NMR Spectroscopic (nmr + spectroscopic)

Distribution by Scientific Domains

Terms modified by NMR Spectroscopic

  • nmr spectroscopic analysis
  • nmr spectroscopic data
  • nmr spectroscopic experiment
  • nmr spectroscopic investigation
  • nmr spectroscopic methods
  • nmr spectroscopic studies
  • nmr spectroscopic study
  • nmr spectroscopic techniques

  • Selected Abstracts

    Crystal Structure, Solid-State NMR Spectroscopic and Photoluminescence Studies of Organic-Inorganic Hybrid Materials (HL)6[Ge6(OH)6(hedp)6]2(L)nH2O, L = hqn or phen,

    Lus Mafra
    Abstract Two germanium,hedp4, solids with heteroaromatic amines 8-hydroxyquinoline (hqn) and 1,10-phenanthroline (phen), (HL)6[Ge6(OH)6(hedp)6]2(L)nH2O (L = hqn or phen), in I and II respectively, have been prepared and characterised by single-crystal XRD, thermogravimetry, FTIR and UV/Vis spectroscopy. The complex hydrogen-bond networks, particularly in compound I, have been studied by advanced high-resolution solid-state NMR spectroscopy that combines homonuclear recoupling techniques (two-dimensional 1H- 1H DQF and 1H- 1H RFDR MAS NMR) and combined rotation and multiple-pulse spectroscopy (two-dimensional 1H- 1H FS-LG, 1H- 31P FS-LG). The fine details of the crystal structure of I have been elucidated, mainly those involving the ,,, stacking of 8-hydroxyquinoline and the relative orientation of adjacent such molecules. Compound II exhibits an emission from the lowest triplet-state energy (,,,* 0-phonon transition) of the aromatic rings at 320 nm (31250 cm,1) from 14 K to room temperature. In contrast, the triplet emission of I at 530 nm (18868 cm,1) is only detected at low temperature, because of thermally activated non-radiative mechanisms. The emission spectra of I and II display a lower-energy component with a larger life time, which results from the formation of an excimer state that originated from the ,,, phenanthroline and hydroxyquinoline interactions, respectively. ( Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006) [source]

    Comparative Solution Equilibrium Study of the Interactions of Copper(II), Iron(II) and Zinc(II) with Triapine (3-Aminopyridine-2-carbaldehyde Thiosemicarbazone) and Related Ligands

    va A. Enyedy
    Abstract The interactions of CuII, ZnII and FeII with Triapine (3-aminopyridine-2-carbaldehyde thiosemicarbazone), which is currently undergoing phase II clinical trials as a chemotherapeutic antitumour agent, were investigated in a water/DMSO mixture. The proton-dissociation constants of the ligands, the stability constants and the coordination modes of the metal complexes formed were determined by pH-potentiometric, UV/Vis spectrophotometric, EPR, 1H NMR spectroscopic and ESI-MS methods. Two N-terminally dimethylated derivatives of Triapine were also studied. Mono- and bis-ligand complexes in different protonation states were identified. Furthermore, the formation of the dinuclear species [Cu2L3]+ was confirmed for all ligands by EPR spectroscopy and ESI-MS measurements. The results showed that the N-terminally dimethylated ligands are much more potent chelators than Triapine for the divalent metal ions studied. All three ligands formed the least stable complexes with ZnII, whereas the FeII complexes were somewhat more stable than the corresponding CuII species. [source]

    Heterometallic CoIII,LnIII (Ln = Gd, Tb, Dy) Complexes on a p -Sulfonatothiacalix[4]arene Platform Exhibiting Redox-Switchable Metal-to-Metal Energy Transfer

    Viktoriya Skripacheva
    Abstract Nuclear magnetic relaxation along with pH metric data have been used to reveal pH-dependent heterometallic CoIII,LnIII (Ln = Gd, Tb, and Dy) complex formation on a p -sulfonatothiacalix[4]arene (TCAS) platform in aqueous solution. The previously obtained 1D and 2D 1H NMR spectroscopic and X-ray data prove the outer sphere binding of the CoIII block with the upper rim of TCAS, whereas the LnIII ion is coordinated with the phenolate groups of the lower rim of TCAS. The inclusive outer-sphere binding of CoIII tris(dipyridyl) and tris(ethylendiaminate) complexes with the upper rim of TCAS favors binding of the inner-sphere lanthanide ions through the lower rim of TCAS, whereas noninclusive binding of CoIII bis(histidinate) provides no effect on the binding of lanthanide ions. The emission properties of [Co(dipy)3]3+,LnIII (Ln = Gd, Tb, Dy) complexes indicate the quenching of 4f luminescence by the 3d block. This quenching can be switched off by electrochemical CoIII/CoII reduction with further switching on by reoxidation. ( Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008) [source]

