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Biomedical subjects

K L Rowlen

Publications and source records attributed to K L Rowlen.

5 recordsLinked to original sources

On-column refractive index detector for flash chromatography.

A universal detector for on-column analysis in flash chromatography is reported. The detection scheme takes advantage of refractive index changes as analytes move through an illuminated region of the column. The column packing material is a diffuse scattering medium when the refractive index of the solvent is significantly different than that of the packing material. The magnitude of the 'signal' depends on the degree to which the refractive index mismatch is changed. An empirical model that qualitatively accounts for the observed trends is presented. This detection scheme provides a simple, inexpensive means to monitor the end of a flash chromatography column in order to determine the exit time of the species of interest, thus greatly reducing the post-column analysis time. Additionally, the detector is movable along the length of the column, offering the potential to monitor separations as they occur.

Calibration↗

Measurement of orientation in organic thin films.

As the potential for applications utilizing oriented thin films grows, so grows the need for accurate, reliable measurements of molecular orientation and surface coverage. Recent work in our laboratory has been directed toward this goal. In this paper the theoretical and experimental effects of surface roughness and the width of the molecular orientation distribution on spectroscopically measured orientation angles are reviewed, the combination of linear and nonlinear spectroscopic techniques for accurate determination of both the mean and width of an orientation distribution is described, and the theory and methodology necessary to obtain orientation-insensitive surface coverage measurements by second harmonic generation for adsorption isotherm and kinetics investigations are reviewed.

Algorithms↗

Derivatization of thymine and thymine photodimers with 4-bromomethyl-7-methoxycoumarin for fluorescence detection in high-performance liquid chromatography.

Exposure of DNA to utraviolet radiation results in the formation of a number of photoproducts, including thymine photodimers. A sensitive and selective analytical method based on high-performance liquid chromatography (HPLC) and fluorescent labeling with 4-bromomethyl-7-methoxycoumarin has been developed to quantify both thymine and thymine photodimers. The identity of the thymine and thymine dimer derivatives were determined by HPLC-electrospray ionization mass spectrometry. The derivatization reaction yield was maximized by optimizing several reaction variables. The limit of detection for HPLC method was 1.0 pmol thymine and 0.4 pmol thymine dimer for S/N = 3.

Calibration↗

Psoralen-olefin photoproducts: first observation of a photo-ene reaction.

Methyl-substituted psoralens (4'-(hydroxymethyl)-4,5',8-trimethylpsoralen and 4,5',8-trimethylpsoralen) are found to yield an ene product as well as the expected [2 + 2] cycloaddition product from photochemical reaction with simple olefins. As determined by absorbance, liquid chromatography-mass spectrometry and nuclear magnetic resonance, both products are formed at the pyrone side of the respective psoralen. The product distribution is dependent on olefin concentration as well as the nature of the olefin. In deoxygenated solutions, cyclic olefins form as much as 50% ene product, while unsubstituted straight-chain olefins form as little as 3%. In oxygenated solutions, the product distribution is strongly affected by singlet oxygen.

Alkenes↗

Evidence for a gamma-turn motif in antifreeze glycopeptides.

Knowledge of the secondary structure of antifreeze peptides (AFPs) and glycopeptides (AFGPs) is crucial to understanding the mechanism by which these molecules inhibit ice crystal growth. A polyproline type II helix is perhaps the most widely accepted conformation for active AFGPs; however, random coil and alpha-helix conformations have also been proposed. In this report we present vibrational spectroscopic evidence that the conformation of AFGPs in solution is not random, not alpha-helical, and not polyproline type II. Comparison of AFGP amide vibrational frequencies with those observed and calculated for beta and gamma-turns in other peptides strongly suggests that AFGPs contain substantial turn structure. Computer-generated molecular models were utilized to compare gamma-turn, beta-turn, and polyproline II structures. The gamma-turn motif is consistent with observed amide frequencies and results in a molecule with planar symmetry with respect to the disaccharides. This intriguing conformation may provide new insight into the unusual properties of AFGPs.

Amino Acid Sequence↗