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Hydrogen-bonding Interactions (hydrogen-bonding + interaction)
Kinds of Hydrogen-bonding Interactions Selected AbstractsHydrogen-bonding interaction of an alternating maleic acid,vinyl acetate copolymer with poly(ethylene glycol), polyacrylamide and poly(N -isopropylacrylamide): a comparative studyPOLYMER INTERNATIONAL, Issue 12 2003C Vasile Abstract The hydrogen-bonding interaction and interpolymer complex formation between an alternating maleic acid,vinyl acetate copolymer, (MAc- alt -VA) and poly(ethylene glycol) (PEG), polyacrylamide (PAM) or poly(N -isopropylacrylamide) (PNIPAM) in aqueous solution was potentiometrically and viscometrically investigated. MAc- alt -VA formed with PEG a strong hydrogen-bonding interpolymer complex with a compact structure, and while its interaction with PAM seems to be very weak, if any, the complex formed with PNIPAM is even stronger than that with PEG. This indicates a very important contribution of hydrophobic interaction to the formation of such hydrogen-bonding interpolymer complexes. Copyright © 2003 Society of Chemical Industry [source] Hydrogen-bonding interaction between poly(,-caprolactone) and low-molecular-weight amino compoundsPOLYMER INTERNATIONAL, Issue 4 2001Takumi Watanabe Abstract The specific interactions between several low-molecular-weight diamino compounds and poly(,-caprolactone) (PCL) have been investigated by FT-IR. It was found that PCL and 3,3,-diaminodiphenylmethane (3,3,-DADPM) interact through strong intermolecular hydrogen bonds in the blend. Thermal and mechanical properties of PCL/3,3,-DADPM blends were investigated by DSC and tensile measurements, respectively. The glass transition temperature of the blend increases while both the melting point and the elongation-at-break of the blend decrease with the increase of 3,3,-DADPM content. Besides 3,3,-DADPM, several other low-molecular-weight compounds containing two amino groups, such as o -phenylenediamine or 1,6-diaminohexane, were also added into PCL and the corresponding blend systems were investigated by FT-IR and DSC. The effect of the chemical structure of the additives on the properties of PCL is discussed. © 2001 Society of Chemical Industry [source] Two-dimensional hydrogen-bonded networks in 1-(diaminomethylene)thiouron-1-ium nitrate and bis[1-(diaminomethylene)thiouron-1-ium] phosphonate monohydrateACTA CRYSTALLOGRAPHICA SECTION C, Issue 3 2009Jan Janczak Crystals of the title compounds, C2H7N4S+·NO3,, (I), and 2C2H7N4S+·HPO32,·H2O, (II), are built up from 1-(diaminomethylene)thiouron-1-ium cations and nitrate anions in (I), and from phosphonate anions and water molecules in (II). In both crystals, the cations and anions are linked together via N,H...O hydrogen bonds. The 1-(diaminomethylene)thiouron-1-ium cations exhibit a twisted conformation. Both arms of the cations are planar and are turned in opposite directions around the C,N bond involving the central N atom. Hydrogen-bonding interactions join oppositely charged units into layers in the nitrate salt and into double layers in the phosphonate monohydrate salt. In addition, the structures are stabilized by ,,, interactions between the delocalized , bonds of the cations. The significance of this study lies in the illustration of the differences between the supramolecular aggregations in the nitrate and phosphonate salts of a small organic molecule. The different geometries of the counter-ions and their different potential for hydrogen-bond formation results in markedly different hydrogen-bond arrangements. [source] Hydrogen-bonding interactions in (3,4-dimethoxyphenyl)acetic acid monohydrateACTA CRYSTALLOGRAPHICA SECTION C, Issue 7 2008Barbara Hachu The crystal structure of the title compound, C10H12O4·H2O, consists of (3,4-dimethoxyphenyl)acetic acid and water molecules linked by O,H...O hydrogen bonds to form cyclic structures with graph-set motifs R12(5) and R44(12). These hydrogen-bond patterns result in a three-dimensional network with graph-set motifs R44(20) and R44(22), and the formation of larger macrocycles, respectively. The C,C bond lengths and the endocyclic angles of the benzene ring show a noticeable asymmetry, which is connected with the charge-transfer interaction of the carboxyl or methoxy groups and the benzene ring. The title compound is one of the simple carboxylic acid systems that form hydrates. Thus, the significance of this study lies in the analysis of the interactions in this structure and the aggregations occurring via hydrogen bonds in two crystalline forms of (3,4-dimethoxyphenyl)acetic acid, namely the present hydrate and the anhydrous form [Chopra, Choudhury & Guru Row (2003). Acta Cryst. E59, o433,o434]. The correlation between the IR spectrum of this compound and its structural data are also discussed. [source] Hydrogen-bond-assisted stereocontrol in the radical polymerization of N -isopropylacrylamide with primary alkyl phosphate: The effect of the chain length of the straight ester groupJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 1 2005Tomohiro Hirano Abstract The radical polymerizations of N -isopropylacrylamide (NIPAAm) were carried out in toluene at low temperatures in the presence of phosphoric acid esters such as trimethyl phosphate, triethyl phosphate (TEP), tri- n -propyl phosphate, and tri- n -butyl phosphate (TBP). Syndiotactically rich poly(NIPAAm)s were obtained from ,60 to 0 °C, and TEP provided the highest syndiotacticity (racemo dyad = 65%) at ,40 °C. On the other hand, lowering the temperature reversed the stereoselectivity of the propagation reaction so that isotactically rich poly(NIPAAm)s were obtained at ,80 °C. In particular, TBP exhibited the most isotactic specificity (meso dyad = 57%). Job's plots for NIPAAm,TBP mixtures revealed that NIPAAm and TBP formed a 1:1 complex at 0 °C and a predominantly 1:2 complex at ,80 °C through a hydrogen-bonding interaction. Therefore, the stereospecificity of NIPAAm polymerization should depend on the stoichiometry of the hydrogen-bond-assisted complex. Thus, the mechanism for this polymerization system was discussed. