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Weak Interactions (weak + interaction)
Selected AbstractsChemInform Abstract: Weak Interactions Between Trivalent Pnictogen Centers: Computational Analysis of Bonding in Dimers X3E···EX3 (E: Pnictogen, X: Halogen).CHEMINFORM, Issue 37 2009Jani Moilanen 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] Weak interactions and molecular recognition in systems involving electron transfer proteinsTHE CHEMICAL RECORD, Issue 4 2001Shun Hirota Abstract Electrostatic interactions and other weak interactions between amino acid side chains on protein surfaces play important roles in molecular recognition, and the mechanism of their intermolecular interactions has gained much interest. We established that charged peptides are useful for investigating the molecular recognition character of proteins and their molecular interaction induced structural changes. Positively charged lysine peptides competitively inhibited electron transfer from reduced cytochrome f (cyt f) or cytochrome c (cyt c) to oxidized plastocyanin (PC), due to neutralization of the negatively charged site of PC by formation of PC,lysine peptide complexes. Lysine peptides also inhibited electron transfer from cyt c to cytochrome c peroxidase. Likewise, negatively charged aspartic acid peptides interacted with the positively charged sites of cyt f and cyt c, and competitively inhibited electron transfer from reduced cyt f or cyt c to oxidized PC and from [Fe(CN)6]4, to oxidized cyt c. Changes in the geometry and a shift to a higher redox potential of the active site Cu of PC on oligolysine binding were detected by spectroscopic and electrochemical measurements, owing to the absence of absorption in the visible region for lysine peptides. Structural and redox potential changes were also observed for cyt f and cyt c by interaction with aspartic acid peptides. ©2001 John Wiley & Sons, Inc. and The Japan Chemical Journal Forum Chem Rec 1:290,299, 2001 [source] Weak interactions in chain polymers [M(,- X)2L2], (M = Zn, Cd; X = Cl, Br; L = substituted pyridine) , an electron density studyACTA CRYSTALLOGRAPHICA SECTION B, Issue 5 2009Ruimin Wang The experimental electron-density distributions in crystals of five chain polymers [M(,- X)2(py)2] (M = Zn, Cd; X = Cl, Br; py = 3,5-substituted pyridine) have been obtained from high-resolution X-ray diffraction data sets (sin,,/, > 1.1,Å,1) at 100,K. Topological analyses following Bader's `Atoms in Molecules' approach not only confirmed the existence of (3, ,1) critical points for the chemically reasonable and presumably strong covalent and coordinative bonds, but also for four different secondary interactions which are expected to play a role in stabilizing the polymeric structures which are unusual for Zn as the metal center. These weaker contacts comprise intra- and inter-strand C,H...X,M hydrogen bonds on the one hand and C,X...X,C interhalogen contacts on the other hand. According to the experimental electron-density studies, the non-classical hydrogen bonds are associated with higher electron density in the (3, ,1) critical points than the halogen bonds and hence are the dominant interactions both with respect to intra- and inter-chain contacts. [source] Unusual Magnetism of an Unsymmetrical Trinickel ChainEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 33 2008F. Albert Cotton Abstract An extended metal atom chain (EMAC) compound with an unsymmetrical trinickel core and the formula [Ni3(dpa)4(CH3CN)](PF6)2·2CH2Cl2 (1·2CH2Cl2, dpa is the anion of 2,2,-dipyridylamine) has the central Ni atom in an essentially square-planar configuration. Besides having four equatorial nitrogen atoms, the two terminal metal centers have axial interactions that are notably different with one having a strongly bound acetonitrile molecule with a Ni(3),N(3) distance of 2.108(5) Å while the other unit has a very weak interaction with an axial PF6 anion [Ni(1)···F(1) separation of 2.690 Å]. In these outer units, the Ni(3) atom is pulled out of the idealized plane of the four equatorial nitrogen atoms by 0.239 Å, while in the one with an axial PF6 anion the metal atom is pulled from the plane of the equatorial nitrogen atoms by only 0.097 Å. In 1 there are two unpaired electrons and an S = 1 state prevails from ca. 25 to 300 K. This magnetic behavior differs considerably from that of symmetrical trinickel EMACs with two strongly pyramidal terminal nickel atoms. A discussion of the effect of various axial ligands on the geometry of the terminal nickel atoms is provided. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008) [source] Synthesis of Triazole-Bridged Unsymmetrical Porphyrin Dyads and Porphyrin,Ferrocene ConjugatesEUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 3 2010Vijayendra S. Shetti Abstract A simple method has been used to synthesize four porphyrin azides with cores such as N4, N3S, N2SO and N2S2 in 60,90,% yields by treating the corresponding aminoporphyrins with tert -butyl nitrite (tBuONO) and azidotrimethylsilane (TMSN3) in THF/CH3CN under mild reaction conditions. The hitherto unknown aminoporphyrins with heteroatom cores were synthesized from their corresponding nitroporphyrins by standard SnCl2/HCl reduction. The azidoporphyrins were used to synthesize six triazole-bridged unsymmetrical porphyrin dyads containing two different types of porphyrin sub-units as well as five triazole-bridged porphyrin,ferrocene conjugates under CuI -catalyzed "click" reaction conditions. Various CuI -catalyzed reaction conditions were studied and the best yields of triazole-bridged dyads and conjugates were obtained with CuI/DIPEA in THF/CH3CN at room temperature for overnight. The unsymmetrical porphyrin dyads and porphyrin,ferrocene conjugates were characterized by various spectroscopic and electrochemical techniques. In unsymmetrical porphyrin dyads, the NMR, absorption and electrochemical studies indicate a weak interaction between the two porphyrin sub-units. However, preliminary photophysical studies support an efficient singlet-singlet energy transfer from one porphyrin unit to another in five unsymmetrical dyads reported here. In porphyrin,ferrocene conjugates, the fluorescence of porphyrin was quenched significantly due to photo-induced electron transfer from ferrocene to porphyrin. [source] Structural consequences of site-directed mutagenesis in flexible protein domainsFEBS JOURNAL, Issue 8 200156)S mutant of RhoGDI, NMR characterization of the L(5 The guanine dissociation inhibitor RhoGDI consists of a folded C-terminal domain and a highly flexible N-terminal region, both of which are essential for biological activity, that is, inhibition of GDP dissociation from Rho GTPases, and regulation of their partitioning between membrane and cytosol. It was shown previously that the double mutation L55S/L56S in the flexible region of RhoGDI drastically decreases its affinity for Rac1. In the present work we study the effect of this double mutation on the conformational and dynamic properties of RhoGDI, and describe the weak interaction of the mutant with Rac1 using chemical shift mapping. We show that the helical content of the region 45,56 of RhoGDI is greatly reduced upon mutation, thus increasing the entropic penalty for the immobilization of the helix, and contributing to the loss of binding. In contrast to wild-type RhoGDI, no interaction with Rac1 could be identified for amino-acid residues of the flexible domain of the mutant RhoGDI and only very weak binding was observed for the folded domain of the mutant. The origins of the effect of the L55S/L56S mutation on the binding constant (decreased by at least three orders of magnitude relative to wild-type) are discussed with particular reference to the flexibility of this part of the protein. [source] The assembly factor P17 from bacteriophage PRD1 interacts with positively charged lipid membranesFEBS JOURNAL, Issue 20 2000Juha M. Holopainen The interactions of the assembly factor P17 of bacteriophage PRD1 with liposomes were investigated by static light scattering, fluorescence spectroscopy, and differential scanning calorimetry. Our data show that P17 binds to positively charged large unilamellar vesicles composed of the zwitterionic 1-palmitoyl-2-oleoyl-phosphatidylcholine and sphingosine, whereas only a weak interaction is evident for 1-palmitoyl-2-oleoyl-phosphatidylcholine vesicles. P17 does not bind to negatively charged membranes composed of 1-palmitoyl-2-oleoyl-phosphatidylglycerol and 1-palmitoyl-2-oleoyl-phosphatidylcholine. Our differential scanning calorimetry results reveal that P17 slightly perturbs the phase behaviour of neutral phosphatidylcholine and negatively charged multilamellar vesicles. In contrast, the phase transition temperature of positively charged dimyristoylphosphatidylcholine/sphingosine multilamellar vesicles (molar ratio 9 : 1, respectively) is increased by approximately 2.4 °C and the half width of the enthalpy peak broadened from 1.9 to 5.6 °C in the presence of P17 (protein : lipid molar ratio 1 : 47). Moreover, the enthalpy peak is asymmetrical, suggesting that lipid phase separation is induced by P17. Based on the far-UV CD spectra, the ,-helicity of P17 increases upon binding to positively charged micelles composed of Triton X-100 and sphingosine. We propose that P17 can interact with positively charged lipid membranes and that this binding induces a structural change on P17 to a more tightly packed and ordered structure. [source] Syntheses and crystal structures of triorganotin (IV) derivatives with 2,2,-bipyridine-4,4,-dicarboxylic acidHETEROATOM CHEMISTRY, Issue 1 2009Ru-Fen Zhang Four organotin complexes with 2,2,-bipyridine-4,4,-dicarboxylic acid, H2dcbp: (Ph3n)2(dcbp) 1, [(PhCH2)3n]2(dcbp) , 2CH3OH 2, [(Me3Sn)2(dcbp)]n3, [(Bu3Sn)2(dcbp)]n4 have been synthesized. The complexes 1,4 were characterized by elemental, IR, 1H, 13C, 119n NMR, and X-ray crystallographic analyses. Crystal structures show that complex 1 is a monomer with one ligand coordinated to two triorganotin moieties, and a 1D infinite polymeric chain generates via intermolecular CH,,,N