Electrospray ionization mass spectrometric analysis of microcystins, cyclic heptapeptide hepatotoxins: modulation of charge states and [M + H]+ to [M + Na]+ ratio

AbstractElectrospray ionization mass spectrometry was used to develop a rapid, sensitive, and accurate method for determination and identification of hepatotoxic microcystins, cyanobacterial cyclic heptapeptides. To optimize the electrospray ionization conditions, factors affecting charge state distribution, such as amino acid components of sample, proton affinity of the additives, and additive concentration, were investigated in detail and a method for controlling charge states was developed to provide molecular-related ions for assignment of molecular weight and reasonably abundant precursor ions for MS/MS analysis. A procedure for identification of microcystins consisting of known amino acids was proposed: for microcystins giving abundant [M + 2H]2+ ions, the addition of nitrogen-containing bases to the aqueous sample solution is effective to obtain an increased intensity of [M + H]+ ions, whereas the addition of Lewis acids containing nitrogen can produce increased abundances of [M + 2H]2+ ions for microcystins giving weak [M + 2H]2+ ions. Microcystins possessing no arginine residue always give sodium adduct ions [M + Na]+ as the base peak, and these are difficult to fragment via low energy collision-induced dissociation to yield structurally informative products; the addition of oxalic acid increases [M + H]+ ion abundances, and these fragment readily

Red supergiants as potential Type IIn supernova progenitors: Spatially resolved 4.6 micron CO emission around VY CMa and Betelgeuse

We present high-resolution 4.6micron CO spectra of the circumstellar environments of two RSGs that are potential SN progenitors: Betelgeuse and VY CMa. Around Betelgeuse, 12CO emission within 3arcsec follows a mildly clumpy but otherwise spherical shell, smaller than its 55arcsec shell in KI lambda7699. In stark contrast, 4.6micron CO emission around VY CMa is coincident with bright KI in its clumpy asymmetric reflection nebula, within 5arcsec of the star. Our CO data reveal redshifted features not seen in KI spectra of VY CMa, indicating a more isotropic distribution of gas punctuated by randomly distributed asymmetric clumps. The relative CO and KI distribution in Betelgeuse arises from ionization effects within a steady wind, whereas in VY CMa, KI is emitted from skins of CO cloudlets resulting from episodic mass ejections 500--1000 yr ago. In both cases, CO and KI trace potential pre-SN circumstellar matter: we conclude that an extreme RSG like VY CMa might produce a Type IIn event like SN1988Z if it were to explode in its current state, but Betelgeuse will not. VY CMa demonstrates that LBVs are not necessarily the only progenitors of SNe IIn, but it underscores the requirement that SNe IIn suffer enhanced episodic mass loss shortly before exploding.Comment: 16 pages, AJ accepte

Phase 2 Study of the Safety and Tolerability of Maraviroc-Containing Regimens to Prevent HIV Infection in Men Who Have Sex With Men (HPTN 069/ACTG A5305)

Maraviroc (MVC) is a candidate for human immunodeficiency virus (HIV) pre-exposure prophylaxis

2011 American College of Rheumatology recommendations for the treatment of juvenile idiopathic arthritis: Initiation and safety monitoring of therapeutic agents for the treatment of arthritis and systemic features

Guidelines and recommendations developed and/or endorsed by the American College of Rheumatology (ACR) are intended to provide guidance for particular patterns of practice and not to dictate the care of a particular patient. The ACR considers adherence to these guidelines and recommendations to be voluntary, with the ultimate determination regarding their application to be made by the physician in light of each patient’s individual circumstances. Guidelines and recommendations are intended to promote beneficial or desirable outcomes but cannot guarantee any specific outcome. Guidelines and recommendations developed or endorsed by the ACR are subject to periodic revision as warranted by the evolution of medical knowledge, technology, and practice

Introduction to organic chemistry

viii, 323 p.; 21 cm