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 50,62, 2005 [source] Effect of hydrogen-bonding interaction on radical polymerization of di- n -butyl itaconateJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 21 2003Tomohiro Hirano Radical polymerizations of di- n -butyl itaconate (DBI) were examined in the presence of amide compounds that could form a complex with DBI monomer via a hydrogen-bonding interaction. The use of amide compounds as solvents succeeded to suppress the intramolecular chain-transfer reaction significantly, whereas catalytic amounts of amide compounds were of little effect. It was also assumed that a hydrogen-bonding interaction plays an important role not only for suppression of the intramolecular chain-transfer reaction but for stereospecificity of polymerization. These results suggested that even a weak hydrogen-bonding interaction could be used for control of a radical polymerization reaction. [source] QSAR of Human Steroid 5,-Reductase Inhibitors: Where are the differences between isoenzyme type 1 and 2?MOLECULAR INFORMATICS, Issue 6 2004Michael Abstract Quantitative Structure Activity Relationships have been established for inhibitors of human steroid 5,-reductase including 6-azasteroids and non-steroidal compounds. From the applied descriptors, those related to the molecular geometry, electronic properties, and the electrostatic surface were derived from semi-empirical AM1 calculations. A chemical reaction as part of the inhibitory action is indicated by the presence of the ionization potential in the descriptor space. Strong similarities between the variables for the prediction of the binding affinity to the type 1 and IC50 values for the type 2 isoform of the 5,-reductase were observed. The most pronounced differences in the linear regression QSAR equations were found for the descriptors accounting for the hydrogen-bonding interaction, suggesting a different hydrogen-bonding pattern in the binding pocket of both isoforms. Furthermore, the topological indices together with the surface related descriptors point towards a lower content of aromatic amino acids in the binding site of the type 2 isoenzyme. Consequences for the design of new inhibitors are discussed. [source] Correlation between hydrogen-bonding interaction and mechanical properties of polyimide fibersPOLYMERS FOR ADVANCED TECHNOLOGIES, Issue 4 2009Xiangyang Liu Abstract Novel co-polymerization polyimide (PI) fibers based on 4,4,-oxydianiline (ODA)-pyromellitic dianhydride (PMDA) were prepared. 2-(4-Aminophenyl)-5-aminobenzimidazole (PABZ) containing the NH group was introduced into the structure of the fibers as the proton donor. The results of Fourier transform infrared (FTIR) and dynamic mechanical analysis (DMA) showed that hydrogen bonding occured between the NH group and chains, which strongly enhanced interchain interaction. This hydrogen bonding interaction increased the tensile strength and initial modulus of the PI fibers up to 2.5 times and 26 times, respectively, compared to those of homo-PI PMDA-ODA fibers with no hydrogen-bonding interaction because of the absence of proton donors after the imidization process. In the mean time, glass transition temperature (Tg) of the modified PI fibers was found to be 410,440°C, which was higher than that of the homo-PI PMDA-ODA fibers. From the result, a novel access to molecular design and manufacture of high performance PI fibers with good properties could be provided. Copyright © 2009 John Wiley & Sons, Ltd. [source] The study of the miscibility and morphology of poly(styrene-co-4-vinylphenol)/poly(propylene carbonate) blendsPOLYMERS FOR ADVANCED TECHNOLOGIES, Issue 8 2004Furong Qiu Abstract Blends of poly(propylene carbonate) (PPC) with copolymer poly(styrene-co-4-vinyl phenol) (STVPh) have been studied by electron spin resonance (ESR) spin probe method and Raman spectroscopy. The ESR results indicated that the nitroxide radical existed in a PPC-rich and an STVPh-rich micro domain in the blends, corresponding to the fast-motion and slow-motion component in the ESR spectra, respectively. And in the temperature dependence composite spectra, the fast-motion fraction increased with increasing the hydroxyl group content in copolymer STVPh. Moreover, the ESR parameter T5mT, rotational correlation times (,c) and activation energies (Ea) showed similar dependence on the hydroxyl group content as the fast-motion fraction. It resulted from the enhancement of the hydrogen-bonding interaction between the hydroxyl groups in STVPh and the carboxyl groups and ether oxygen in PPC. However, the distinct band shift and intensity change among the Raman spectra of pure polymer components and those of the blends were observed. In the carboxyl-stretching region, the band shifted to lower frequency with increasing the hydroxyl groups. Furthermore, the phase morphologies of the blends were obtained by optical microscopy. All could be concluded that the hydrogen-bonding interaction between the