bis-monodentate mode. Furthermore, two interwoven chains create a cavity of ca 8.6 × 8.6,Å, which produces a three-dimensional channel. Water molecules are held in the channel by hydrogen bonds. [source] Water molecules in the crystal structure of tricyclic acyclovirACTA CRYSTALLOGRAPHICA SECTION C, Issue 6 2001Kinga Suwi The biologically important molecule tricyclic acyclovir, presented here as 3-[(2-hydroxyethoxy)methyl]-6-methyl-3H -imidazolo[1,2- a]purin-9(5H)-one dihydrate, C11H13N5O3·2H2O, shows conformational flexibility, which is observed in the solid state as two symmetrically independent molecules with different side-chain conformations. Additionally, one of these molecules exhibits side-chain disorder, such that there are three different conformations in the crystal. Water molecules found in the crystal form (H2O)8 clusters which are located between molecules of tricyclic acyclovir. The complex hydrogen-bond network formed between water and tricyclic acyclovir in the solid state may be related to the solvation of the molecules in solution. [source] Adsorption of Insulin Peptide on Charged Single-Walled Carbon Nanotubes: Significant Role of Ordered Water MoleculesCHEMPHYSCHEM, Issue 8 2009Jia-Wei Shen Abstract Ordered hydration shells: The more ordered hydration shells outside the charged CNT surfaces prevent more compact adsorption of the peptide in the charged CNT systems (see picture), but peptide binding strengths on the charged CNT surfaces are stronger due to the electrostatic interaction. Studies of adsorption dynamics and stability for peptides/proteins on single-walled carbon nanotubes (SWNTs) are of great importance for a better understanding of the properties and nature of nanotube-based biosystems. Herein, the dynamics and mechanism of the adsorption of the insulin chain B peptide on different charged SWNTs are investigated by explicit solvent molecular dynamics simulations. The results show that all types of surfaces effectively attract the model peptide. Water molecules play a significant role in peptide adsorption on the surfaces of charged carbon nanotubes (CNTs). Compared to peptide adsorption on neutral CNT surfaces, the more ordered hydration shells outside the tube prevent more compact adsorption of the peptide in charged CNT systems. This shield effect leads to a smaller conformational change and van der Waals interaction between the peptide and surfaces, but peptide binding strengths on charged CNT surfaces are stronger than those on the neutral CNT surface due to the strong electrostatic interaction. The result of these simulations implies the possibility of improving the binding strength of peptides/proteins on CNT surfaces, as well as keeping the integrity of the peptide/protein conformation in peptide/protein,CNT complexes by charging the CNTs. [source] Acid,Base Chemistry at the Ice Surface: Reverse Correlation Between Intrinsic Basicity and Proton-Transfer Efficiency to Ammonia and Methyl AminesCHEMPHYSCHEM, Issue 17 2007Seong-Chan Park Dr. Abstract Proton transfer from the hydronium ion to NH3, CH3NH2, and (CH3)2NH is examined at the surface of ice films at 60 K. The reactants and products are quantitatively monitored by the techniques of Cs+ reactive-ion scattering and low-energy sputtering. The proton-transfer reactions at the ice surface proceed only to a limited extent. The proton-transfer efficiency exhibits the order NH3>(CH3)NH2=(CH3)2NH, which opposes the basicity order of the amines in the gas phase or aqueous solution. Thermochemical analysis suggests that the energetics of the proton-transfer reaction is greatly altered at the ice surface from that in liquid water due to limited hydration. Water molecules constrained at the ice surface amplify the methyl substitution effect on the hydration efficiency of the amines and reverse the order of their proton-accepting abilities. [source] One-Dimensional Coordination Polymers of MnII, CuII, and ZnII Supported by Carboxylate-Appended (2-Pyridyl)alkylamine Ligands , Structure and MagnetismEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 22 2009Himanshu Arora Abstract Four new