PubMed Health⌕ Search

PubMed · 15862239

Convection-compensating diffusion experiments with phase-sensitive double-quantum filtering.

Abstract

We present a design scheme for phase-sensitive, convection-compensating diffusion experiments with gradient-selected homonuclear double-quantum filtering. The scheme consists of three blocks: a 1/2J evolution period during which antiphase single-quantum coherences are created; a period of double-quantum evolution; and another 1/2J period, during which antiphase single-quantum coherences are converted back into an in-phase state. A single coherence transfer pathway is selected using an asymmetric set of gradient pulses, and both diffusion sensitization and convection compensation are built into the gradient coherence transfer pathway selection. Double-quantum filtering can be used either for solvent suppression or spectral editing, and we demonstrate examples of both applications. The new experiment performs well in the absence of a field-frequency lock and does not require magnitude Fourier transformation. The proposed scheme may offer advantages in diffusion measurements of spectrally crowded systems, particularly small molecules solubilized in colloidal solutions or bound to macromolecules.

Explore related subjects

Keep this discovery

Explore connections, maps & timelines

BibTeXRIS

Konstantin I Momot, Philip W Kuchel. 2005. Convection-compensating diffusion experiments with phase-sensitive double-quantum filtering.. https://doi.org/10.1016/j.jmr.2005.02.003

Cite the original work for its findings. Save a collection to share your selection of sources.

KEEP EXPLORING

Related citations

Near IR overtone spectral investigations of liquid phase imidazole and the blue-shifting hydrogen bonds.

The near infrared vibrational overtone absorption spectrum of imidazole dissolved in carbon tetrachloride is examined in the region Delta v = 2, 3 and 4. Instead of the standard hydrogen bonding, unusual blue-shifted hydrogen bonds are observed in NH positions. This observation is in agreement with the recent conclusions drawn from theoretical studies of the coupling character between the Imidazole-Imidazolium complex, which is strongly hydrogen bonded. The NH local mode mechanical frequency values and anharmonicity values obtained from fitting the overtones are analysed. The anharmonicity of blue-shifted hydrogen bonded NH stretching bands is greater compared to those of the free NH stretching bands. It is contrary to the decrease in anharmonicity due to the standard red shifting of NH bonds.

Carbon Tetrachloride↗

Transformation of carbon tetrachloride by thiol reductants in the presence of quinone compounds.

Quinones are present in trace amounts in natural organic matter. The addition of thiol compounds to quinones produces reactive electron-transfer species that may be important for the transformation of chlorinated hydrocarbons under sulfate-reducing conditions. This study systematically investigated the transformation of carbon tetrachloride (CCl4) in homogeneous aqueous solutions containing quinones as electron-transfer mediators and thiol compounds as bulk reductants. The thiol compounds, including sodium hydrosulfide (NaHS) and cysteine, were found to effectively transform CCl4. The transformation of CCl4 followed pseudo-first-order kinetics, and the pseudo-first-order rate constants (kobs) were (3.24 +/- 0.46) x 10(-7) and 1.04 x 10(-7) s(-1), respectively, when solutions contained NaHS and cysteine alone. Addition of quinone compounds, including anthraquinone-2,6-disulfonate (AQDS), benzoquinone (BQ), juglone (JQ), naphthoquinone (NQ), lawsone (LQ), and menadione (MQ), increased the transformation rate and efficiency of CCl4. The kobs values for CCl4 transformation in the presence of quinones were 2.6-71 times higher than those for the thiol compounds alone. The enhancement efficiency followed the order JQ > NQ > BQ >> AQDS > LQ > MQ. Spectroscopic studies indicated that the quinone compounds generated various active electron-transfer mediators to transfer electrons from the bulk reductants to CCl4. BQ and NQ produced mercaptoquinones as active redox mediators that significantly enhanced the transformation rate of CCl4 in the presence of NaHS. The addition of thiol reductants produced large amounts of AQDS semiquinone radical as the electron shuttle. In addition, MQ and LQ were reduced by NaHS to give hydroquinone, which slightly enhanced the transformation efficiency of CCl4. These results clearly indicate that the enhanced efficiency of quinones for the transformation of chlorinated hydrocarbons is specifically related to the produced reactive species. Mercaptoquinone is a more active mediator than either semiquinone or hydroquinone for transferring electrons in a reducing environment containing thiol reductants.

Carbon Tetrachloride↗

An experimental study of melting of CCl4 in carbon nanotubes.

We report dielectric relaxation spectroscopy measurements of the melting point of carbon tetrachloride confined within open-tip multi-walled carbon nanotubes with two different pore diameters, 4.0 and 2.8 nm. In both cases, a single transition temperature well above the bulk melting point was obtained for confined CCl4. These results contrast with what was obtained in our previous measurements using carbon nanotubes with a pore diameter of 5.0 nm, where multiple transition temperatures both above and below the bulk melting point of CCl4 were observed. Our experimental measurements are consistent with our recent molecular simulation results (F. R. Hung, B. Coasne, E. E. Santiso, K. E. Gubbins, F. R. Siperstein and M. Sliwinska-Bartkowiak, J. Chem. Phys., 2005, 122, 144706). Although the simulations overestimate the temperatures in which melting upon confinement occurs, both simulations and experiments suggest that all regions of adsorbate freeze at the same temperature, and that freezing occurs at higher temperatures upon reduction of the pore diameter.

Carbon Tetrachloride↗