two components was progressively favorable to the mixing process and was the driving force for the miscibility enhancement in the blends. Copyright © 2004 John Wiley & Sons, Ltd. [source] Combinatorial engineering to enhance thermostability of amylosucrasePROTEIN SCIENCE, Issue 6 2008Stéphane Emond Abstract Amylosucrase is a transglucosidase that catalyzes amylose-like polymer synthesis from sucrose substrate. About 60,000 amylosucrase variants from two libraries generated by the MutaGen random mutagenesis method were submitted to an in vivo selection procedure leading to the isolation of more than 7000 active variants. These clones were then screened for increased thermostability using an automated screening process. This experiment yielded three improved variants (two double mutants and one single mutant) showing 3.5- to 10-fold increased half-lives at 50°C compared to the wild-type enzyme. Structural analysis revealed that the main differences between wild-type amylosucrase and the most improved variant (R20C/A451T) might reside in the reorganization of salt bridges involving the surface residue R20 and the introduction of a hydrogen-bonding interaction between T451 of the B, domain and D488 of flexible loop 8. This double mutant is the most thermostable amylosucrase known to date and the only one usable at 50°C. At this temperature, amylose synthesis by this variant using high sucrose concentration (600 mM) led to the production of amylose chains twice as long as those obtained by the wild-type enzyme at 30°C. [source] Crystallographic characterization of the first reported crystalline form of the potent hallucinogen (R)-2-amino-1-(8-bromobenzo[1,2- b;5,4- b,]difuran-4-yl)propane or `bromodragonfly': the 1:1 anhydrous proton-transfer compound with 3,5-dinitrosalicylic acidACTA CRYSTALLOGRAPHICA SECTION C, Issue 5 2010Graham Smith The 1:1 proton-transfer compound of the potent substituted amphetamine hallucinogen (R)-2-amino-1-(8-bromobenzo[1,2- b;5,4- b,]difuran-4-yl)propane (common trivial name `bromodragonfly') with 3,5-dinitrosalicylic acid, namely 1-(8-bromobenzo[1,2- b;5,4- b,]difuran-4-yl)propan-2-aminium 2-carboxy-4,6-dinitrophenolate, C13H13BrNO2+·C7H3N2O7,, forms hydrogen-bonded cation,anion chain substructures comprising undulating head-to-tail anion chains formed through C(8) carboxyl,nitro O,H...O associations and incorporating the aminium groups of the cations. The intrachain cation,anion hydrogen-bonding associations feature proximal cyclic R33(8) interactions involving both an N+,H...Ophenolate and the carboxyl,nitro O,H...O associations and aromatic ,,, ring interactions [minimum ring centroid separation = 3.566,(2),Å]. A lateral hydrogen-bonding interaction between the third aminium H atom and a carboxyl O-atom acceptor links the chain substructures, giving a two-dimensional sheet structure. This determination represents the first of any form of this compound and is in the (R) absolute configuration. The atypical crystal stability is attributed both to the hydrogen-bonded chain substructures provided by the anions, which accommodate the aminium proton-donor groups of the cations and give crosslinking, and to the presence of the cation,anion aromatic ring ,,, interactions. [source] Three-dimensional hydrogen-bonded structures in the 1:1 proton-transfer compounds of l -tartaric acid with the associative-group monosubstituted pyridines 3-aminopyridine, 3-carboxypyridine (nicotinic acid) and 2-carboxypyridine (picolinic acid)ACTA CRYSTALLOGRAPHICA SECTION C, Issue 1 2010Graham Smith The 1:1 proton-transfer compounds of l -tartaric acid with 3-aminopyridine [3-aminopyridinium hydrogen (2R,3R) -tartrate dihydrate, C5H7N2+·C4H5O6,·2H2O, (I)], pyridine-3-carboxylic acid (nicotinic acid) [anhydrous 3-carboxypyridinium hydrogen (2R,3R)-tartrate, C6H6NO2+·C4H5O6,, (II)] and pyridine-2-carboxylic acid [2-carboxypyridinium hydrogen (2R,3R)-tartrate monohydrate, C6H6NO2+·C4H5O6,·H2O, (III)] have been determined. In (I) and (II), there is a direct pyridinium,carboxyl N+,H...O hydrogen-bonding interaction, four-centred in (II), giving conjoint cyclic R12(5) associations. In contrast, the N,H...O association in (III) is with a water O-atom acceptor, which provides links to separate tartrate anions through Ohydroxy acceptors. All three compounds have the head-to-tail C(7) hydrogen-bonded chain substructures commonly associated with 1:1 proton-transfer hydrogen tartrate salts. These chains are extended into two-dimensional sheets which, in hydrates (I) and (III) additionally involve the solvent water molecules. Three-dimensional hydrogen-bonded structures are generated via crosslinking through the associative functional groups of the substituted pyridinium cations. In the sheet struture of (I), both water molecules act as donors and acceptors in interactions with separate carboxyl and hydroxy O-atom acceptors of the primary tartrate chains, closing conjoint cyclic R44(8), R34(11) and R33(12) associations. Also, in (II) and (III) there are strong cation carboxyl,carboxyl O,H...O hydrogen bonds [O...O = 2.5387,(17),Å in (II) and 2.441,(3),Å in (III)], which in (II) form part of a cyclic R22(6) inter-sheet association. This series of heteroaromatic Lewis base,hydrogen l -tartrate salts provides further examples of molecular assembly facilitated by the presence of the classical two-dimensional hydrogen-bonded hydrogen tartrate or hydrogen tartrate,water sheet substructures which are expanded into three-dimensional frameworks via peripheral cation bifunctional substituent-group crosslinking