complexes [MnII(L1OO)(H2O)][ClO4]·2H2O (1), [ZnII(L1OO)][ClO4]·2H2O (2), [CuII(L3OO)][CF3SO3]·H2O (3), and [ZnII(L3OO)][ClO4] (4) (L1OO, = 3-[(2-(pyridine-2-yl)ethyl){2-(pyridine-2-yl)methyl}amino]propionate; L3OO, = 3-[(2-(pyridine-2-yl)ethyl){(dimethylamino)ethyl}amino]propionate) have been synthesized and characterized by elemental analysis, IR, and UV/Vis spectroscopy. Structural analysis revealed that 1, 3, and 4 are one-dimensional chain-like coordination polymers. In 1 distorted octahedral MnN3O3 and in 3 square-pyramidal CuN3O2 coordination is satisfied by three nitrogen atoms and an appended carboxylate oxygen atom of the ligand, and an oxygen atom belonging to the carboxylate group of an adjacent molecule. In 4 trigonal bipyramidal ZnN3O2 coordination environment is provided by two nitrogen atoms and an appended carboxylate oxygen atom of the ligand in the equatorial plane, and the two axial positions are satisfied by a tertiary amine nitrogen and an oxygen atom belonging to the carboxylate group of an adjacent molecule. In 1 the MnII center is coordinated by an additional water molecule. In these complexes each monomeric unit is sequentially connected by syn - anti carboxylate bridges. Temperature-dependent magnetic susceptibilities for 1 and 3 are measured, revealing antiferromagnetic interactions through syn - anti carboxylate bridges between the MII centers. Analysis of the crystal packing diagram reveals that in 1 extensive ,,, stacking involving alternate pyridine rings of adjacent 1D chain exists, which eventually lead to the formation of a 2D network structure. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009) [source] Kinetics of Bis(p -nitrophenyl)phosphate (BNPP) Hydrolysis Reactions with Trivalent Lanthanide Complexes of N -Hydroxyethyl(ethylenediamine)- N,N,,N, -triacetate (HEDTA),EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 8 2009C. Allen Chang Abstract Kinetic studies of hydrolysis reactions of BNPP [sodium bis(p -nitrophenyl)phosphate] with trivalent lanthanide (Ln3+) complexes of HEDTA [HEDTA = N -hydroxyethyl(ethylenediamine)- N,N,,N, -triacetate] were performed at pH 6.96,11.34 and 25 °C by a spectrophotometric method and by HPLC analysis. The reaction rates increase with increasing atomic number of lanthanide and solution pH from PrHEDTA to EuHEDTA and then decrease for heavier LnHEDTA complexes. Plots of pseudo-first-order rate constants (kobs) vs. pH could be fitted to the equation kobs = kLnL(OH)[LnL]T/{1,+,exp[,2.303(pH,,,pKh)]}, where kLnL(OH) is the rate constant for the reaction of LnHEDTA(OH), with BNPP, Kh is the hydrolysis constant of LnHEDTA, and [LnL]T is the total concentration of LnHEDTA. The pKh values obtained by the kinetic method are in the range 8.2,10.3 and are similar to those measured by potentiometric methods. At [LnL]T = 10,70 mM and pH 10.5, most of the observed pseudo-first-order rate constants could be fitted to a simple saturation kinetic model, kobs = k1K[LnHEDTA(OH),]/{1 + K[LnHEDTA(OH),]}, where K is the equilibrium constant for the formation for LnHEDTA(OH),BNPP and is in the range 2,147 M,1. The k1 values are in the range 1.12,×,10,5,2.71,×,10,3 s,1. The kobs data for TbHEDTA and HoHEDTA were fitted to a quadratic equation. It was observed that the dinuclear species are more reactive. ESI mass spectrometry confirmed that the reaction between BNPP and EuHEDTA is a simple hydrolysis but not a transesterification, presumably because the three inner-sphere coordinated water molecules are far away from the coordinated hydroxyethyl group. Hydrolysis is likely to occur by proton transfer from one inner-sphere coordinated water molecule to the deprotonated ethyl oxide group followed by nucleophilic attack of the resulting hydroxide ion on the bonded BNPP anion.