    Red Pyrroloquinoline Alkaloids from the Mushroom Mycena haematopus

    Silke Peters
    Abstract Four so far unknown red alkaloid pigments, haematopodin B (1) and the mycenarubins D (3), E (5) and F (6), were isolated from fruiting bodies of Mycena haematopus. The structures of these pyrroloquinoline alkaloids were established by 2D NMR spectroscopic and MS (ESI) methods. Their absolute configurations were determined by comparison of their CD spectra with that of haematopodin (2) or mycenarubin A (4). Metabolic profiling of the red pigments of intact and injured fruiting bodies revealed that the known degradation product haematopodin (2) originates from haematopodin B (1), which is the native main pigment of M. haematopus.( Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008) [source]

    An Acyclic Aminonaphthyridine-Based Receptor for Carbohydrate Recognition: Binding Studies in Competitive Solvents

    Monika Mazik
    Abstract 1H NMR spectroscopic and microcalorimetric titrations revealed that receptor 3b, consisting of three protonated 2-amino-1,8-naphthyridine units, binds N -acetylneuraminic acid (Neu5Ac), the most commonly occurring sialic acid, with high affinity in competitive solvents such as water/dimethyl sulfoxide. Receptor 3b is able to form neutral/charge-reinforced hydrogen bonds and ion pairs with Neu5Ac, similar to sialic acid-binding proteins. Furthermore, indications for weak binding of neutral sugars, such as methyl ,- D -glucopyranoside, D -maltose and D -cellobiose were provided by NMR spectroscopy. Molecular modelling calculations, synthesis and binding studies in aqueous media are described. ( Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007) [source]

    Synthesis and characterization of the PEG-based nonionic surfactants endowed with carboxylic acid moiety at the hydrophobic terminal

    Hiroshi Morikawa
    As a new class of stimulus-responsive surfactants, a series of ,-methyl-,-alkyl PEGs endowed with a carboxylic acid moiety at the hydrophobic terminal was successfully synthesized with 56,97% yields. They were characterized by IR, NMR spectroscopic and MALDI-TOF MS analyses. It is suggested by DLS measurement that the collapse of the micelle-like aggregation occurred under basic condition. This synthetic procedure would be applicable to surfactants with sufficient hydrophilic and lipophilic balances, allowing precise control of pH-responsive micellar systems. [source]

    Vibrational 13C-cross-polarization/magic angle spinning NMR spectroscopic and thermal characterization of poly(alanine-glycine) as model for silk I Bombyx mori fibroin

    BIOPOLYMERS, Issue 5 2003
    Patrizia Monti
    Abstract This study focuses on the conformational characterization of poly(alanine-glycine) II (pAG II) as a model for a Bombyx mori fibroin silk I structure. Raman, IR, and 13C-cross-polarization/magic angle spinning NMR spectra of pAG II are discussed in comparison with those of the crystalline fraction of B. mori silk fibroin (chymotryptic precipitate, Cp) with a silk I (silk I-Cp) structure. The spectral data give evidence that silk I-Cp and the synthetic copolypeptide pAG II have similar conformations. Moreover, the spectral findings reveal that silk I-Cp is more crystalline than pAG II; consequently, the latter contains a larger amount of the random coil conformation. Differential scanning calorimetry measurements confirm this result. N-Deuteration experiments on pAG II allow us to attribute the Raman component at 1320 cm,1 to the amide III mode of a ,-turn type II conformation, thus confirming the results of those who propose a repeated ,-turn type II structure for silk I. The analysis of the Raman spectra in the ,NH region confirms that the silk I structure is characterized by the presence of different types of H-bonding arrangements, in agreement with the above model. 2003 Wiley Periodicals, Inc. Biopolymers (Biospectroscopy) 72: 329,338, 2003 [source]

    Reversible Double-Helix,Random-Coil Transition Process of Bis{hexa(ethynylhelicene)}s

    Hiroki Sugiura Dr.
    Abstract Two compounds with two hexa(ethynylhelicene) parts connected by a flexible haxadecamethylene and a rigid butadiyne linker were synthesized. The 1H,NMR spectroscopic and CD analyses and vapor-pressure osmometry (VPO) of these two compounds revealed intramolecular double-helix formation. Upon heating a 5-,M solution in toluene, the double-helix structure unfolded to form a random coil, and on cooling it folded again into a double helix. The thermodynamic stabilities of both structures were dependent on temperature, and the structural change in both compounds is due to the large enthalpies and entropies under equilibrium. The rate constants of their unfolding were obtained by assuming a pseudo-first-order reaction; the compound with a rigid linker unfolded slower than that with a flexible linker. The former has a larger activation energy, and its double-helix and random-coil conformers were separated by chromatography. The rate of folding was also faster for the flexible-linker compound with larger activation energy. The rate constants for the folding of both compounds slightly decreased with increasing temperature, which was ascribed to the presence of exothermic pre-equilibrium and rate-determining steps. The folding was markedly accelerated with increasing random-coil concentration, which suggests the involvement of self-catalysis. A mechanism of folding was proposed. The involvement of different mechanisms of folding and unfolding was suggested by the kinetic studies, and it was confirmed by the presence of hysteresis in the melting profiles. The difference in linker structure also affected the thermal-switching profiles of the double-helix,random-coil structural changes. [source]