hydrogen bond; complex 2 is also a monomer and forms a 2D network by intermolecular O,H,,,O weak interaction; both of complexes 3 and 4 form 2D network structures where 2,2,-bipyridine-4,4,-dicarboxylate acts as a tetradentate ligand coordinated to trimethyltin and tri-n-butyltin ions, respectively. © 2009 Wiley Periodicals, Inc. Heteroatom Chem 20:19,28, 2009; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/hc.20506 [source] Fabrication of aragonite rosette superstructure through the weak interaction between nonionic polymers and Ca2+JOURNAL OF APPLIED POLYMER SCIENCE, Issue 6 2010Shuxian Shi Abstract The controlled formation of aragonite by simple method under ambient condition is a big challenge for biomaterial scientists. In this article, we took poly (N -vinyl pyrrolidone) (PVP) as an example to investigate the influence of water-soluble nonionic polymers on the polymorphs of CaCO3 via CO2 diffusion method under ambient pressure and temperature, and found that the existence of PVP molecules favors the formation of aragonite with rosette superstructure. A possible mechanism is proposed that nonionic polymers can be doped into amorphous calcium carbonate (ACC) particles and further participate in the transformation process from ACC to aragonite and then promotes the formation of rosette superstructure through parallel aggregation by crosslinking the aragonite nuclei. The experiments of CaCO3 crystallization in presence of poly(ethylene oxide) (PEO) and poly(vinyl alcohol) (PVA) confirmed the mechanism. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010 [source] Application of the distributed activation energy model to biomass and biomass constituents devolatilizationAICHE JOURNAL, Issue 10 2009María V. Navarro Abstract In this study, an investigation about the thermal behavior of four different woods was carried out. The distributed activation energy model was applied to study the effect of heating rate on the reaction of single solids. Results obtained were used in the curve prediction of fraction of mass remaining and rate of mass loss vs. temperature at more realistic heating rates. The possible calculation of biomass samples behavior in pyrolysis conditions as the summation of their constituents, lignin, cellulose, and hemi-cellulose is also explored. All the samples show a weak interaction between the constituents which produce slight differences between experimental and calculated behavior. However, differences between experimental and calculated data lower than 2% offer a robust test of the applicability of the model on kinetic studies of a wide range of biomass samples, heating rates, data input format and equipment layout. © 2009 American Institute of Chemical Engineers AIChE J, 2009 [source] Differences in the interaction between aryl propionic acid derivatives and poly(vinylpyrrolidone) K30: A multi-methodological approachJOURNAL OF PHARMACEUTICAL SCIENCES, Issue 11 2009Zehadin Gashi Abstract The present work aims at the application of several methods to explain differences in the physical interaction of some aryl propionic acid derivatives (ibuprofen [IBP], ketoprofen [KET], flurbiprofen [FLU], naproxen [NAP], fenbufen [FEN]) with poly(vinylpyrrolidone) (PVP) K30, stored together at 298,±,0.5 K and 22% RH. X-ray powder diffractometry and 13C-solid state NMR demonstrated that IBP was able to strongly interact with the polymer, while weak interaction was observed for KET, FLU, NAP, and the least for FEN. The interaction of comelted drug and PVP was studied by differential scanning calorimetry by applying the Gordon,Taylor equation, which revealed that small molar drug volumes may favour the drug diffusion through the PVP amorphous chains increasing the polymer free volume and decreasing the mixture Tg. The molecular docking study revealed that intermolecular energy is mainly due to the contribution of van der Waals energy component, causing the differences among the drugs, and is related to the drug,PVP surface contact area in the complex formed. Solid-state kinetic study demonstrated that IBP molecules are involved in a three-dimensional diffusion mechanism within the polymer favoured by its low molar volume that reduces molecular hindrance, and by the weakness of its crystal lattice, which facilitates crystallinity loss and stabilisation of the amorphous phase. © 2009 Wiley-Liss, Inc. and the American Pharmacists Association J Pharm Sci 98:4216,4228, 2009 [source] Study of the adsorption of benzimidazole and 2-mercaptobenzothiazole on an iron surface by confocal micro-Raman spectroscopyJOURNAL OF RAMAN SPECTROSCOPY, Issue 12 2004G. Wang Abstract Benzimidazole (BIMH) and 2-mercaptobenzothiazole (HMBT) dissolved in ethanol were chosen for the investigation of the interaction between organic molecules and surface atoms of iron or iron oxide by confocal micro-Raman spectroscopy. Both BIMH and HMBT show enhanced and highly structured spectra in the 200,1500 cm,1 region when the iron is at a potential of ca ,0.7 to ,0.9 V in a neutral medium. BIMH had a weak interaction with the iron