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009) [source] Base-Induced Formation of Two Magnesium Metal-Organic Framework Compounds with a Bifunctional Tetratopic LigandEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 23 2008Pascal D. C. Dietzel Abstract Two coordination polymers constructed from magnesium and the tetratopic organic linker 2,5-dihydroxyterephthalic acid are reported, denominated CPO-26-Mg and CPO-27-Mg. The organic component carries two different types of protic functional groups. The degree of deprotonation of the organic component can be regulated by the amount of sodium hydroxide employed in the synthesis, thus determining which of the compounds forms. In CPO-26-Mg, only the carboxylic acid groups of the linker are deprotonated and take part in the construction of the three-dimensional framework. The structure is non-porous, and its topology is based on the PtS net. In CPO-27-Mg, both the carboxylic acid and the hydroxy groups are deprotonated and involved in the construction of a microporous three-dimensional framework which is based on a honeycomb motif containing large solvent-filled channels. The metal atoms are arranged in chiral chains along the intersection of the honeycomb and contain one water molecule in their coordination sphere, which allows for the creation of coordinatively unsaturated metal sites upon dehydration. CPO-27-Mg is a potentially useful lightweight adsorbent with a pore volume of 60,% of the total volume of the structure and an apparent Langmuir surface area of up to 1030 m2,g,1. Its thermal stability was investigated by thermogravimetry and variable-temperature powder X-ray diffraction, which shows framework degradation to commence at 160 °C in air, at 235 °C under nitrogen, and at 430 °C in a dynamic vacuum. Thermogravimetric dehydration and re-hydration experiments at miscellaneous temperatures indicate that it is possible to obtain open metal sites in CPO-27-Mg, but the water is more tightly bound in this material than in the previously reported isostructural nickel compound.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008) [source] Controlled Assembly of [Nb6,xWxO19](8,x), (x = 0,4) Lindqvist Ions with (Amine)copper ComplexesEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 21 2008Travis M. Anderson Abstract The mixed addenda isopolyanion, [N(CH3)4]2Na2[cis -Nb2W4O19]·18H2O, reacts with Cu(NO3)2 in water and in the presence of NH2CH2CH2NH2 (en) or NH4OH at 60 °C to yield a phase that is decorated {[Cu(en)2(H2O)]2[Nb2W4O19]·2H2O (1)} or charge-balanced {[Cu(NH3)4(H2O)]2[Nb2W4O19]·8H2O (2)}, respectively, by (amine)copper complexes. The prolonged heating at 95 °C of [N(CH3)4]6[Nb10O28]·6H2O, [N(CH3)4]2Na2[cis -Nb2W4O19]·18H2O, or Na4K2[cis -Nb4W2O19]·12H2O and Cu(NO3)2 in a mixed water/amine [en or NH2CH2CH2CH2NH2 (dap)] solution results in the formation of two-dimensional materials with alternate layers of (amine)copper complexes linking Lindqvist [Nb6,xWxO19](8,x), (x = 0,4) clusters. These phasesinclude: [Cu(dap)2]3[Nb4W2O19]·7H2O (3), [Cu(dap)2]3[H2Nb6O19]·6H2O (4), [Cu(dap)2]3[Nb3W3O19]·Cl·6H2O (5), and [Cu(en)2]3[Nb4W2O19]·6H2O (6). Complexes 4 and 5 result from the decomposition of [Nb10O28]6, and [cis -Nb2W4O19]4, to [H2Nb6O19]6, and [fac -Nb3W3O19]5,, respectively, in alkaline solution. Complex 5 contains an extra-framework site that is occupied by Cl,, but this site is occupied by a water molecule in 3 and is vacant in structures 4 and 6. The results of this study suggest that charge density, cluster charge and symmetry, and cluster-cation pairing are all important parameters in the incorporation of d-electron metals onto the surfaces of [Nb6,xWxO19](8,x), (x = 0,4) clusters or into the frameworks of Lindqvist-based complex materials.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008) [source] Anion-Directed Template Synthesis and Hydrolysis of Mono-Condensed Schiff Base of 1,3-Pentanediamine and o -Hydroxyacetophenone in NiII and CuII ComplexesEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 21 2008Pampa Mukherjee Abstract Bis(o -hydroxyacetophenone)nickel(II) dihydrate, on reaction with 1,3-pentanediamine, yields a bis-chelate complex [NiL2]·2H2O (1) of mono-condensed tridentate Schiff baseligand HL {2-[1-(3-aminopentylimino)ethyl]phenol}. The Schiff base has been freed from the complex by precipitating the NiII as a dimethylglyoximato complex. HL reacts smoothly with Ni(SCN)2·4H2O furnishing the complex [NiL(NCS)] (2) and