Biomedical subjects

D W Alderman

Publications and source records attributed to D W Alderman.

12 recordsLinked to original sources

PubMed2002

Obtaining molecular and structural information from 13C-14N systems with 13C FIREMAT experiments.

The effect of dipolar coupling to 14N on 13C FIREMAT (five pi replicated magic angle turning) experiments is investigated. A method is developed for fitting the 13C FIREMAT FID employing the full theory to extract the 13C-14N dipolar and 13C chemical shift tensor information. The analysis requires prior knowledge of the electric field gradient (EFG) tensor at the 14N nucleus. In order to validate the method the analysis is done for the amino acids alpha-glycine, gamma-glycine, l-alanine, l-asparagine, and l-histidine on FIREMAT FIDs recorded at 13C frequencies of 50 and 100 MHz. The dipolar and chemical shift data obtained with this analysis are in very good agreement with the previous single-crystal 13C NMR results and neutron diffraction data on alpha-glycine, l-alanine, and l-asparagine. The values for gamma-glycine and l-histidine obtained with this new method are reported for the first time. The uncertainties in the EFG tensor on the resultant 13C chemical shift and dipolar tensor values are assessed.

Alanine↗

PubMed2001

Investigation of the polymorphs of dimethyl-3,6-dichloro-2,5-dihydroxyterephthalate by (13)C solid-state NMR spectroscopy.

Two of the three conformational polymorphs of dimethyl-3,6-dichloro-2,5-dihydroxyterephthalate are studied by solid-state NMR techniques. The structural differences between the polymorphs have previously been studied by X-ray. In these two polymorphs named white and yellow due to their color, the major structural difference is the torsional angle between the ester group and the aromatic ring. The yellow form has a dihedral angle of 4 degrees between the plane of the aromatic ring and the plane of the ester group, while the white form has two different molecules per unit cell with dihedral angles of 70 degrees and 85 degrees. This change greatly affects the conjugation in the pi-electronic system. In addition, there are differences in the hydrogen-bonding patterns, with the white form having intermolecular hydrogen bonds and the yellow form having intramolecular hydrogen bonds. In this work, the carbon isotropic chemical shift values and the chlorine electric field gradient (EFG) tensor information are extracted from the (13)C MAS spectra, and the principal values of the chemical shift tensors of the carbons are obtained from 2D FIREMAT experiments. Quantum chemical calculations of the chemical shift tensor data as well as the EFG tensor are performed at the HF and DFT levels of theory on individual molecules and on stacks of three molecules to account for the important intermolecular interactions in the white form. The differences between the spectral data on the two polymorphs are discussed in terms of the known electronic and structural differences.

Carbon Isotopes↗

PubMed1999

Resolution enhancement in 13C and 15N magic-angle turning experiments with TPPM decoupling.

Many solid-state spectra have been shown to have problems related to the poor proton decoupling of carbon nuclei in methylene groups under conditions of slow magic-angle turning. Two-pulse phase-modulation (TPPM) decoupling during the 2D PHORMAT chemical shift separation experiment is shown to be more effective in comparison to that obtainable at much higher spin rates using conventional CW decoupling. TPPM decoupling can also alleviate similar inadequacies when observing the 15N nucleus, particularly with NH2 groups. This is demonstrated in the 15N resonances of fully labeled l-arginine hydrochloride, where a line narrowing of about a factor of two was observed at moderate rotation rates. This significant advantage was also obtained at turning frequencies as low as 500 Hz.

Anisotropy↗

PubMed1997

Technique for importing greater evolution resolution in multidimensional NMR spectrum.

A very simple and general procedure that extracts constant-evolution-frequency data from a truncated multidimensional (2D, 3D, 4D, etc.) FID is described, generalized, analyzed, and illustrated. The method replaces Fourier transformation of the evolution dimension with a linear model created from a separate, high-quality 1D FID. The equivalent of high resolution in the evolution dimension can be achieved without obtaining an extensive multidimensional FID. The analysis of the 1D FID can also be used to predict the signal to noise ratio of the extracted slices that will result from various evolution dimension sampling protocols, making it possible to develop a priori an optimal sampling strategy for the multidimensional FID. The evolution dimension need not be sampled periodically. The procedure has a potential signal-to-noise ratio advantage because it extracts usable information from a multidimensional FID at short evolution times before the magnetization has decayed significantly.

Data Interpretation, Statistical↗

PubMed1995

Relationship of 13C NMR chemical shift tensors to diffraction structures.

13C chemical shift tensor measurements on single crystals provide a powerful method to study changes in the electron environment of nuclei with changes in molecular structure. Thus, diffraction structures are critical to an understanding of chemical shift tensors. This work explores the general reliability of using structural data to predict components of the symmetrical chemical shift tensor. Imprecision in the hydrogen positions introduces considerable scatter in the simulated 13C shift tensors, and optimized C-H bond distances in methyl-beta-D-glucopyranoside used with the X-ray positions of the heavier C and O atoms greatly improve the simulated chemical shifts. Acenaphthene, with two crystallographically different molecules per unit cell, offers an excellent example for comparing and contrasting structural differences in the two molecules. A recently improved X-ray structure of naphthalene obtained at low temperature provides chemical shift simulations which are comparable to those from neutron diffraction methods and appear to reflect breaks in the D2h symmetry measured in the NMR chemical shift tensors. These data illustrate the close relationship between NMR and diffraction structures.

Carbohydrate Conformation↗

PubMed1995

Use of relaxation agent doping to shorten very long spin-lattice relaxation times in a magic-angle turning experiment.

