Menstrual toxic shock syndrome (mTSS) is thought to be associated with colonization with toxic shock syndrome toxin 1 (TSST-1)-producing Staphylococcus aureus in women with insufficient antibody titers. mTSS has been associated with menstruation and tampon use, and although it is rare, the effects can be life threatening. It remains of interest because of the widespread use of tampons, reported to be about 70% of women in the United States, Canada, and much of Western Europe. This comprehensive study was designed to determine S. aureus colonization and TSST-1 serum antibody titers in 3,012 menstruating women in North America between the ages of 13 and 40, particularly among age and racial groups that could not be assessed reliably in previous small studies. One out of every four subjects was found to be colonized with S. aureus in at least one of three body sites (nose, vagina, or anus), with approximately 9% colonized vaginally. Eighty-five percent of subjects had antibody titers (>1:32) to TSST-1, and the vast majority (81%) of teenaged subjects (13 to 18 years) had already developed antibody titers. Among carriers of toxigenic S. aureus, a significantly lower percentage of black women than of white or Hispanic women were found to have antibody titers (>1:32) to TSST-1 (89% versus 98% and 100%). These findings demonstrate that the majority of teenagers have antibody titers (>1:32) to TSST-1 and are presumed to be protected from mTSS. These findings also suggest that black women may be more susceptible to mTSS than previously thought.
1. General Methods All reagents were purchased from commercial suppliers (Aldrich or Fisher) and used without further purification. Cyclobis(paraquat-4,4′-biphenylene) tetrakis(hexafluorophosphate) S1 (1•4PF6), 4,4′(5′)-bis[2-(2-{2-(propargyl)ethoxy}ethoxy)ethoxy]tetrathiafulvalene S2 (7), the TTF/ DNP macrocycle S3 4, and 1,1ʹ′-[4,4ʹ′-biphenylenebis-(methylene)]bis(4,4ʹ′-bipyridinium) bis (hexafluorophosphate) S4 (5•2PF6) were prepared according to literature procedures. Thin layer chromatography (TLC) was performed on silica gel 60 F254 (E. Merck). Column chromatography was performed on silica gel 60F (Merck 9385, 0.040-0.063 nm). Nuclear magnetic resonance (NMR) spectra were recorded at 25 ˚C (unless otherwise noted) on Bruker Avance 500 and 600 spectrometers, with working frequencies of 500 and 600 MHz for 1 H, and 125 and 150 MHz for 13 C nuclei, respectively. Chemical shifts are reported in ppm relative to the signals corresponding to the residual non-deuterated solvents S5. All 13 C spectra were recorded with the simultaneous decoupling of proton nuclei. UV-Vis-NIR absorbance spectra
Cation-radicals and dications corresponding to hydrogen atom adducts to N-terminus-protonated N(alpha)-glycylphenylalanine amide (Gly-Phe-NH(2)) are studied by combined density functional theory and Møller-Plesset perturbational computations (B3-MP2) as models for electron-capture dissociation of peptide bonds and elimination of side-chain groups in gas-phase peptide ions. Several structures are identified as local energy minima including isomeric aminoketyl cation-radicals, and hydrogen-bonded ion-radicals, and ylid-cation-radical complexes. The hydrogen-bonded complexes are substantially more stable than the classical aminoketyl structures. Dissociations of the peptide N-C(alpha) bonds in aminoketyl cation-radicals are 18-47 kJ mol(-1) exothermic and require low activation energies to produce ion-radical complexes as stable intermediates. Loss of the side-chain benzyl group is calculated to be 44 kJ mol(-1) endothermic and requires 68 kJ mol(-1) activation energy. Rice-Ramsperger-Kassel-Marcus (RRKM) and transition-state theory (TST) calculations of unimolecular rate constants predict fast preferential N-C(alpha) bond cleavage resulting in isomerization to ion-molecule complexes, while dissociation of the C(alpha)bond;CH(2)C(6)H(5) bond is much slower. Because of the very low activation energies, the peptide bond dissociations are predicted to be fast in peptide cation-radicals that have thermal (298 K) energies and thus behave ergodically.
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