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Relaxation Measurements (relaxation + measurement)
Selected AbstractsNMR T1 -Relaxation Measurements on Paramagnetic Organolanthanides:An Alternative Tool for Structure Determination in SolutionEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 12 2005Laurent Brachais Abstract 1H NMR investigations were conducted on four paramagnetic organolanthanides, all bearing the tetraisopropylcyclopentadienyl ligand Cp4i (HC5iPr4) in order to verify whether or not interactions observed in the solid state are maintained in solution. In some cases variable-temperature experiments were necessary to enhance the resolution and determine the best conditions for the study. The 1D NMR spectrum could be interpreted in every case. Complementary 2D COSY experiments allowed the full attribution of the signals. T1 (1H) relaxation values were determined for all the paramagnetic complexes at the most suitable temperature, and compared with those of the diamagnetic KCp4i. The same tendency was observed, with particular features concerning the isopropyl groups. Among the four methyl groups, one exhibits a much higher T1 value and one a much lower value; the two others are intermediate. This was interpreted as the result of a privileged conformation of the Cp4i ligand: the two ,-isopropyl groups take up a spatial orientation with one methyl group in the exo position, opposite to the metal atom, whereas the methyl groups of the two ,-isopropyl groups are equidistant from the metal atom. Whatever the nature of the metal (Nd, Sm), the oxidation state (SmII, SmIII) or the temperature (298, 363 K), this conformation is retained. The structure in solution seems to be different from that previously determined in the solid state. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005) [source] Wide-ranging molecular mobilities of water in active pharmaceutical ingredient (API) hydrates as determined by NMR relaxation timesJOURNAL OF PHARMACEUTICAL SCIENCES, Issue 10 2008Sumie Yoshioka Abstract In order to examine the possibility of determining the molecular mobility of hydration water in active pharmaceutical ingredient (API) hydrates by NMR relaxation measurement, spin,spin relaxation and spin,lattice relaxation were measured for the 11 API hydrates listed in the Japanese Pharmacopeia using pulsed 1H-NMR. For hydration water that has relatively high mobility and shows Lorentzian decay, molecular mobility as determined by spin,spin relaxation time (T2) was correlated with ease of evaporation under both nonisothermal and isothermal conditions, as determined by DSC and water vapor sorption isotherm analysis, respectively. Thus, T2 may be considered a useful parameter which indicates the molecular mobility of hydration water. In contrast, for hydration water that has low mobility and shows Gaussian decay, T2 was found not to correlate with ease of evaporation under nonisothermal conditions, which suggests that in this case, the molecular mobility of hydration water was too low to be determined by T2. A wide range of water mobilities was found among API hydrates, from low mobility that could not be evaluated by NMR relaxation time, such as that of the water molecules in pipemidic acid hydrate, to high mobility that could be evaluated by this method, such as that of the water molecules in ceftazidime hydrate. © 2008 Wiley-Liss, Inc. and the American Pharmacists Association J Pharm Sci 97:4258,4268, 2008 [source] Parallel imaging of knee cartilage at 3 TeslaJOURNAL OF MAGNETIC RESONANCE IMAGING, Issue 4 2007Jin Zuo PhD Abstract Purpose To evaluate the feasibility and reproducibility of quantitative cartilage imaging with parallel imaging at 3T and to determine the impact of the acceleration factor (AF) on morphological and relaxation measurements. Materials and Methods An eight-channel phased-array knee coil was employed for conventional and parallel imaging on a 3T scanner. The imaging protocol consisted of a T2-weighted fast spin echo (FSE), a 3D-spoiled gradient echo (SPGR), a custom 3D-SPGR T1rho, and a 3D-SPGR T2 sequence. Parallel imaging was performed with an array spatial sensitivity technique (ASSET). The left knees of six healthy volunteers were scanned with both conventional and parallel imaging (AF = 2). Results Morphological parameters and relaxation maps from parallel imaging methods (AF = 2) showed comparable results with conventional method. The intraclass correlation coefficient (ICC) of the two methods for cartilage volume, mean cartilage thickness, T1rho, and T2 were 0.999, 0.977, 0.964, and 0.969, respectively, while demonstrating excellent reproducibility. No significant measurement differences were found when AF reached 3 despite the low signal-to-noise ratio (SNR). Conclusion The