surface in a basic medium but it was chemically adsorbed in a neutral medium. HMBT was chemically adsorbed on the iron via the exocyclic S and N atoms in acidic and neutral solutions, whereas in basic media it was bound electrostatically. Copyright © 2004 John Wiley & Sons, Ltd. [source] Structural and mechanical properties of polystyrene nanocomposites with 1D titanate nanostructures prepared by an extrusion processPOLYMER COMPOSITES, Issue 9 2009Polona Umek Polystyrene (PS) nanocomposites with titanate nanotubes and titanate nanoribbons were prepared by an extrusion process at 180°C. Nanocomposites with 1 wt% of nanofillers and pure PS that had also been exposed to the extrusion process were comparatively examined with scanning electron microscopy (SEM), electron dispersive X-ray spectrometry (EDS) mapping, solid state proton nuclear magnetic resonance measurements (1H NMR), tensile tests, and shear creep measurements. SEM images and EDS mapping analysis show that titanate nanoribbons homogeneously distribute at a micrometer length-scale in the PS matrix during the extrusion process. This is not the case for titanate nanotubes, which show a stronger tendency to form clusters. Solid state 1H NMR studies, however, proved that the nanocomposites are inhomogeneous at a nanometric scale where structural components with highly mobile PS molecules coexist with domains of rigid PS molecules. Differences in the 1H spin-lattice relaxation at and above the glass transition temperature Tg = 373 K suggest that nanofillers affect the thermodynamic properties of nanocomposite domains. Only a slight increase in mechanical tensile properties was observed in the case of the nanocomposite containing 1 wt% of titanate nanoribbons (TiNRs) probably reflecting a weak interaction between the polymer matrix and the nanofiller. Nevertheless, our results prove that the use of functionalized TiNRs may, in combination with the extrusion process, represent a very promising starting point for the preparation of TiNR nanocomposites at the industrial level. POLYM. COMPOS., 2009. © 2008 Society of Plastics Engineers [source] Characterization and functional analysis of ABSCISIC ACID INSENSITIVE3 -like genes from Physcomitrella patensTHE PLANT JOURNAL, Issue 6 2006Heather H. Marella Summary Although the moss Physcomitrella patens is known to respond to abscisic acid (ABA) by activating gene expression, the transcriptional components involved have not been characterized. Initially, we used the ABA-responsive Em promoter from wheat linked to , -glucuronidase (GUS) to determine whether ABI3/VP1, transcriptional regulators in the ABA-signaling pathway in angiosperms, were similarly active in the ABA response of P. patens. We show by particle bombardment that ABI3 and VP1 affect Em,GUS expression in P. patens in a manner similar to angiosperms. We also show the involvement of ABI1 in the pathway, utilizing the abi1-1 mutant allele. We isolated three ABI3 -like genes from P. patens. Using an Em-like ABA-responsive promoter from P. patens (PpLea1), we demonstrate that PpABI3A, only in the presence of ABA, strongly enhances PpLea1,GUS expression in P. patens. PpABI3A also enhances ABA-induced Em,GUS expression in P. patens. In barley aleurone, PpABI3A transactivates Em,GUS but to a lesser extent than VP1 and ABI3. PpABI3A:GFP is localized to the nucleus of both protonemal cells and barley aleurone, indicating that the nuclear localization signals are conserved. We show that at least a part of the inability of PpABI3A to fully complement the phenotypes of the Arabidopsis abi3-6 mutant is due to a weak interaction between PpABI3A and the bZIP transcription factor ABI5, as assayed functionally in barley aleurone and physically in the yeast-two-hybrid assay. Our data clearly demonstrate that P. patens will be useful for comparative structural and functional studies of components in the ABA-response pathway such as ABI3. [source] Interactions between Oxygen Atoms on Pt(100): Implications for Ordering during Chemisorption and CatalysisCHEMPHYSCHEM, Issue 10 2010Da-Jiang Liu Abstract We present a DFT analysis of the interactions between chemisorbed oxygen on the unreconstructed (1×1)-Pt(100) surface. These interactions control ordering of O not just for single-species adsorption, but also within O domains during coadsorption and reaction with other species such as CO. The calculations indicate that O prefers bridge sites, as deduced previously. In addition, we find a large difference in the interactions between O at different types of bridge site pairs separated by one lattice constant. There is strong repulsion for pairs separated by a Pt atom, but only a weak interaction for pairs separated by a fourfold hollow site. This finding elucidates the tendency for striped (n×1)-O ordering often observed in chemisorption and reaction studies. [source] Computational Investigation of Hydrogen Adsorption by Alkali-Metal-Doped Organic Molecules: Role of AromaticityCHEMPHYSCHEM, Issue 2 2009Kancharlapally Srinivasu Abstract Hydrogen storage: Simple organic