interactions. [source] Poly[[aqua(4,4,-diazenediyldibenzoato-,4O,O,:O,,,O,,,)cadmium(II)]: a twofold interpenetrated three-dimensional coordination polymer of PtS topologyACTA CRYSTALLOGRAPHICA SECTION C, Issue 10 2009Ru-Guo Wang In the title coordination compound, [Cd(C14H8N2O4)(H2O)]n, the CdII cation and the coordinated water molecule lie on a twofold axis, whereas the ligand lies on an inversion center. The CdII center is five-coordinated in a distorted square-pyramidal geometry by four carboxylate O atoms from four different 4,4,-diazenediyldibenzoate (ddb) anions and one water O atom. The three-dimensional frameworks thus formed by the bridging ddb anions interpenetrate to generate a three-dimensional PtS-type network. Additionally, the coordination water molecule and the carboxylate O atom form a hydrogen-bonding interaction, stabilizing the three-dimensional framework structure. [source] Proton transfer versus nontransfer in compounds of the diazo-dye precursor 4-(phenyldiazenyl)aniline (aniline yellow) with strong organic acids: the 5-sulfosalicylate and the dichroic benzenesulfonate salts, and the 1:2 adduct with 3,5-dinitrobenzoic acidACTA CRYSTALLOGRAPHICA SECTION C, Issue 10 2009Graham Smith The structures of two 1:1 proton-transfer red,black dye compounds formed by reaction of aniline yellow [4-(phenyldiazenyl)aniline] with 5-sulfosalicylic acid and benzenesulfonic acid, and a 1:2 nontransfer adduct compound with 3,5-dinitrobenzoic acid have been determined at either 130 or 200,K. The compounds are 2-(4-aminophenyl)-1-phenylhydrazin-1-ium 3-carboxy-4-hydroxybenzenesulfonate methanol solvate, C12H12N3+·C7H5O6S,·CH3OH, (I), 2-(4-aminophenyl)-1-phenylhydrazin-1-ium 4-(phenyldiazenyl)anilinium bis(benzenesulfonate), 2C12H12N3+·2C6H5O3S,, (II), and 4-(phenyldiazenyl)aniline,3,5-dinitrobenzoic acid (1/2), C12H11N3·2C7H4N2O6, (III). In compound (I), the diazenyl rather than the aniline group of aniline yellow is protonated, and this group subsequently takes part in a primary hydrogen-bonding interaction with a sulfonate O-atom acceptor, producing overall a three-dimensional framework structure. A feature of the hydrogen bonding in (I) is a peripheral edge-on cation,anion association also involving aromatic C,H...O hydrogen bonds, giving a conjoint R12(6)R12(7)R21(4) motif. In the dichroic crystals of (II), one of the two aniline yellow species in the asymmetric unit is diazenyl-group protonated, while in the other the aniline group is protonated. Both of these groups form hydrogen bonds with sulfonate O-atom acceptors and these, together with other associations, give a one-dimensional chain structure. In compound (III), rather than proton transfer, there is preferential formation of a classic R22(8) cyclic head-to-head hydrogen-bonded carboxylic acid homodimer between the two 3,5-dinitrobenzoic acid molecules, which, in association with the aniline yellow molecule that is disordered across a crystallographic inversion centre, results in an overall two-dimensional ribbon structure. This work has shown the correlation between structure and observed colour in crystalline aniline yellow compounds, illustrated graphically in the dichroic benzenesulfonate compound. [source] 4,-[2-(2-Ethoxyethoxy)ethoxy]biphenyl-4-carboxylic acid: correlation between its crystalline and smectic phasesACTA CRYSTALLOGRAPHICA SECTION C, Issue 3 2009Rosana S. Montani The crystal structure of the dimeric title compound, C19H22O5, is dominated by a head-to-head hydrogen-bonding interaction between centrosymmetrically related carboxyl groups in each monomer. The result is a dimeric axis of unusual length (ca 34,Å), but still shorter than what could be expected for a fully extended chain, owing to two turning points in the oligoethoxy ends. This allows for an explanation of the structure of the smectic mesophase exhibited by this compound and at the same time fully validates former geometric estimations based on PM3 calculations. [source] Noncovalent Modulation of pH-Dependent Reactivity of a Mn,Salen Cofactor in Myoglobin with Hydrogen PeroxideCHEMISTRY - A EUROPEAN JOURNAL, Issue 30 2009Jun-Long Zhang Dr. Abstract To demonstrate protein modulation of metal-cofactor reactivity through noncovalent interactions, pH-dependent sulfoxidation and 2,2,-azino-bis(3-ethylbenzthiazoline-6-sulphonic acid) (ABTS) oxidation reactivity of a designed myoglobin (Mb) containing non-native Mn,salen complex (1) was investigated using H2O2 as the oxidant. Incorporation of 1 inside the Mb resulted in an increase in the turnover numbers through exclusion of water from the metal complex and prevention of Mn,salen dimer formation. Interestingly, the presence of protein in itself is not enough to confer the increase activity as mutation of the distal His64 in Mb to Phe to remove hydrogen-bonding interactions resulted in no increase in the turnover numbers, while mutation His64 to Arg, another residue with ability to hydrogen-bond interactions, resulted in an increase in reactivity. These results strongly suggest that the distal ligand His64, through its hydrogen-bonding interaction, plays important roles in enhancing and fine-tuning reactivity of the Mn,salen complex. Nonlinear least-squares fitting of rate versus pH plots demonstrates that 1,Mb(H64X) (X=H, R and F) and the control Mn,salen 1 exhibit pKa values varying from pH,6.4 to 8.3, and that the lower pKa of the distal ligand in 1,Mb(H64X), the higher the reactivity it achieves. Moreover, in addition to the pKa at high pH, 1,Mb displays another pKa at low pH, with pKa of 5.0±0.08. A