Home About us Contact
|
Home About us Contact | ||
|
|
||
Deuterated Solvents (deuterated + solvent)
Selected AbstractsHigh-resolution H/D exchange studies on the HET-s218,295 prion proteinJOURNAL OF MASS SPECTROMETRY (INCORP BIOLOGICAL MASS SPECTROMETRY), Issue 5 2005Alexis Nazabal Abstract In a search for improved resolution of hydrogen/deuterium (H/D) exchange experiments analyzed by mass spectrometry (HXMS), we evaluated two methodologies for a detailed structural study of solvent accessibility in the case of the HET-s218,295 prion protein. For the first approach, after incubation in the deuterated solvent, aggregated HET-s218,295 was digested with pepsin and the generated peptides were analyzed by nanospray mass spectrometry in an ion trap, with and without collision-induced dissociation (CID). We compared deuterium incorporation in peptides as determined on peptide pseudomolecular ions and on b and y fragments produced by longer peptides under CID conditions. For both b and y fragment ions, an extensive H/D scrambling phenomenon was observed, in contrast with previous studies comparing CID-MS experiments and 1H NMR data. Thus, the spatial resolution of HXMS experiments could not be improved by means of MS/MS data generated by an ion trap mass spectrometer. In a second approach, the incorporation of deuterium was analyzed by MS for 76 peptides of the HET-s218,289 peptide mass fingerprint, and the use of shared boundaries among peptic peptides allowed us to determine deuteration levels of small regions ranging from one to four amino acids. This methodology led to evidence of highly protected regions along the HET-s218,295 sequence. Copyright © 2005 John Wiley & Sons, Ltd. [source] Structure and dynamics of silica-filled polymers by SANS and coherent SAXSMACROMOLECULAR SYMPOSIA, Issue 1 2002Erik Geissler Random crosslinking in elastomers gives birth to local variations in the crosslink density. When the network is swollen in a low-molecular-weight solvent, competition between the osmotic pressure and the local elastic constraints transforms these variations into differences in polymer concentration, the range and amplitude of which can be measured by small-angle X-ray or neutron scattering (SAXS or SANS). In filled systems, the distribution both of the polymer and of the elastic constraints is modified. By varying the proportion of deuterated solvent in the network, the scattering function of the polymer can be distinguished from that of the filler using SANS. Such measurements yield not only the internal surface area of the filler particles but also the fraction of that surface in contact with the polymer. The recently developed technique of quasi-elastic SAXS detects slow dynamic processes at wave vectors larger than those accessible with visible light lasers. This technique is used to investigate the dynamics of filler particles in uncrosslinked polymer melts. It is directly shown that the structural reorganization process of the filler following an external mechanical perturbation is diffusion-controlled. [source] High-resolution magic-angle spinning NMR for the identification of reaction products directly from thin-layer chromatography spotsMAGNETIC RESONANCE IN CHEMISTRY, Issue 10 2007Scott A. Bradley Abstract We have investigated the prospect of identifying organic reaction products directly from separated thin-layer chromatography (TLC) spots with high-resolution magic-angle spinning (HRMAS) NMR. The concept is to use the TLC spots for NMR analysis so that spectra can be obtained before the reaction is worked up, but without having to elute the product from the TLC stationary phase. Thus, the separated spot is scraped from the plate, transferred to an HRMAS sample rotor, and suspended with a deuterated solvent. Herein, we describe the effects of having the stationary phase present during NMR acquisition. Using a Varian 4 mm gHX Nanoprobe and rotenone as a test compound, we found that the presence of the stationary phase during NMR acquisition resulted in (i) a large, broad ,background' signal near 4.6 ppm and (ii) a decrease in the signal-to-noise ratio due to the adsorption of the product molecules to the adsorbent. However, both effects could be adequately and conveniently eliminated. The background signal was removed by using either a CPMG pulse sequence or chemical exchange. The adsorption was avoided by using a more polar solvent system. Finally, we found that spectra with good signal-to-noise ratio and resolution could be acquired in a matter of minutes even for cases of limited product concentration. Therefore, we believe the technique has value and provides the organic chemist with another option to obtain NMR data critical for structural elucidation or verification. Copyright © 2007 John Wiley & Sons, Ltd. [source] A