study demonstrated that parallel imaging can be applied to current knee cartilage quantification at AF = 2 without degrading measurement accuracy with good reproducibility while effectively reducing scan time. Shorter imaging times can be achieved with higher AF at the cost of SNR. J. Magn. Reson. Imaging 2007;26:1001,1009. © 2007 Wiley-Liss, Inc. [source] Correlation Between Thermal and Mechanical Relaxation in Chalcogenide Glass FibersJOURNAL OF THE AMERICAN CERAMIC SOCIETY, Issue 9 2009Pierre Lucas Enthalpy relaxation processes in chalcogenide fibers at room temperature are investigated by differential scanning calorimetry and compared with bending-stress relaxation measurements obtained by rolling fibers on a mandrel and recording the viscoelastic relaxation parameters. While the kinetics of the two processes is very different, several qualitative correlations are demonstrated between the enthalpy state and the mechanical properties of chalcogenide glass fibers. It is observed that the ability to undergo stress relaxation is dependent upon the fictive temperature of the glass. Stress relaxation in a glass far from thermodynamic equilibrium is contingent upon its ability to undergo enthalpy relaxation and is minimal in glasses that have already relaxed enthalpy or in which relaxation time is overwhelmingly large. [source] Investigation of Soft Component Mobility in Thermoplastic Elastomers using Homo- and Heteronuclear Dipolar Filtered 1H Double Quantum NMR ExperimentsMACROMOLECULAR CHEMISTRY AND PHYSICS, Issue 1 2004Marko Bertmer Abstract Summary: Information about segmental mobility in thermoplastic elastomers was obtained using static 1H double quantum (DQ) NMR experiments in combination with homo- and heteronuclear dipolar filters, e.g. 13C editing of 1H DQ buildup curves. Block copolymers of poly(butylene terephthalate) (PBT) as hard blocks and poly(tetramethylene oxide) (PTMO) as soft blocks (PBT- block -PTMO) were investigated by varying composition and block length. By simulation of the DQ buildup curves, residual dipolar couplings and with this the average order parameter were deduced for the mobile PTMO blocks which are sensitive to the segmental mobility responsible for the viscoelastic properties of thermoplastic elastomers. A strong correlation exists between residual dipolar coupling and composition. Furthermore, the average order parameter correlates linearly with the amount of PTMO in a PTMO-rich phase as determined in previous studies. Additionally, 1H transverse magnetization relaxation measurements revealed a direct correlation between the effective T2 relaxation time of the soft domain and the composition of the thermoplastic elastomers. Correlation of the average order parameter vs. the fraction of PTMO in the PTMO-rich phase. [source] Studies on inclusion complexes of calix[4]arenes capped by diamide bridges with small organic molecules,MAGNETIC RESONANCE IN CHEMISTRY, Issue 8 2008Barbara Balázs Abstract The inclusion of small neutral organic guests (acetonitrile, toluene, pyrazine, butylamine, nitromethane) by cyclic calix[4]arene diamide receptors was studied by 1H NMR spectroscopy. The binding constants determined by 1H NMR titration, and the results obtained by T1 relaxation measurements and DOSY confirm the importance of the acidity of the CH bond of the guests and highlight the role of steric interactions including conformational properties of the receptors in the recognition process. Copyright © 2008 John Wiley & Sons, Ltd. [source] Characterisation of indomethacin and nifedipine using variable-temperature solid-state NMRMAGNETIC RESONANCE IN CHEMISTRY, Issue 11 2005David C. Apperley Abstract We have characterised the stable polymorphic forms of two drug molecules, indomethacin (1) and nifedipine (2) by 13C CPMAS NMR and the resonances have been assigned. The signal for the CCl carbon of indomethacin has been studied as a function of applied magnetic field, and the observed bandshapes have been simulated. Variable-temperature 1H relaxation measurements of static samples have revealed a T1, minimum for indomethacin at 17.8 °C. The associated activation energy is 38 kJ mol,1. The relevant motion is probably an internal rotation and it is suggested that this involves the COCH3 group. Since the two drug compounds are potential candidates for formulation in the amorphous state, we have examined quench-cooled melts in detail by variable-temperature 13C and 1H NMR. There is a change in slope for and at the glass transition temperature (Tg) for indomethacin, but this occurs a few degrees below Tg for nifedipine, which is perhaps relevant to the lower real-time stability of the amorphous form for the latter compound. Comparison of relaxation time data for the crystalline and amorphous forms of each