molecular systems (CnHn, n=4, 5, 6, 8) are proposed for hydrogen storage purposes based on the concept of aromaticity. The adsorption of hydrogen is attributed to pronounced charge transfer from the sodium atom (green, see picture) to the organic systems and the electrostatic interaction between the ion and hydrogen molecules. Theoretical studies on hydrogen adsorption in small organic molecular systems, such as cyclobutadiene (C4H4), the cyclopentadienyl radical (C5H5), benzene (C6H6), and cyclooctatetraene (C8H8) and their metal-doped modifications, are carried out. Our results reveal that the simple van der Waals surfaces of pure organic molecules are not good enough for hydrogen adsorption due to the weak interaction between hydrogen molecules and the organic molecular surface. However, doping of alkali-metal atoms in the above organic molecular systems increases their hydrogen adsorption ability significantly, mainly due to electron transfer from the metal atom to the carbon surface. This charged surface created around the metal atom is found to enhance the hydrogen adsorption capacity of the complex considerably, both in terms of interaction energy and the number of adsorbed hydrogen molecules, with a hydrogen adsorption capacity ranging from 10 to 12 wt,%. The role of aromaticity in such molecular systems is important in stabilizing these ionized organo-alkali-metal complexes. [source] New assay to detect low-affinity interactions and characterization of leukocyte receptors for collagen including leukocyte-associated Ig-like receptor-1 (LAIR-1)EUROPEAN JOURNAL OF IMMUNOLOGY, Issue 4 2009Lei Jiang Abstract Leukocyte activity is controlled by numerous interactions between membrane receptors and ligands on the cell surface. These interactions are of low affinity making detection difficult. We developed a sensitive assay that could readily detect extremely weak interactions such as that between CD200 and the activating receptor CD200RLa (Kd>500,,M) at the protein level. We used the new technology to screen for interactions of inhibitory receptors for collagens. We confirmed that both human and mouse leukocyte-associated Ig-like receptor-1, and in addition the related inhibitory leukocyte Ig-like receptor subfamily B member 4 (CD85K, Gp49B), bound collagen specifically, whereas other cell surface proteins gave no binding. The monomeric affinities of the interactions were then determined to allow comparison with other leukocyte interactions and indicate conditions when these interactions might lead to inhibitory signals. [source] Crystal Structure and Surface Photovoltage Properties of MnII Coordination SupramoleculesEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 24 2007Li-Ping Sun Abstract Three MnII coordination supramolecular complexes [Mn(pdc)(H2O)]n1, {[Mn(pdc) (phen)(H2O)]·3H2O}n2, and {[Mn(cyan)2(H2O)4]·2HCl·2(Hcyan)} 3 (H2pdc = pyridine-2,3-dicarboxylic acid, Hcyan = cyanuric acid, phen = 1,10-phenanthroline) were hydrothermally synthesized and their structures determined by single-crystal X-ray diffraction. The pdc group in complex 1 bridges the MnII ions to form an infinite 3D structure. In complex 2, the MnII ion is bridged to a 1D infinite chain by pdc groups and the chain is further connected to a 2D structure by hydrogen bonds. The 3D structure of complex 3 is formed by hydrogen bonds and O···Cl weak interactions. Surface photovoltage spectroscopy (SPS) of complexes 1,3 indicate that they all possess positive SPV response in the range of 300,800 nm and show p -type semiconductor characteristic. The intensities of the SPV responses are obviously different, and this can mainly be attributed to the differences in their structures. Field-induced surface photovoltage spectroscopy (FISPS) of complexes 1,3 confirms their p -type semiconductor characteristic.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007) [source] Synthesis and Structural Characterisation of Palladium and Group-12 Metal Complexes with a Hybrid Phosphanylphosphonate Ferrocene LigandEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 5 2006Abstract Diethyl [1,-(diphenylphosphanyl)ferrocenyl]phosphonate (1) was synthesised by stepwise metallation/functionalisation of 1,1,-dibromoferrocene and studied as a ligand for palladium(II) and group-12 metals. Treatment of [PdCl2(cod)] (cod = ,2:,2 -cycloocta-1,5-diene) with 1 in 1:1 or 1:2 molar ratios gave, respectively, the dinuclear, chloride-bridged complex [{Pd(,-Cl)Cl(1 -,P2)}2] (2) and the mononuclear complex trans -[PdCl2(1 -,P2)2] (3), where 1 coordinates exclusively through the phosphane function. The reactions between 1 and group-12 metal bromides MBr2 in a 1:1 molar ratio gave the adducts [MBr2(1)] [M = Zn (4), Cd (5), and Hg (6)], whose crystal structures change considerably with the metal ion. Thus, whereas 4 is a molecular complex with 1 coordinating as an O1,P2 -chelate, its cadmium(II) analogue is a polymer built up from symmetric {CdBr(,-Br)}2 units interconnected by pairs of O1,P2 -bridging phosphanylphosphonate ligands. Finally, the mercury(II) complex 6 is a halide-bridged dimer, [{Hg(,-Br)Br(1 -,P2)}2]. However, this compound is structurally fluxional in solution (NMR spectra) and, in the crystal, it attains a structure similar to 5 owing to weak interactions between mercury and phosphonate-O1 atoms from adjacent molecules. An isomer to 6, [{HgBr2(1 -,2O1,P2)}2] (7), was isolated from attempted alkylation of 6 and structurally characterised as a dimer, where ligands 1 bridge two {HgBr2} units. All compounds were studied by spectroscopic methods (IR, NMR, mass) and the solid-state structures of 1, 2·,H2O, 3·4,CHCl3, 4, 5, 6·5,C6H6, and 7 have been determined by single-crystal X-ray diffraction. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006) [source] Synthesis and Molecular Structures of Nickel(II) and Cobalt(III) Complexes with 2-(Arylimino)-3-(hydroxyimino)butaneEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 14 2003Ennio Zangrando Abstract We report new series of NiII and CoIII complexes with nitrogen-donor chelating ligands of the (E,E)-2-(arylimino)-3-(hydroxyimino)butane type (Ar,N,N,OH). These ligands are characterized by a hydrophilic (OH group) and a hydrophobic region (aryl group). NiII derivatives were obtained either as trimers of formula [Ni3(Ar,N,N,OH)3Br4(OH)][Br], with the hydrophobic groups oriented on the same side, or as bis(chelated) derivatives with cis geometry, depending on the steric hindrance of the aryl groups. CoIII complexes were obtained only as bis(chelated) derivatives, with the two ligands coplanar. The "iso -oriented" arrangement of ligands in bis(chelated) CoIII complexes is favored by weak interactions between the two ligands, namely O,H···O hydrogen bond and stacking interactions between the aryl groups. CoIII complexes might find application as catalysts for living or controlled radical polymerization of polar olefins, and preliminary results are reported. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003) [source] Investigations on 1-MetallaindanesEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 4 2003Marcel Schreuder Goedheijt Abstract 1-Mercuraindane (6) was prepared in three steps from 1-bromo-2-(2-bromoethyl)benzene (3) and converted into 1-magnesaindane (1) by reaction with magnesium. In solution, 6 was observed to occur in a remarkable dimer/trimer equilibrium, whereas 1 forms a dimer. From 1 and dichlorozirconocene, the 1-zirconaindane 2 was obtained, which reacted with B(C6F5)3 to form the adduct 13. According to spectroscopic data, 13 is formed by attack of the ,-methylene carbon atom at the boron atom and has a zwitterionic structure with weak interactions between the zirconium ion and one of the ortho -fluorine atoms. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003) [source] Distance dependence and salt sensitivity of pairwise, coulombic interactions in a proteinPROTEIN SCIENCE, Issue 5 2002Kelly K. Lee Abstract Histidine pKa values were measured in charge-reversal (K78E, K97E, K127E, and K97E/K127E) and charge-neutralization (E10A, E101A, and R35A) mutants of staphylococcal nuclease (SNase) by 1H-NMR spectroscopy. Energies of interaction between pairs of charges (,Gij) were obtained from the shifts in pKa values relative to wild-type values. The data describe the distance dependence and salt sensitivity of pairwise coulombic interactions. Calculations with a continuum electrostatics method captured the experimental ,Gij when static structures were used and when the protein interior was treated empirically with a dielectric constant of 20. The ,Gij when rij , 10 Å were exaggerated slightly in the calculations. Coulomb's law with a dielectric constant near 80 and a Debye-Hückel term to account for screening by the ionic strength reproduced the salt sensitivity and distance dependence of ,Gij as well as the structure-based method. In their interactions with each other, surface charges behave as if immersed in water; the Debye length describes realistically the distance where interactions become negligible at a given ionic strength. On average, charges separated by distances (rij) ,5 Å interacted with ,Gij , 0.6 kcal/mole in 0.01 M KCl, but ,Gij decayed to ,0.10 kcal/mole when rij = 20 Å. In 0.10 M KCl, ,Gij , 0.10 kcal/mole when rij = 10 Å. In 1.5 M KCl, only short-range interactions with rij , 5 Å persisted. Although at physiological ionic strengths the interactions between charges separated by more than 10 Å are extremely weak, in situations where charge imbalance exists many weak interactions can cumulatively produce substantial effects. [source] Weak interactions and molecular recognition in systems involving electron transfer proteinsTHE CHEMICAL RECORD, Issue 4 2001Shun Hirota Abstract Electrostatic interactions and other weak interactions between amino acid side chains on protein surfaces play important roles in molecular recognition, and the mechanism of their intermolecular interactions has gained much interest. We established that charged peptides are useful for investigating the molecular recognition character of proteins and their molecular