Common Variable Immunodeficiency Associated With Noninfectious Pulmonary Complications and Its Treatment: Beyond Immunoglobulin Therapy.

Common variable immunodeficiency (CVID) is a type of primary immunodeficiency that presents as a heterogenous disorder characterized by hypogammaglobinemia, poor response to vaccines, recurrent sinopulmonary infections, and can have noninfectious systemic manifestations. We performed a single-center, retrospective, observational study of five patients with noninfectious complications of CVID. All patients had CVID as defined by the European Society of Immunodeficiencies criteria and had received intravenous immunoglobulin therapy.

Probing the Exit Channel of the OH + CHOH → HO + CHO Reaction by Photodetachment of CHO(HO).

Transition state dynamics of bimolecular reactions can be probed by photodetachment of a precursor anion when the Franck-Condon region of the corresponding neutral potential energy surface is near a saddle point. In this study, photodetachment of anions at / = 49 enabled investigation of the exit channel of the OH + CHOH → HO + CHO reaction using photoelectron-photofragment coincidence spectroscopy. High-level coupled-cluster calculations of the stationary points on the anion surface show that the methoxide-water cluster CHO(HO) is the stable minimum on the anion surface.

Dissociative Photodetachment Dynamics of the OH(CH) Anion Complex.

Photoelectron-photofragment coincidence (PPC) measurements on OH(CH) anions at a photon energy of 3.20 eV revealed stable and dissociative photodetachment product channels, OH-CH + e and OH + CH + e, respectively. The main product channel observed was dissociation to the reactants (>67%), OH + CH ( = 0, 1, 2) + e, where vibrational excitation in the C-H stretching modes of the CH photofragments corresponds to a minor channel.

Quantum Chemical and Statistical Rate Theory Studies of the Vinyl Hydroperoxides Formed in trans-2-Butene and 2,3-Dimethyl-2-butene Ozonolysis.

The vinyl hydroperoxide (VHP), the major isomerization product of the syn-alkyl Criegee intermediate (CI) formed in alkene ozonolysis, is a direct precursor of hydroxyl radical (OH), the most important oxidant in the troposphere. While simulations of CI reactivity have usually assumed the VHP to be a prompt and quantitative source of OH, recent quantum chemical studies have revealed subtleties in VHP reactivity such as a barrier to peroxy bond homolysis and a possible rearrangement to a hydroxycarbonyl. In this work, we use M06-L, Weizmann-1 Brueckner Doubles, and equation-of-motion spin-flip coupled-cluster theories to calculate a comprehensive reaction mechanism for the syn and anti conformers of the parent VHP formed in trans-2-butene ozonolysis and the 1-methyl VHP formed in 2,3-dimethyl-2-butene ozonolysis.