compound reveals a greater difference for nifedipine than for indomethacin, which again probably relates to real-time stabilities. Recrystallisation of the two drugs has been followed by proton bandshape measurements at higher temperatures. It is shown that, under the conditions of the experiments, recrystallisation of nifedipine can be detected already at 70 °C, whereas this does not occur until 110 °C for indomethacin. The effect of crushing the amorphous samples has been studied by 13C NMR; nifedipine recrystallises but indomethacin does not. The results were supported by DSC, powder XRD, FTIR and solution-state NMR measurements. Copyright © 2005 John Wiley & Sons, Ltd. [source] Fishtail effect in twinned and detwinned YBCO single crystalsPHYSICA STATUS SOLIDI (C) - CURRENT TOPICS IN SOLID STATE PHYSICS, Issue 9 2006M. Boudissa Abstract We have studied the magnetization hysteresis loops of a twinned and detwinned single crystals in a temperature range between 4.2 and 100 K and a magnetic field (H) range between 0 and 6 T. We carried out relaxation measurements on the samples at different temperatures and magnetic fields. We investigated the twin pinning as a function of temperature (T) and the fishtail anomaly in the critical current density of the two samples. We tried in this study to confirm or infirm the different models which explain the fishtail effect by confronting them to our experimental results We found that the collective creep theory is consistent with the results of our experiment in the field region where the magnetization is at its minimum. This field marks a crossover between the small and large bundle pinning regimes. (© 2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) [source] Enthalpy relaxation in bisphenol-A polycarbonate/poly(methyl methacrylate) blendsPOLYMER ENGINEERING & SCIENCE, Issue 3 2007Maurizio Penco Bisphenol-A polycarbonate (PC)/poly(methyl methacrylate) (PMMA) blends (PC/PMMA) were prepared by melt mixing with and without a trans-esterification catalyst (tetrabutylammoniun tetraphenylborate), which is able to promote inter-exchange reactions between PC and PMMA. Evidences of the ester,ester exchange reaction taking place were pointed out via Fourier Transform Infra-Red and size exclusion chromatography analyses. A series of enthalpy relaxation measurements were carried out for the pure polymers and for blends thereof. The data were analyzed on the basis of the Tool,Narayanaswamy,Moynihan/Kohlraush,Williams,Watts model. This model characterizes the structural relaxation in the glass transition region by means of four parameters: the apparent activation energy (,h*), the nonlinearity (x), the nonexponentiality (,), and the pre-exponential factor (,0). The apparent activation energy can be determined from the cooling rate dependence of the fictive temperature (Tf) measured using DSC. ,h* values of homogeneous blend and of the starting polymers were determined in this way, while an estimation of x, , and ,0 was proposed. Comparisons were made between a single glass transition temperature PC/PMMA blend and homopolymers data. The experimental values of ,h* suggest that the degree of cooperativity decreases on going from the starting polymers to the blend. POLYM. ENG. SCI., 47:218,224, 2007. © 2007 Society of Plastics Engineers. [source] Backbone dynamics of SDF-1, determined by NMR: Interpretation in the presence of monomer,dimer equilibriumPROTEIN SCIENCE, Issue 11 2006Olga K. Baryshnikova Abstract SDF-1, is a member of the chemokine family implicated in various reactions in the immune system. The interaction of SDF-1, with its receptor, CXCR4, is responsible for metastasis of a variety of cancers. SDF-1, is also known to play a role in HIV-1 pathogenesis. The structures of SDF-1, determined by NMR spectroscopy have been shown to be monomeric while X-ray structures are dimeric. Biochemical data and in vivo studies suggest that dimerization is likely to be important for the function of chemokines. We report here the dynamics of SDF-1, determined through measurement of main chain 15N NMR relaxation data. The data were obtained at several concentrations of SDF-1, and used to determine a dimerization constant of ,5 mM for a monomer,dimer equilibrium. The dimerization constant was subsequently used to extrapolate values for the relaxation data corresponding to monomeric SDF-1,. The experimental relaxation data and the extrapolated data for monomeric SDF-1, were analyzed using the model free approach. The model free analysis indicated that SDF-1, is rigid on the nano- to picosecond timescale with flexible termini. Several residues involved in the dimer interface display slow micro- to millisecond timescale motions attributable to chemical exchange such as monomer,dimer equilibrium. NMR