A practical method is described for measuring the principal values of the chemical shift tensors in compounds with very long proton spin-lattice relaxation times (T1). This technique involves shortening the effective proton T1. by mixing a compound of interest with another compound having a much shorter T1 value. The doped mixture, partly consisting of a monophasic glass, allows efficient intermolecular spin diffusion between the two compounds. Using a slow magic-angle turning (MAT) experiment, we have successfully used such mixtures to measure the principal values of the chemical shift tensors of all the carbons in dibenzofuran in just four days. Without using this technique the experimental time required for the pure compound would have been several months.

Benzofurans↗

PubMed1994

Measurement of 13C chemical shift tensor principal values with a magic-angle turning experiment.

The magic-angle turning (MAT) experiment introduced by Gan is developed into a powerful and routine method for measuring the principal values of 13C chemical shift tensors in powdered solids. A large-volume MAT probe with stable rotation frequencies down to 22 Hz is described. A triple-echo MAT pulse sequence is introduced to improve the quality of the two-dimensional baseplane. It is shown that measurements of the principal values of chemical shift tensors in complex compounds can be enhanced by using either short contact times or dipolar dephasing pulse sequences to isolate the powder patterns from protonated or non-protonated carbons, respectively. A model compound, 1,2,3-trimethoxybenzene, is used to demonstrate these techniques, and the 13C principal values in 2,3-dimethylnaphthalene and Pocahontas coal are reported as typical examples.

Anisoles↗

PubMed1993

Improvements to the magic angle hopping experiment.

Several improvements to the magic angle hopping experiment first introduced by Bax et al. [J. Magn. Reson., 52 (1983) 147] are presented. A dc servo motor driven sample hopping mechanism which requires less than 60 ms to accomplish a 120 degrees sample rotation is described. Modifications to the data acquisition process, including starting the acquisition period immediately after the second hop and acquiring a hypercomplex data set, are also presented. Principal values of the 13C chemical shielding tensor are measured for 1,2,3-trimethoxybenzene and 2,6-dimethoxynaphthalene.

Magnetic Resonance Spectroscopy↗

PubMed1990

The crossover surface coil: an efficient in vivo NMR detector.

The crossover surface coil is constructed with two turns of copper foil using a unique transposition construction which incorporates an explicit center tap ground of the widened bottom layer. The coil reduces dielectric and inductive losses by effective shielding of electric fields and uniform distribution of magnetic fields for minimum Q losses upon loading of the coil. Flexible, copper foil construction permits easy conformation to tissues of interest, enhancing coil performance. Construction details of the crossover coil and Q data for coils of various sizes operating at a number of frequencies are given.

Equipment Design↗

PubMed1990

The slotted crossover surface coil: a detector for in vivo NMR of skin.

An elongated, narrow, slotted crossover surface coil provides surface localization capable of resolving in vivo 31P NMR spectra from skin tissues. The shallow B1 field penetration achieves localization objectives while the probe length maintains signal-to-noise requirements. Dielectric and inductive losses are minimized via the crossover design (see T. L. Nagel et al., Magn. Reson. Med. 13, xxx (1990). In vivo spectra with millimeter depth resolution were acquired in 5 min at 2 T without pulse localization sequences. Preliminary 31P NMR spectra of normal and thermally injured rat skin were completed using a 25 X 3-mm slotted probe with a 3 X 2-cm surface region of excitation. Normal rat skin tissue PCr/Pi ratios ranged from 3.8 to 4.7 for 5-, 10-, and 30-mus pulse widths, while partial- and full-thickness scald injured tissues ranged from 0 to 2.8. Evaluation of a single minor partial thickness injury 1 to 5 h postburn shows evidence of a localized hypermetabolic response associated with hyperemia. Determination of burn depth and tissue viability appears feasible using: (1) PCr/Pi ratios and (2) observation of localized hypermetabolism.

Animals↗

PubMed1989

In vivo [31P]NMR studies on the influence of age on rat brain hypoxia.

In this paper the response of cerebral phosphate metabolism to mild hypoxia in young, medium and old rats has been studied via in-vivo [31P]nuclear magnetic resonance (NMR). It was found that the young adults (5-6 months) were more sensitive to this mild stress than either the mature adult (11-12 months) or senescent (23-24 months) rats even though the depth of hypoxia (paO2 = 45-55 mm Hg) was equal for all age groups. They displayed an earlier onset of acidosis, a greater fall in PCr and larger rise in Pi. This response is presumably an attempt to maintain adequate adenosine triphosphate (ATP) levels via anaerobic glycolysis. In contrast, mature adults and senescent adults appear to be able to maintain ATP levels by increasing mitochondrial rates. Acidosis is less severe as are drops in PCr and rises in Pi. Recovery is less complete for the young rats: Pi levels remain high while PCr and pHi levels stay low after normoxia has been reinstigated. All metabolite levels in the mature and senescent adults return to within 10% of control levels. All the data were analyzed and differences were found to be statistically significant. This study reveals that, contrary to popular belief, mature and old rats respond more favorably to reduced O2 than younger individuals. This is due to a more severe anaerobic acidosis in the latter age group. Speculations to explain this disparity are based on the fact that previous in-vitro studies involve systems that are totally or partially disconnected from the organism will not account for important feedback control present in an in-vivo system as studied here.

Aging↗

PubMed1987

Effects of age on apparent 31P spin-lattice relaxation times of rat brain phosphates.

Apparent 31P spin-lattice relaxation times have been measured in vivo for brain phosphates in young adult, mature adult, and aged rats at 4.7 T and 35 degrees C. Statistically significant differences were found for most phosphate species, except PCr and gamma-ATP, among the three age groups, particularly between the young and mature adults. Age-related changes in tissue composition and exchange reactions are discussed as possible contributors to these results.

Adenosine Triphosphate↗