interaction induced structural changes. Positively charged lysine peptides competitively inhibited electron transfer from reduced cytochrome f (cyt f) or cytochrome c (cyt c) to oxidized plastocyanin (PC), due to neutralization of the negatively charged site of PC by formation of PC,lysine peptide complexes. Lysine peptides also inhibited electron transfer from cyt c to cytochrome c peroxidase. Likewise, negatively charged aspartic acid peptides interacted with the positively charged sites of cyt f and cyt c, and competitively inhibited electron transfer from reduced cyt f or cyt c to oxidized PC and from [Fe(CN)6]4, to oxidized cyt c. Changes in the geometry and a shift to a higher redox potential of the active site Cu of PC on oligolysine binding were detected by spectroscopic and electrochemical measurements, owing to the absence of absorption in the visible region for lysine peptides. Structural and redox potential changes were also observed for cyt f and cyt c by interaction with aspartic acid peptides. ©2001 John Wiley & Sons, Inc. and The Japan Chemical Journal Forum Chem Rec 1:290,299, 2001 [source] Halogen, hydrogen and electrostatic interactions in 2-amino-5-chloro-1,3-benzoxazol-3-ium nitrate and 2-amino-5-chloro-1,3-benzoxazol-3-ium perchlorateACTA CRYSTALLOGRAPHICA SECTION C, Issue 9 2010Rafal Kruszynski In the title compounds, C7H6ClN2O+·NO3, and C7H6ClN2O+·ClO4,, the ions are connected by N,H...O hydrogen bonds and halogen interactions. Additionally, in the first compound, co-operative ,,, stacking and halogen..., interactions are observed. The energies of the observed interactions range from a value typical for very weak interactions (1.80,kJ,mol,1) to one typical for mildly strong interactions (53.01,kJ,mol,1). The iminium cations exist in an equilibrium form intermediate between exo- and endocyclic. This study provides structural insights relevant to the biochemical activity of 2-amino-5-chloro-1,3-benzoxazole compounds. [source] A structural systematic study of four isomers of difluoro- N -(3-pyridyl)benzamideACTA CRYSTALLOGRAPHICA SECTION C, Issue 7 2009Joyce McMahon The four isomers 2,4-, (I), 2,5-, (II), 3,4-, (III), and 3,5-difluoro- N -(3-pyridyl)benzamide, (IV), all with formula C12H8F2N2O, display molecular similarity, with interplanar angles between the C6/C5N rings ranging from 2.94,(11)° in (IV) to 4.48,(18)° in (I), although the amide group is twisted from either plane by 18.0,(2),27.3,(3)°. Compounds (I) and (II) are isostructural but are not isomorphous. Intermolecular N,H...O=C interactions form one-dimensional C(4) chains along [010]. The only other significant interaction is C,H...F. The pyridyl (py) N atom does not participate in hydrogen bonding; the closest H...Npy contact is 2.71,Å in (I) and 2.69,Å in (II). Packing of pairs of one-dimensional chains in a herring-bone fashion occurs via,-stacking interactions. Compounds (III) and (IV) are essentially isomorphous (their a and b unit-cell lengths differ by 9%, due mainly to 3,4-F2 and 3,5-F2 substitution patterns in the arene ring) and are quasi-isostructural. In (III), benzene rotational disorder is present, with the meta F atom occupying both 3- and 5-F positions with site occupancies of 0.809,(4) and 0.191,(4), respectively. The N,H...Npy intermolecular interactions dominate as C(5) chains in tandem with C,H...Npy interactions. C,H...O=C interactions form R22(8) rings about inversion centres, and there are ,,, stacks about inversion centres, all combining to form a three-dimensional network. By contrast, (IV) has no strong hydrogen bonds; the N,H...Npy interaction is 0.3,Å longer than in (III). The carbonyl O atom participates only in weak interactions and is surrounded in a square-pyramidal contact geometry with two intramolecular and three intermolecular C,H...O=C interactions. Compounds (III) and (IV) are interesting examples of two isomers with similar unit-cell parameters and gross packing but which display quite different intermolecular interactions at the primary level due to subtle packing differences at the atom/group/ring level arising from differences in the peripheral ring-substitution patterns. [source] A one-dimensional nickel(II) coordination polymer containing 2,6-dipicolinate and dipyrido[3,2- a:2,,3,- c]phenazineACTA CRYSTALLOGRAPHICA SECTION C, Issue 12 2007Yi Ma A new coordination polymer, catena -poly[[(dipyrido[3,2- a:2,,3,- c]phenazine-,2N,N,)nickel(II)]-,-2,6-dipicolinato-,4O2,N,O6:O2,], [Ni(C7H3NO4)(C18H10N4)]n, exhibits a one-dimensional structure in which 2,6-dipicolinate acts as a bridging ligand interconnecting adjacent nickel(II) centers to form a chain structure. The asymmetric unit contains one NiII center, one dipyrido[3,2- a:2,,3,- c]phenazine ligand and one 2,6-dipicolinate ligand. Each NiII center is six-coordinated and surrounded by three N atoms and three O atoms from one dipyrido[3,2- a:2,,3,- c]phenazine ligand and two different 2,6-dipicolinate ligands, leading to a distorted octahedral geometry. Adjacent chains are linked by ,,, stacking interactions and weak interactions