with CuCl2·2H2O in the presence of NaN3 or NH4SCN producing [CuL(N3)]2 (3) or [CuL(NCS)] (4). On the other hand, upon reaction with Cu(ClO4)2·6H2O and Cu(NO3)2·3H2O, the Schiff base undergoes hydrolysis to yield ternary complexes [Cu(hap)(pn)(H2O)]ClO4 (5) and [Cu(hap)(pn)(H2O)]NO3 (6), respectively (Hhap = o -hydroxyacetophenone and pn = 1,3-pentanediamine). The ligand HL undergoes hydrolysis also on reaction with Ni(ClO4)2·6H2O or Ni(NO3)2·6H2O to yield [Ni(hap)2] (7). The structures of the complexes 2, 3, 5, 6, and 7 have been confirmed by single-crystal X-ray analysis. In complex 2, NiII possesses square-planar geometry, being coordinated by the tridentate mono-negative Schiff base, L and the isothiocyanate group. The coordination environment around CuII in complex 3 is very similar to that in complex 2 but here two units are joined together by end-on, axial-equatorial azide bridges to result in a dimer in which the geometry around CuII is square pyramidal. In both 5 and 6, the CuII atoms display the square-pyramidal environment; the equatorial sites being coordinated by the two amine groups of 1,3-pentanediamine and two oxygen atoms of o -hydroxyacetophenone. The axial site is coordinated by a water molecule. Complex 7 is a square-planar complex with the Ni atom bonded to four oxygen atoms from two hap moieties. The mononuclear units of 2 and dinuclear units of 3 are linked by strong hydrogen bonds to form a one-dimensional network. The mononuclear units of 5 and 6 are joined together to form a dimer by very strong hydrogen bonds through the coordinated water molecule. These dimers are further involved in hydrogen bonding with the respective counteranions to form 2-D net-like open frameworks. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008) [source] Lanthanide-Based Conjugates as Polyvalent Probes for Biological LabelingEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 18 2008Stéphanie Claudel-Gillet Abstract A series of lanthanide complexes of [LnL(H2O)] composition, suitable for biological labeling has been studied, in which L is a strongly chelating ligand containing chromophoric bipyridylcarboxylate units and Ln = Sm, Eu, Gd, Tb, and Dy. For the Gd complex, a combined 17O NMR and 1H NMRD study has been performed. The water exchange rate obtained, kex298 = (5.2,±,0.6),×,106 s,1, is slightly higher than those for [Gd(dota)(H2O)], or [Gd(dtpa)(H2O)]2,. Transformation of the uncoordinated carboxylate function of the ligand into an activated ester ensures covalent linking of the complex to bovine serum albumine (BSA). The relaxivity properties of the Gd complex labeled on BSA revealed a limited increase of both longitudinal and transversal relaxivities. This can be related to the partial replacement of the inner-sphere water molecules by coordinating functions of the protein. Additionally, the Sm and Dy complexes are described and chemically characterized. Their photophysical properties were investigated by means of absorption, steady-state and time-resolved spectroscopy, evidencing efficient photosensitization of the lanthanide emission by ligand excitation (antenna effect). Luminescence lifetime measurements confirmed the presence of a water molecule in the first coordination sphere that partly explained the relatively poor luminescence properties of the Dy and Sm complexes in aqueous solutions. The spectroscopic properties of the series of complexes are questioned in terms of time-resolved acquisition techniques. Finally, their availability for use in time-resolved luminescence microscopy is demonstrated by staining experiments of rat brain slices, where the complex showed enhanced localization in some hydrophilic regions of the blood,brain barrier (BBB).