relaxation measurements are shown to be applicable for studying oligomerization processes such as the dimerization of SDF-1,. [source] NMR solution structure and backbone dynamics of domain III of the E protein of tick-borne Langat flavivirus suggests a potential site for molecular recognitionPROTEIN SCIENCE, Issue 6 2006Munia Mukherjee Abstract Flaviviruses cause many human diseases, including dengue fever, yellow fever, West Nile viral encephalitis, and hemorrhagic fevers, and are transmitted to their vertebrate hosts by infected mosquitoes and ticks. Domain III of the envelope protein (E-D3) is considered to be the primary viral determinant involved in the virus,host-cell receptor interaction, and thus represents an excellent target for antiviral drug development. Langat (LGT) virus is a naturally attenuated BSL-2 TBE virus and is a model for the pathogenic BSL-3 and BSL-4 viruses in the serogroup. We have determined the solution structure of LGT-E-D3 using heteronuclear NMR spectroscopy. The backbone dynamics of LGT-E-D3 have been investigated using 15N relaxation measurements. A detailed analysis of the solution structure and dynamics of LGT-E-D3 suggests potential residues that could form a surface for molecular recognition, and thereby represent a target site for antiviral therapeutics design. [source] Interaction of angiotensin II with the C-terminal 300,320 fragment of the rat angiotensin II receptor AT1a monitored by NMRBIOPOLYMERS, Issue 2 2003Nicola D'Amelio Abstract Interaction between angiotensin II (Ang II) and the fragment peptide 300,320 (fCT300,320) of the rat angiotensin II receptor AT1a was demonstrated by relaxation measurements, NOE effects, chemical shift variations, and CD measurements. The correlation times modulating dipolar interactions for the bound and free forms of Ang II were estimated by the ratio of the nonselective and single-selective longitudinal relaxation rates. The intermolecular NOEs observed in NOESY spectra between HN protons of 9LysfCT and 6Hisang, 10PhefCT and 8Pheang, HN proton of 3TyrfCT and H, of 4Tyrang, 5PhefCTH, and H, of 4Tyrang indicated that Ang II aromatic residues are directly involved in the interaction, as also verified by relaxation data. Some fCT300,320 backbone features were inferred by the CSI method and CD experiments revealing that the presence of Ang II enhances the existential probability of helical conformations in the fCT fragment. Restrained molecular dynamics using the simulated annealing protocol was performed with intermolecular NOEs as constraints, imposing an ,-helix backbone structure to fCT300,320 fragment. In the built model, one strongly preferred interaction was found that allows intermolecular stacking between aromatic rings and forces the peptide to wrap around the 6Leu side chain of the receptor fragment. © 2003 Wiley Periodicals, Inc. Biopolymers 70: 134,144, 2003 [source] Self-Assembly of Two-Component Gels: Stoichiometric Control and Component SelectionCHEMISTRY - A EUROPEAN JOURNAL, Issue 2 2009Andrew Abstract Two-component systems capable of self-assembling into soft gel-phase materials are of considerable interest due to their tunability and versatility. This paper investigates two-component gels based on a combination of a L -lysine-based dendron and a rigid diamine spacer (1,4-diaminobenzene or 1,4-diaminocyclohexane). The networked gelator was investigated using thermal measurements, circular dichroism, NMR spectroscopy and small angle neutron scattering (SANS) giving insight into the macroscopic properties, nanostructure and molecular-scale organisation. Surprisingly, all of these techniques confirmed that irrespective of the molar ratio of the components employed, the "solid-like" gel network always consisted of a 1:1 mixture of dendron/diamine. Additionally, the gel network was able to tolerate a significant excess of diamine in the "liquid-like" phase before being disrupted. In the light of this observation, we investigated the ability of the gel network structure to evolve from mixtures of different aromatic diamines present in excess. We found that these two-component gels assembled in a component-selective manner, with the dendron preferentially recognising 1,4 - diaminobenzene (>70,%), when similar competitor diamines (1,2- and 1,3-diaminobenzene) are present. Furthermore, NMR relaxation measurements demonstrated that the gel based on 1,4-diaminobenzene was better able to form a selective ternary complex with pyrene than the gel based on 1,4-diaminocyclohexane, indicative of controlled and selective ,,, interactions within a three-component assembly. As such, the results in this paper demonstrate how component selection processes in two-component gel systems can control hierarchical self-assembly. [source] | |||||||||||||