to form a three-dimensional supramolecular network. [source] The copper(II) complexes di-,-bromo-bis{[2,6-bis(pyrazol-1-yl)pyridine]perchloratocopper(II)} and [2,6-bis(pyrazol-1-yl)pyridine]dibromocopper(II)ACTA CRYSTALLOGRAPHICA SECTION C, Issue 12 2004Surajit Chakrabarty The two title compounds, di-,-bromo-bis{[2,6-bis(pyrazol-1-yl-,N2)pyridine-,N](perchlorato-,O)copper(II)}, [Cu2Br2(ClO4)2(C11H9N5)2], (I), and [2,6-bis(pyrazol-1-yl)pyridine]dibromocopper(II), [CuBr2(C11H9N5)], (II), were synthesized by only slight modifications of the same reaction; compound (II) was formed by adding one molar equivalent of pyrazole (C3N2H4) to the reaction mixture of (I). Compound (I) is a bromo-bridged dinuclear copper(II) compound stabilized by weak interactions with the perchlorate anions (ClO4,), while (II) is a related mononuclear species, which has a distorted square-pyramidal geometry. [source] Synthesis, structural characterization and cytotoxic activity of diorganotin(IV) complexes of N -(5-halosalicylidene)tryptophaneAPPLIED ORGANOMETALLIC CHEMISTRY, Issue 1 2009Laijin Tian Abstract Four new diorganotin(IV) complexes of N -(5-halosalicylidene)tryptophane, R2Sn[5-X-2-OC6H3CHNCH(CH2Ind)COO] [Ind = 3-indolyl; R, X = Et, Cl (1); Et, Br(2); n -Bu, Cl (3); n -Bu, Br (4)], were synthesized and characterized by elemental analysis, IR and NMR (1H, 13C and 119Sn) spectra. The crystal structures of complexes 1,3 were determined by X-ray single crystal diffraction and showed that the tin atoms are in a distorted trigonal bipyramidal geometry and form five- and six-membered chelate rings with the tridentate ligand. Intermolecular weak interactions in 1,3 link molecules, respectively, into a two-dimensional array, a one-dimensional infinite chain and a one-dimensional double-chain supramolecular structure. Bioassay results of the compounds indicated that the dibutyltin complexes 3 and 4 have potent in vitro cytotoxic activity against two human tumor cell lines, CoLo205 and Bcap37, while the diethyltin complexes 1 and 2 display weak cytotoxic activity. Copyright © 2008 John Wiley & Sons, Ltd. [source] Terahertz pulsed imaging of basal cell carcinoma ex vivo and in vivoBRITISH JOURNAL OF DERMATOLOGY, Issue 2 2004V.P. Wallace Summary Background, Terahertz radiation lies between the infrared and microwave regions of the electromagnetic spectrum and can be used to excite large amplitude vibrational modes of molecules and probe the weak interactions between them. Terahertz pulsed imaging (TPI) is a noninvasive imaging technique that utilises this radiaton. Objectives, To determine whether TPI could differentiate between basal cell carcinoma (BCC) and normal tissue and to test whether it can help facilitate delineation of tumour margins prior to surgery. Methods, A portable TPI system was used in the clinic to image 18 BCCs ex vivo and five in vivo. Results, The diseased tissue showed a change in terahertz properties compared with normal tissue, manifested through a broadening of the reflected terahertz pulse. Regions of disease identified in the terahertz image correlated well with histology. Conclusions, This study has confirmed the potential of TPI to identify the extent of BCC in vivo and to delineate tumour margins. Further clinical study of TPI as a surgical tool is now required. [source] A Targeted Releasable Affinity Probe (TRAP) for In Vivo PhotocrosslinkingCHEMBIOCHEM, Issue 9 2009Ping Yan Dr. Abstract A protein TRAP: The in vivo photocrosslinking of TRAP after its intracellular targeting to a binding sequence on the bait protein stabilizes protein interactions. Because the crosslinker is releasable, simple mass spectrometry can be used to identify the protein binding sites after purification. Protein crosslinking, especially coupled to mass-spectrometric identification, is increasingly used to determine protein binding partners and protein,protein interfaces for isolated protein complexes. The modification of crosslinkers to permit their targeted use in living cells is of considerable importance for studying protein-interaction networks, which are commonly modulated through weak interactions that are formed transiently to permit rapid cellular response to environmental changes. We have therefore synthesized a targeted and releasable affinity probe (TRAP) consisting of a biarsenical fluorescein linked to benzophenone that binds to a tetracysteine sequence in a protein engineered for specific labeling. Here, the utility of TRAP for capturing protein binding partners upon photoactivation of the benzophenone moiety has been demonstrated in living bacteria and mammalian cells. In addition, ligand exchange of the arsenic,sulfur bonds between TRAP and the tetracysteine sequence to added dithiols results in fluorophore transfer to the crosslinked binding partner. In isolated protein complexes, this release from the original binding site permits the identification of the proximal binding interface through mass spectrometric fragmentation and computational sequence identification. [source] | |||||||||||||||||||||||||||||||