(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008) [source] A Trinuclear Aqua Cyano-Bridged Ruthenium Complex [{(,5 -C5H5)(PPh3)2Ru(,-CN)}2RuCl2(PPh3)(H2O)]PF6: Synthesis, Characterization and Crystal StructureEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 13 2007Viatcheslav Vertlib Abstract The organometallic trinuclear aqua cyano-bridged complex [{(,5 -C5H5)(PPh3)2Ru(,-CN)}2RuCl2(PPh3)(H2O)]PF6 (1), in which the fragment [RuCl2(PPh3)(H2O)] acts as a bridge and an acceptor group between the two terminal cyclopentadienyl ruthenium cyano moieties, was isolated in moderate yield from the reaction of [(,5 -C5H5)(PPh3)2RuCN] with [RuCl2(PPh3)3] in THF. To the best of our knowledge, compound 1 is one of the few examples of a trinuclear array of ruthenium fragments bridged by the nitrogen atom of the,C,N, group (Ru,C,N,Ru,,N,C,Ru) with a Ru-coordinated water molecule. The new aqua complex was structurally characterized by FTIR, 1H, 13C, and 31P NMR spectroscopy, mass spectrometry, elemental analysis, single-crystal X-ray diffraction, and cyclic voltammetry. The title complex crystallizes in a triclinic unit cell a = 17.3477(6) Å, b = 17.8551(5) Å, c = 18.2460(7) Å, , = 95.693(2)°, , = 111.648(2)°, and , = 97.839(2)° in the space group P with Z = 2.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007) [source] One-Dimensional Oxalato-Bridged Metal(II) Complexes with 4 - Amino-1,2,4-triazole as Apical LigandEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 21 2005Urko García-Couceiro Abstract The synthesis, chemical characterization, thermal behavior and magnetic properties of six new one-dimensional oxalato-bridged metal(II) complexes of formula [M(,-ox)(4atr)2]n [MII = Cu (1), Ni (2), Co (3), Zn (4), Fe(5)] and [Cd(,-ox)(4atr)2(H2O)]n (6) (ox = oxalato dianion, 4atr = 4-amino-1,2,4-triazole) are reported. The crystal structures of 1 and 6 have been solved by single-crystal X-ray diffraction, whereas the remaining compounds have been studied by means of X-ray powder diffraction methods. Compounds 1,5 are isomorphous and crystallize in the triclinic space group P1¯ with unit cell parameters for 1 of a = 5.538(1) Å, b = 7.663(1) Å, c = 7.711(2) Å, , = 62.21(1)°, , = 73.91(1)°, , = 86.11(1)°, and Z = 1. The crystal structures are comprised of one-dimensional linear chains in which the trans -[M(4atr)2]2+ units are sequentially bridged by bis(bidentate) oxalato ligands, resulting in an octahedral O4N2 donor set. Cryomagnetic susceptibility measurements show the occurrence of antiferromagnetic intrachain interactions for 2, 3, and 5, whereas compound 1 exhibits a weak ferromagnetic coupling in agreement with the out-of-plane exchange pathway involved. The magnetic behavior of 1 and 2 is analyzed and discussed in the light of the available magneto-structural data for analogous systems. CdII complex crystallizes in the monoclinic space group C2/c with unit cell parameters of a = 16.128(2) Å, b = 6.757(1) Å, c = 11.580(2) Å, , = 104.46(1)°, and Z = 4. Its crystal structure contains one-dimensional chains in which metal centers are heptacoodinated to four oxygen atoms from two symmetry-related bis(bidentate) oxalato bridges, two endocyclic nitrogen atoms of trans -coordinated triazole ligands and one water molecule, to give a CdO4OwN2 pentagonal-bipyramidal geometry. Thermoanalytical and variable-temperature X-ray powder diffraction analyzes show that compound 6 undergoes a reversible dehydration,hydration process in which the anhydrous residue crystallizes with a different crystal lattice retaining the dimensionality of the oxalato,metal framework. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005) [source] Dinuclear Complexes of MII Thiocyanate (M = Ni and Cu) Containing a Tridentate Schiff-Base Ligand: Synthesis, Structural Diversity and Magnetic PropertiesEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 12 2005Suparna Banerjee Abstract A dinuclear NiII complex, [Ni2(L)2(H2O)(NCS)2]·3H2O (1) in which the metal atoms are bridged by one water molecule and two ,2 -phenolate ions, and a thiocyanato-bridged dimeric CuII complex, [Cu(L)NCS]2 (2) [L = tridentate Schiff-base ligand, N -(3-aminopropyl)salicylaldimine, derived from 1:1 condensation of salicylaldehyde and 1,3-diaminopropane], have been synthesized and characterized by IR and UV/Vis spectroscopy, cyclic voltammetry and single-crystal X-ray diffraction studies. The structure of 1 consists of dinuclear units with crystallographic C2 symmetry in which each NiII atom is in a distorted octahedral environment. The Ni,O distance and the Ni,O,Ni angle, through the bridged water molecule, are 2.240(11) Å and 82.5(5)°, respectively. The structure of 2 consists of dinuclear units bridged asymmetrically by di-,1,3 -NCS ions; each CuII ion is in a square-pyramidal environment with , = 0.25. Variable-temperature magnetic susceptibility studies indicate the presence of dominant ferromagnetic exchange coupling in complex 1 with J = 3.1 cm,1, whereas complex 2 exhibits weak antiferromagnetic coupling between the CuII centers with J = ,1.7 cm,1. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005) [source] Structure Comparison of Early and Late Lanthanide(III) Homodinuclear Macrocyclic Complexes with the Polyamine Polycarboxylic Ligand H8OHECEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 19 2004Ulrike A. Böttger Abstract The solid-state structures of two new homodinuclear chelate complexes with the late lanthanide(III) ions Yb and Lu, [Na2(Yb2OHEC)].14.5H2O (1), and [Na2(Lu2OHEC)].14.5H2O (2) (H8OHEC = 1,4,7,10,14,17,20,23-octaazacyclohexacosane- 1,4,7,10,14,17,20,23-octaacetic acid), have been determined by X-ray crystal structure analysis. Each lanthanide(III) ion is coordinated by eight donor atoms of the ligand and the geometry of the coordination polyhedron approaches a bicapped trigonal prism. These structures are compared with those of the homodinuclear chelate complexes with the same ligand and the mid to early lanthanide(III) ions Gd, Eu, La and also Y. A distinctive structural change occurs across the lanthanide series. The centrosymmetric mid to early lanthanide(III) complexes are all ninefold-coordinated in a capped square antiprismatic arrangement with a water molecule coordinated in a prismatic position. This structure is maintained in aqueous solution, together with an asymmetric minor isomer. The late lanthanide(III) OHEC complexes not only lack the inner-sphere water, but the change of coordination sphere also results in a loss of symmetry of the whole complex molecule. The observed change of coordination mode and number of the lanthanide ion may offer a geometric model for the isomerization process in eight- and ninefold-coordinated complex species that are isomers in a possible coordination equilibrium observed by NMR in aqueous solution. This model may also explain the intramolecular rearrangements necessary during water exchange in the inner coordination sphere of the complex [(Gd2OHEC)(H2O)2]2, through a slow dissociative mechanism. Protonation constants of the H8OHEC ligand and complex formation constants of this ligand with GdIII, CaII, CuII and ZnII have been determined by solution thermodynamic studies. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004) [source] Funnel Complexes with CoII and NiII: New Probes into the Biomimetic Coordination Ability of the Calix[6]arene-Based Tris(imidazole) SystemEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 9 2004Olivier Sénèque Abstract The coordination properties of the calix[6]arene-based tris(imidazole) ligand X6Me3Imme3 were further explored with CoII and NiII. This imidazole system stabilizes tetrahedral mononuclear CoII complexes with an exchangeable fourth exogenous ligand (water, alcohol, amide) located at the heart of the hydrophobic calixarene cavity. With a weak donor ligand such as a nitrile, both four-coordinate tetrahedral and five-coordinate trigonal bipyramidal complexes were obtained. The latter contains a second nitrile molecule trans to the included guest nitrile. These complexes were characterized in solution as well as in the solid state. The NiII complexes are square-based pyramidal five-coordinate edifices with a guest nitrile inside the cavity and a water molecule outside. A comparison with previously described ZnII and CuII complexes emphasizes the flexibility of this ligand. A comparison with carbonic anhydrase, a mononuclear zinc enzyme with a tris(histidine) coordination core, shows that X6Me3Imme3 displays many structural features of this enzyme except for the cis coordination of the exogenous ligands. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004) [source] Supramolecular Chemistry Based on [W3S4(H2O)6Cl3]+ , A Versatile Building BlockEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 1 2004Maxim N. Sokolov Abstract The cluster [W3S4(H2O)6Cl3]+ (which is present in solutions of [W3S4(H2O)9]4+ in 1,4 M HCl) reacts with the macrocyclic cavitand cucurbituril (C36H36N24O12) to form supramolecular adducts of 2:1 cluster/cucurbituril stoichiometry, where two portals of cucurbituril (which contains a water molecule in its cavity) are closed by two cluster cations. These aggregates are bound together in the solid by complementary hydrogen bonds between coordinated Cl, and the cations H9O4+ to give chains. Thus, a supramolecular architecture is achieved from three different but complementary building blocks. The packing of the chains affords a honeycomb structure (hexagonal symmetry) with channels (about 5.2 Å in diameter). The overall stoichiometry is (H9O4){[W3S4(H2O)6Cl3]2(C36H36N24O12)}Cl3·16.15H2O (1). [W3S4(H2O)6Cl3]+ reacts with SbCl3 in 6 M HCl to give cuboidal [W3(SbCl3)S4(H2O)6Cl3]+, which forms with the macrocyclic cavitand cucurbituril a 2:1 cluster/cucurbituril adduct , a discrete supramolecule consisting of five independent molecular units. In the solid it crystallizes as a salt of very rare anion [SbCl6]3, with the stoichiometry {[W3(SbCl3)S4(H2O)6Cl3]2(C36H36N24O12)}(SbCl6)2/3·12H2O (2). (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004) [source] Spirocyclic Pyridoazepine Analogues of Galanthamine: Synthesis, Modelling Studies and Evaluation as Inhibitors of AcetylcholinesteraseEUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 15 2008Sofie Vanlaer Abstract Spirocyclic pyridoazepines, designed as simplified analogues of the alkaloid galanthamine, were synthesised and evaluated as inhibitors of acetylcholinesterase. The key cyclisation step involved internal displacement of 2-chloro or 2-iodopyridine by either nucleophilic aromatic substitution or a Heck reaction. The target compounds showed significant inhibition of acetylcholinesterase but lower than that of galanthamine. This result could be rationalised by comparative docking simulation studies based on the known crystal structure of the acetylcholinesterase,galanthamine complex; multiple hydrogen bonding of a cocrystallised water molecule to both the receptor and the ligand was found to be of crucial importance for effective binding to the active site of the enzyme. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008) [source] A Combined Theoretical and Experimental Research Project into the Aminolysis of ,-Lactam Antibiotics: The Importance of Bifunctional CatalysisEUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 21 2003Natalia Díaz Abstract This paper reports the results of experimental work on the aminolysis of penicillin (6-APA) and monobactam (aztreonam) antibiotics by propylamine or ethanolamine. In general, aztreonam is slightly more reactive than 6-APA, despite the common assumption that the amide bond should be less activated in monobactams. Intriguingly, when ethanolamine acts as the nucleophile, the corresponding rate law has a kinetic term proportional to [RNH2][RNH3+]. To complement the experimental observations, the rate-determining free energy barriers in aqueous solution for various mechanistic pathways were computed by standard quantum chemical methodologies. From previous theoretical work it was assumed that the aminolysis of ,-lactams proceeds through mechanisms in which either a water molecule or a second amine molecule may act as bifunctional catalysts, assisting proton transfer from the attacking amine molecule to the leaving amino group. The energy barriers as computed have moderate values (ca. 26,34 kcal·mol,1) and reproduce most of the experimentally observed kinetic trends. Furthermore, the calculations predict that positively charged ethanolamine molecules can act as bifunctional catalysts as well, thus explaining the presence of the kinetic term proportional to [RNH2][RNH3+] in the rate law. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003) [source] | ||||||||||||||||||||||||||||||||||||||||||||||