PCP-Pincer RuII,Terpyridine Building Block as a Potential "Antenna Unit" for Intramolecular SensitizationEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 18 2007Marcella Gagliardo Abstract The redox- and photoactive mononuclear complex [Ru(PCP)(tpy,DTTANa4)]Cl {PCP = [C6H3(CH2PPh2)2 -2,6],; tpy,DTTA4, = 4,-(2,2,:6,,2,-terpyridine)-diethylenetriamine- N,N,N,,N, -tetraacetate} possesses an externally directed, vacant N3O4 polyaminocarboxylate-type binding site that coordinates to lanthanide(III) ions to give the neutral heterodinuclear RuII,LnIII complexes [Ru(PCP)(tpy,DTTA)Ln(H2O)2] (Ln = Gd3+, Eu3+). The photophysical properties of solutions of the mononuclear complex [Ru(PCP)(tpy,DTTANa4)]Cl were investigated in MeOH/EtOH (1:4) and compared to those of the solutions of heterodinuclear complexes [Ru(PCP)(tpy,DTTA)Ln(H2O)2] (Ln = Gd3+, Eu3+). Rigid matrix excitation at 77 K of the ,,* level of the ruthenium chromophore in the [Ru(PCP)(tpy,DTTA)Eu(H2O)2] complex results in a weak europium(III) emission pointing to a transfer of energy from Ru,Eu as a result of the metal-to-ligand charge-transfer (MLCT) excited state of the ruthenium component to the luminescent lanthanide ion. The excited state lifetime of the europium complex is 0.2 ms in methanol solution. In deuterated solvents, the lifetime increases to 0.4 ms, which indicates that the process is solvent-dependent as a result of the strongly coordinated molecules of water that are responsible for the quenching in nondeuterated solvents.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007) [source] Effect of hydrophobic side-chains on the solvation of imidazolium saltsJOURNAL OF PHYSICAL ORGANIC CHEMISTRY, Issue 10 2005Allan D. Headley Abstract The chemical shifts of the aromatic hydrogens of 12 symmetrical imidazolium salts were determined in different deuterated solvents. Based on the magnitude of the chemical shift change for the hydrogens of the imidazolium ion in the various solvents, relationships were developed to determine the relative solute/solvent interactions for these compounds. Owing to different degrees of interactions involving the aromatic hydrogens of the imidazolium cations and anions, there is a variation in the interaction of the hydrogens with the solvent molecules. The intimate interaction that exists between the hydrogens of the imidazolium cation and the BF anion results in the BF salts being less solvated compared with salts containing BF and SbF anions. For imidazolium salts that contain C2H5, C4H9 and C8H17 side-chains bonded in the 1 and 3 positions, the interaction between H2 and the solvents was observed to be greater than for imidazolium salts with C16H33 substituents. On the other hand, for imidazolium salts that have C16H33 substituents the interaction between H2 and the solvents is similar to that for H4 and H5. Copyright © 2005 John Wiley & Sons, Ltd. [source] Solvent Effects on the NMR Chemical Shifts of Imidazolium-Based Ionic Liquids and Cellulose ThereinMACROMOLECULAR SYMPOSIA, Issue 2 2010Stephanie Hesse-Ertelt Abstract The interactions of ionic liquids (IL) with solvents usually used in liquid-state nuclear magnetic resonance (NMR) spectroscopy are studied. The 1H- and 13C-NMR chemical shift values of 1-n-butyl-3-methyl (BM)- and 1-ethyl-3-methyl (EM)-substituted imidazolium (IM) -chlorides (Cl) and -acetates (Ac) are determined before and after diluting with deuterated solvents (DMSO-d6, D2O, CD3OD, and CDCl3). The dilution offers structural modifications of the IL due to the solvents capacity to ionization. For further investigation of highly viscous cellulose dopes made of imidazolium-based IL, solid-state NMR spectroscopy enables the reproducibility of liquid-state NMR data of pure IL. The correlation of liquid- and solid-state NMR is shown on EMIM-Ac and cellulose/EMIM-Ac dope (10 wt %). [source] Use of (S)-BINOL as NMR chiral solvating agent for the enantiodiscrimination of omeprazole and its analogsCHIRALITY, Issue 5 2010Jordi Redondo Abstract The application of (S)-1,1,-binaphthyl-2,2,-diol as NMR chiral solvating agent (CSA) for omeprazole, and three of its analogs (lanso-, panto-, and rabe-prazole) was investigated. The formation of diastereomeric host,guest complexes in solution between the CSA and the racemic substrates produced sufficient NMR signal splitting for the determination of enantiomeric excesses by 1H- or 19F-NMR spectroscopy. Using of hydrophobic deuterated solvents was mandatory for obtaining good enantiodiscrimination, thus suggesting the importance of intermolecular hydrogen bonds in the stabilization of the complexes. The method was applied to the fast quantification of the enantiomeric purity of in-process samples of S -omeprazole. Chirality, 2010. © 2009 Wiley-Liss, Inc. [source] | ||||||||||