Proton affinity of β-oxalylaminoalanine (BOAA): Incorporation of direct entropy correction into the single-reference kinetic method

A new version of the single-reference-extended kinetic method is presented in which direct entropy correction is incorporated. Results of calibration experiments with the monodentate base pyridine and the bidentate base ethylenediamine are presented for which the method provides proton affinities in excellent agreement with published values and reasonable predictions for the protonation entropies. The method is then used to determine the proton affinity and protonation entropy of the non-protein amino acid beta-oxalylaminoalanine (BOAA). The PA of BOAA is found to be 933.1 +/- 7.8 kJ/mol and a prediction for the protonation entropy of -39 J mol(-1) K(-1) is also obtained, indicating a significant degree of intramolecular hydrogen bonding in the protonated form. These results are supported by hybrid density functional theory calculations at the B3LYP/6-311++G**//B3LYP/6-31+G* level. They indicate that the preferred site of protonation is the alpha-nitrogen atom (PA = 935.0 kJ/mol) and that protonated BOAA has a strong hydrogen bond between the hydrogen on the alpha-amino group and one of the carbonyl oxygen atoms on the side chain.     

Proton affinity of canavanine and canaline, oxyanalogues of arginine and ornithine, from the extended kinetic method

The absolute proton affinities of the nonprotein amino acids canavanine and canaline have been determined using the extended kinetic method in an electrospray ionization quadrupole ion trap instrument. Canavanine results from the substitution of an oxygen atom for the delta-CH2 group in the side chain of the protein amino acid arginine, whereas canaline results from a similar substitution at the delta-CH2 group in the side chain of ornithine. Absolute proton affinities of 1001+/-9 and 950+/-7 kJ/mol are obtained for canavanine and canaline, respectively. For canaline, this proton affinity is in excellent agreement with theoretical predictions obtained using the hybrid density functional theory method B3LYP/6-311++G**//B3LYP/6-31+G*. For canavanine, theory predicts a somewhat larger proton affinity of 1015 kJ/mol. Oxygen atom substitution in these nonprotein amino acids results in a decrease in their proton affinities of 40-50 kJ/mol compared to arginine and ornithine.     

cis-1,5-Diaminocyclooctane: the most basic gaseous primary amine?

The gas phase basicity of the title compound has been determined to be greater than that of putrescine, making it the most basic primary diamine measured to date.     

MR imaging of benign prostatic hypertrophy using a Helmholtz-type surface coil.

MR examinations of the prostate were performed on six healthy volunteers and 18 patients with well-documented symptomatic benign prostatic hypertrophy, using an organ-encompassing Helmholtz-type surface coil at 1.5 T. The healthy volunteers were also imaged with a standard circumferential body coil. The morphologic features and signal intensity characteristics of the prostate and adjacent structures were analyzed in the patient group. Several recognizable patterns of benign prostate hypertrophy were identified including bilaterally symmetrical nodules in the central gland, multiple central gland nodules, and a diffusely heterogeneous central gland without appreciable nodules. The peripheral zone was of moderate to high signal intensity on T2-weighted images, and was diffusely heterogeneous in 78% of patients. The false prostatic capsule, peripheral venous plexus, and seminal vesicles were also characterized. A good correlation was shown between prostatic glandular volume and prostate-specific antigen. Calculated signal-to-noise ratios (S/N) were significantly greater on images acquired with the Helmholtz-type receiver coil than on those acquired with the body coil. We conclude that the hyperplastic prostate gland has a variety of MR appearances, but that recognizable patterns are frequently seen. High resolution imaging with a Helmholtz-type surface coil provides excellent anatomical depiction of the prostate and adjacent structures.