comparison of the effect of different pH on sulfoxidation and ABTS oxidation indicates that, while the intermediate produced at low pH conditions could only perform sulfoxidation, the intermediate at high pH could oxidize both sulfoxides and ABTS. Such a fine-control of reactivity through hydrogen-bonding interactions by the distal ligand to bind, orient and activate H2O2 is very important for designing artificial enzymes with dramatic different and tunable reactivity from catalysts without protein scaffolds. [source] Platinum(IV) Complexes of 3- and 4-Picolinic Acids Containing Ammine or Isopropylamine Ligands , Synthesis, Characterization, X-ray Structures, and Evaluation of Their Cytotoxic Activity against Cancer Cell Lines,EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 30 2008María J. Macazaga Abstract The preparation and characterization of the new complexes trans -[PtCl4(NH3)(3-picolinic acid)] (1), trans -[PtCl4{NH2CH(CH3)2}(3-picolinic acid)] (2), trans -[PtCl4(NH3)(4-picolinic acid)] (3), and trans -[PtCl4{NH2CH(CH3)2}(4-picolinic acid)] (4) are described. The main structural feature of these complexes is the presence of ligands capable of multiple hydrogen-bonding interactions. Crystals of 1, 2, 3, and 4 suitable for single-crystal X-ray diffraction were grown, and the molecular structures of these compounds are discussed. In contrast to the inactive parent PtII complexes, the PtIV complexes displayed cytotoxic activity against various cancer cell lines used at the National Cancer Institute (NCI) for in vitro screens. Once more, the isopropylamine derivatives showed the best cytotoxicity values. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008) [source] Mixed-Ligand Oxidovanadium(V) Complexes with N, -Salicylidenehydrazides: Synthesis, Structure, and 51V Solid-State MAS NMR Investigation,EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 14 2008Simona Nica Abstract The synthesis and spectroscopic characterization of a series of three oxidovanadium(V) complexes with 8-hydroxyquinoline and Schiff-base ligands derived from salicylaldehyde and ,-hydroxy-functionalized carbohydrazides with different chain lengths are reported. The complex with the hydrazone ligand containing the shortest chain length was crystallographically characterized. This complex crystallizes in the triclinic space group P with two structurally similar but crystallographically independent oxidovanadium(V) complexes. Each vanadium atom is six-coordinate in a distorted-octahedral geometry. The two molecules are assembled through hydrogen-bonding interactions between the hydroxyl groups of the side-chain substituted Schiff-base ligand and the oxido group of one of the two complexes. Electrochemical measurements performed in acetonitrile solution reveal two reversible one-electron reduction steps. The observed pre-wave feature of the second reduction step indicates the presence of dissociation equilibria related to the 8-hydroxyquinoline coligand. Magic-angle spinning solid-state 51V NMR spectroscopy allowed to characterize the full series of complexes with alkyl and hydroxy alkyl-substituted hydrazone ligands that were used. The quadrupolar coupling constants are small with a value of about 4 MHz and show little variation within the series. The asymmetry of the chemical shift tensor indicates a rather axial symmetric environment around the vanadium(V) center. The isotropic chemical shifts observed in the solid state occur at about 30 ppm, which is in the same order of magnitude as the solvent induced variations, about 10 ppm, found for different solvents.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008) [source] Hexaazamacrocycle Containing Pyridine and Its Dicopper Complex as Receptors for Dicarboxylate AnionsEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 22 2005Feng Li Abstract The host,guest binding interactions of the hexaazamacrocycle [26]py2N4, in its tetraprotonated form H4[26]py2N44+ as well as in its dicopper(II) complex [Cu2([26]py2N4)(H2O)4]4+, with dicarboxylate anions of different stereoelectronicrequirements, such as oxalate (ox2,), malonate (mal2,), succinate (suc2,), fumarate (fu2,) and maleate (ma2,), were evaluated. The association constants were determined using potentiometric methods in aqueous solution, at 298.0 K and 0.10 mol·dm,3 KCl. These values for the tetraprotonated ditopic receptor with the dicarboxylate anions revealed that the main species in solution corresponds to the formation of {H4[26]py2N4(A)}2+ (pH , 4,9), A being the substrate anion. The values determined are not especially high, but the receptor exhibits selectivity for the malonate anion. The study of the cascade complexes revealed several species in solution, involving mononuclear and dinuclear complexes, mainly protonated and hydrolysed species, as well as the expected complexes [Cu2([26]py2N4)(A)(H2O)x]2+ or [Cu2([26]py2N4)(A)2(H2O)y]. Ox2, and mal2, form cascade complexes with only one anion, which will necessarily bridge the two copper atoms because of the symmetrical arrangement of the dinuclear complex. The two other studied anions, suc2, and ma2,, form species involving two substrate anions, although species with only one suc2, anion were also found. UV/Vis and EPR spectroscopy have shown that the dicopper complex can operate as a sensor to detect and quantitatively determine oxalate spectrophotometrically because of the red shift of the maximum of the visible band observed by addition of ox2, to an aqueous solution of the dinuclear copper complex. However the selectivity of [Cu2([26]py2N4)(H2O)4]4+ as a receptor for ox2, in the studied series is not sufficiently high to detect ox2, spectrophotometrically in the presence of the other anions. Molecular dynamics simulations indicated that the H4[26]py2N44+ receptor provides a large and flexible cavity to accommodate the studied anions. Molecular recognition is based in electrostatic interactions rather than in multiple hydrogen-bonding interactions acting cooperatively. By contrast, the [Cu2([26]py2N4)]4+ receptor has a well-shaped cavity with adequate size to uptake these anions as bridging ligands with formation of four Cu,O bonds. The ox2, anion is encapsulated within the cascade complex while the remaining anions are located above the N6 macrocyclic plane, suggesting a selective coordination behaviour of this receptor. In spite of our molecular simulation being carried out in gas phase, the modelling results are consistent with the solution studies. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005) [source] Synthesis, Crystal Structure and Characterisation of a Novel Chiral Mixed-Valence Vanadium Oxide Hybrid, [V5O11(dien)3]EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 15 2005Ming-Lai Fu Abstract The novel chiral mixed-valence vanadium oxide hybrid [V5O11(dien)3] (1) (dien = NH2C2H4NHC2H4NH2) has been synthesised by a hydrothermal reaction of V2O5 and dien in aqueous solution and characterised by elemental analysis, IR spectroscopy, TG-DSC analysis, magnetism, EPR spectroscopy, single-crystal X-ray diffraction and powder XRD. The X-ray diffraction analysis revealed that the structure of 1 can be regarded as being constructed from two [VVO4]3, groups bicapping three [VIVO(dien)]2+ units to form a discrete asymmetric pentanuclear vanadium complex with the dien ligands coordinating directly to the vanadium(IV) centres. Compound 1 exhibits an interesting tube-like 3D supramolecular structure due to abundant hydrogen-bonding interactions between the oxygen atoms of the inorganic backbone and the hydrogen atoms of the dien ligands from adjacent molecules. The variable-temperature magnetic susceptibility data of 1 suggest a weak ferromagnetic interaction among V4+ ions in the cluster. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005) [source] (Pyrazole)silver(I) and -gold(I) Complexes with Strong and Weak Hydrogen-Bonding Interactions as the Basis of One- or Two-Dimensional StructuresEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 15 2004M. Luz Gallego Abstract New AuI/AgI complexes containing one or two substituted pyrazole ligands [Au(Hpzbp2)(PPh3)](p -CH3C6H4SO3) [Hpzbp2 = 3,5-bis(4- n -butoxyphenyl)pyrazole] (1) and [M(HpzR2)2]nX [HpzR2 = Hpzbp2, M = Au, n = 1, X = p -CH3C6H4SO3 (2), NO3, (3); n = 2, X = 1,5-naphthalenedisulfonate (1,5nds) (4); HpzR2 = Hpzbp2, M = Ag, n = 1, X = BF4, (5), CF3SO3, (6); HpzR2 = HpzNO2 (3,5-dimethyl-4-nitropyrazole), M = Ag, n = 1, X = BF4, (7), CF3SO3, (8)], have been prepared and characterized. Compounds 1, 2, 5 and 8 have been proved to be useful for supramolecular assembly from their single X-ray diffraction analysis. In all cases strong hydrogen bonds maintain the cationic units bonded to their corresponding counterions. The crystal packing arrangement of 1, 2 and 5 is, however, determined by weak C,H···O/F hydrogen-bonding interactions involving the remaining O/F atoms of the counterion. By contrast, for 8 a two-dimensional layer-type polymeric network is formed by ,···, (NO2···NO2) and coordinative Ag···O interactions in which the NO2 substituent on the pyrazole is implicated. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004) [source] Designing Ionic Liquids: 1-Butyl-3-Methylimidazolium Cations with Substituted Tetraphenylborate CounterionsEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 15 2003Joep van den Broeke Abstract The hydrophobic, low melting, 1-butyl-3-methylimidazolium (BMIm) salts [BMIm][BPh4] (1), [BMIm][B(C6H4Me-4)4] (2), [BMIm][B{C6H4(CF3)-4}4] (3), [BMIm][B{C6H3(CF3)2 -3,5}4] (4), [BMIm][B{C6H4(C6F13)-4}4] (5), [BMIm][B{C6H4(SiMe3)-4}4] (6), [BMIm][B(C6H4{SiMe2(CH2CH2CF3)}-4)4] (7), [BMIm][B{C6H4(SiMe2C8H17}-4}4] (8) and [BMIm][B(C6H4{SiMe2(CH2CH2C6F13)}-4)4] (9) have been prepared. Systematic variation of the substituents on the tetraphenylborate anion allowed an assessment of their influence on the physical properties of the imidazolium salts. Structural investigations using NMR and IR spectroscopy, combined with single crystal X-ray structure determinations for 2, 3, 5 and 6, revealed hydrogen-bonding interactions between the imidazolium ring protons and the borate anion, both in the solid state and in solution. These interactions are weakened upon the introduction of electron-withdrawing substituents in the anion and follow the order 3,5-(CF3)2 < ,C6F13 < ,CF3 < ,SiMe2CH2CH2C6F13 < ,SiMe2CH2CH2CF3 < ,H < ,Me < ,SiMe3. The melting points of the salts depend primarily on the bulk of the lipophilic substituents, and decrease with increasing size. Bulky lipophilic substituents dramatically enhance the solubility of the imidazolium borates 8 and 9 in hexane and reduce their relative polarity. These unique properties make imidazolium borates 8 and 9 interesting as amphiphilic ionic liquids with low polarity. Attempts to crystallise 7 resulted in decomposition. A single-crystal X-ray structure determination of the product, isolated in 6% yield, showed that a carbene,tris[4-{dimethyl(3,3,3-trifluoropropyl)silyl}phenyl]borane adduct was formed. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003) [source] Calix[4]arene-Based Chromogenic Chemosensor for the ,-Phenylglycine Anion: Synthesis and Chiral RecognitionEUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 6 2006Guang-Yan Qing Abstract Calix[4]arene-based two-armed chiral anion receptors 3a and 3b have been synthesized and examined for their chiral anion-binding abilities by UV/Vis absorption and 1H NMR spectroscopy. The results of nonlinear curve fitting indicate that 3a and 3b form 1:1 stoichiometric complexes with the L - or D -,-phenylglycine anion by multiple hydrogen-bonding interactions and exhibit good enantioselective recognition for the enantiomers of the ,-phenylglycine anions (3a: Kass(L)/Kass(D) = 4.76; 3b: Kass(D)/Kass(L) = 2.84). The marked colour changes observed for the complexation of 3a with the chiral anions and the good enantioselective recognition reveal that receptor 3a could be used as a good chiral chromogenic chemosensor for the enantiomers of the ,-phenylglycine anion. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006) [source] Dual Stimuli-Responsive Supramolecular Polypeptide-Based Hydrogel and Reverse Micellar Hydrogel Mediated by Host,Guest ChemistryADVANCED FUNCTIONAL MATERIALS, Issue 4 2010Yi Chen Abstract Versatile strategies are currently being discovered for the fabrication of synthetic polypeptide-based hybrid hydrogels, which have potential applications in polymer therapeutics and regenerative medicine. Herein, a new concept,the reverse micellar hydrogel,is introduced, and a versatile strategy is provided for fabricating supramolecular polypeptide-based normal micellar hydrogel and reverse micellar hydrogels from the same polypeptide-based copolymer via the cooperation of host,guest chemistry and hydrogen-bonding interactions. The supramolecular hydrogels are thoroughly characterized, and a mechanism for their self-assembly is proposed. These hydrogels can respond to dual stimuli,temperature and pH,and their mechanical and controlled drug-release properties can be tuned by the copolymer topology and the polypeptide composition. The reverse micellar hydrogel can load 10% of the anticancer drug doxorubicin hydrochloride (DOX) and sustain DOX release for 45 days, indicating that it could be useful as an injectable drug delivery system. [source] Synthesis and characterization of a cured epoxy resin with a benzoxazine monomer containing allyl groupsJOURNAL OF APPLIED POLYMER SCIENCE, Issue 6 2010Shiao-Wei Kuo Abstract Vinyl-terminated benzoxazine (VB-a), which can be polymerized through ring-opening polymerization, was synthesized through the Mannich condensation of bisphenol A, formaldehyde, and allylamine. This VB-a monomer was then blended with epoxy resin and then concurrently thermally cured to form an epoxy/VB-a copolymer network. To understand the curing kinetics of this epoxy/VB-a copolymer, dynamic differential scanning calorimetry measurements were performed by the Kissinger and Flynn,Wall,Ozawa methods. Fourier transform infrared (FTIR) analyses revealed the presence of thermal curing reactions and hydrogen-bonding interactions of the epoxy/VB-a copolymers. Meanwhile, a significant enhancement of the ring-opening and allyl polymerizations of the epoxy was observed. For these interpenetrating polymer networks, dynamic mechanical analysis and thermogravimetric analysis results indicate that the thermal properties increased with increasing VB-a content in the epoxy/VB-a copolymers. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010 [source] How resonance assists hydrogen bonding interactions: An energy decomposition analysisJOURNAL OF COMPUTATIONAL CHEMISTRY, Issue 1 2007John Frederick Beck Abstract Block-localized wave function (BLW) method, which is a variant of the ab initio valence bond (VB) theory, was employed to explore the nature of resonance-assisted hydrogen bonds (RAHBs) and to investigate the mechanism of synergistic interplay between , delocalization and hydrogen-bonding interactions. We examined the dimers of formic acid, formamide, 4-pyrimidinone, 2-pyridinone, 2-hydroxpyridine, and 2-hydroxycyclopenta-2,4-dien-1-one. In addition, we studied the interactions in ,-diketone enols with a simplified model, namely the hydrogen bonds of 3-hydroxypropenal with both ethenol and formaldehyde. The intermolecular interaction energies, either with or without the involvement of , resonance, were decomposed into the Hitler-London energy (,EHL), polarization energy (,Epol), charge transfer energy (,ECT), and electron correlation energy (,Ecor) terms. This allows for the examination of the character of hydrogen bonds and the impact of , conjugation on hydrogen bonding interactions. Although it has been proposed that resonance-assisted hydrogen bonds are accompanied with an increasing of covalency character, our analyses showed that the enhanced interactions mostly originate from the classical dipole,dipole (i.e., electrostatic) attraction, as resonance redistributes the electron density and increases the dipole moments in monomers. The covalency of hydrogen bonds, however, changes very little. This disputes the belief that RAHB is primarily covalent in nature. Accordingly, we recommend the term "resonance-assisted binding (RAB)" instead of "resonance-assisted hydrogen bonding (RHAB)" to highlight the electrostatic, which is a long-range effect, rather than the electron transfer nature of the enhanced stabilization in RAHBs. © 2006 Wiley Periodicals, Inc. J Comput Chem 28: 455,466, 2007 [source] Determination of cubic equation of state parameters for pure fluids from first principle solvation calculationsAICHE JOURNAL, Issue 8 2008Chieh-Ming Hsieh Abstract A new method for estimation of parameters in cubic equations of state from ab initio solvation calculations is presented. In this method, the temperature-dependent interaction parameter a(T) is determined from the attractive component of solvation free energy, whereas the volume parameter b is assumed to be that of solvation cavity. This method requires only element-specific parameters, i.e., atomic radius and dispersion coefficient, and nine universal parameters for electrostatic and hydrogen-bonding interactions. The equations of state (EOS) parameters so determined allow the description of the complete fluid phase diagram, including the critical point. We have examined this method using the Peng,Robinson EOS for 392 compounds and achieved an accuracy of 43% in vapor pressure, 17% in liquid density, 5.4% in critical temperature, 11% in critical pressure, and 4% in critical volume. This method is, in principle, applicable to any chemical species and is especially useful for those whose experimental data are not available. © 2008 American Institute of Chemical Engineers AIChE J, 2008 [source] Drug,polymer interaction and its significance on the physical stability of nifedipine amorphous dispersion in microparticles of an ammonio methacrylate copolymer and ethylcellulose binary blendJOURNAL OF PHARMACEUTICAL SCIENCES, Issue 1 2008Jingjun Huang Abstract Using spectroscopic and thermal analysis, this study investigated drug,polymer interaction and its significance on the physical stability of drug amorphous dispersion in microparticles of an ammonio polymethacrylate copolymer (Eudragit RL®) (RL) and ethylcellulose (EC) binary blend (RL/EC,=,2:1 w/w) prepared for use in controlled release of poorly water-soluble drugs. Solid dispersion of the model drug, nifedipine in the microparticles could be described as an ideal amorphous mixture for drug loadings up to 11% w/w. The antiplasticizing effect of the polymer blend was indicated by a significant increase in the glass transition point from ,50°C for the amorphous nifedipine to ,115°C for its solid solution. Moreover, shifts in infrared vibration wavenumber of nifedipine carbonyl and amine groups suggested that the hydrogen bonds (H-bonds) originally formed among nifedipine molecules were broken and replaced by those formed between nifedipine and polymers in the microparticles. Further infrared analysis on nifedipine amorphous dispersions with a single polymer, namely RL or EC, confirmed the proposed hydrogen-bonding interactions; and their stability study results suggested that both antiplasticizing effects and hydrogen bonding of EC and RL with nifedipine might be responsible for the physical stability of the microparticles of nifedipine amorphous dispersion with a RL/EC binary blend. © 2007 Wiley-Liss, Inc. and the American Pharmacists Association J Pharm Sci 97:251,262, 2008 [source] Preparation of oligoamide-ended poly(ethylene glycol) and hydrogen-bonding-assisted formation of aggregates and nanoscale fibersJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 5 2005Fengjun Hua Abstract An oligoamide-ended poly(ethylene glycol) (PEG) with a PEG weight-average molecular weight of 5000 (PEG-5000-oligoamide), with 3,5-bis-[2-(5-acetylamino-2-isobutoxy-benzoylamino)-acetylamino]-benzoyl as the oligoamide, was synthesized. PEG-5000-oligoamide aggregated in chloroform or toluene via hydrogen-bonding interactions among the oligoamide strands as a core and PEG, which was soluble in the solvents, as a shell. When a chloroform solution of PEG-5000-oligoamide at a concentration of approximately 0.06 g/L was cast onto a silicon wafer or a mica plate, rapid solvent evaporation induced its self reassembly as nanofibers. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 1119,1128, 2005 [source] Comparison of Raman spectroscopic methods for the determination of supercooled and liquid water temperatureJOURNAL OF RAMAN SPECTROSCOPY, Issue 8 2005Dubravko Risovi Abstract Raman spectroscopy provides an efficient method for non-contact determination of liquid water temperature with high spatial resolution. It can be also used for remote in situ determination of subsurface water temperature. The method is based on temperature-dependent changes of the molecular OH stretching band in the Raman spectra of liquid water. These in turn are attributed to a decrease in intermolecular hydrogen-bonding interactions with increase in temperature. Here, the results of an experimental study employing three different approaches in the determination of temperature from recorded OH stretching band in the Raman spectra of liquid and supercooled water are presented and discussed. The first two methods are based on deconvolution of the spectral band into Gaussian components whose intensities and associated specific spectral markers are temperature dependent, and the third approach is based on Raman difference spectroscopy (RDS). The presented measurements were conducted on distilled and deionized supercooled and liquid water in the temperature range between ,12.5 and +32.5 °C. The results are compared in terms of linearity of response, sensitivity and accuracy. It is shown that the method based on RDS even in the supercooled temperature range provides better accuracy (the standard deviation from the true temperature is ±0.4 K) and linearity in temperature determination than more complicated methods based on Gaussian deconvolution of the OH stretching band. Copyright © 2005 John Wiley & Sons, Ltd. [source] | |||||||||||||