Resonance Raman Spectroscopy Reveals pH-Dependent Active Site Structural Changes of Lactoperoxidase Compound 0 and Its Ferryl Heme O–O Bond Cleavage Products

The first step in the enzymatic cycle of mammalian peroxidases, including lactoperoxidase (LPO), is binding of hydrogen peroxide to the ferric resting state to form a ferric-hydroperoxo intermediate designated as Compound 0, the residual proton temporarily associating with the distal pocket His109 residue. Upon delivery of this “stored” proton to the hydroperoxo fragment, it rapidly undergoes O–O bond cleavage, thereby thwarting efforts to trap it using rapid mixing methods. Fortunately, as shown herein, both the peroxo and the hydroperoxo (Compound 0) forms of LPO can be trapped by cryoradiolysis, with acquisition of their resonance Raman (rR) spectra now permitting structural characterization of their key Fe–O–O fragments. Studies were conducted under both acidic and alkaline conditions, revealing pH-dependent differences in relative populations of these intermediates. Furthermore, upon annealing, the low pH samples convert to two forms of a ferryl heme O–O bond-cleavage product, whose ν(Fe═O) frequencies reflect substantially different Fe═O bond strengths. In the process of conducting these studies, rR structural characterization of the dioxygen adduct of LPO, commonly called Compound III, has also been completed, demonstrating a substantial difference in the strengths of the Fe–O linkage of the Fe–O–O fragment under acidic and alkaline conditions, an effect most reasonably attributed to a corresponding weakening of the trans-axial histidyl imidazole linkage at lower pH. Collectively, these new results provide important insight into the impact of pH on the disposition of the key Fe–O–O and Fe═O fragments of intermediates that arise in the enzymatic cycles of LPO, other mammalian peroxidases, and related proteins

Consonant Context Effects on Vowel Sensorimotor Adaptation

Speech sensorimotor adaptation is the short-term learning of modified articulator movements evoked through sensory-feedback perturbations. A common experimental method manipulates acoustic parameters, such as formant frequencies, using real time resynthesis of the participant\u27s speech to perturb auditory feedback. While some studies have examined phrases comprised of vowels, diphthongs, and semivowels, the bulk of research on auditory feedback-driven sensorimotor adaptation has focused on vowels in neutral contexts (/hVd/). The current study investigates coarticulatory influences of adjacent consonants on sensorimotor adaptation. The purpose is to evaluate differences in the adaptation effects for vowels in consonant environments that vary by place and manner of articulation. In particular, we addressed the hypothesis that contexts with greater intra-articulator coarticulation and more static articulatory postures (alveolars and fricatives) offer greater resistance to vowel adaptation than contexts with primarily inter-articulator coarticulation and more dynamic articulatory patterns (bilabials and stops). Participants completed formant perturbation-driven vowel adaptation experiments for varying CVCs. Results from discrete formant measures at the vowel midpoint were generally consistent with the hypothesis. Analyses of more complete formant trajectories suggest that adaptation can also (or alternatively) influence formant onsets, offsets, and transitions, resulting in complex formant pattern changes that may reflect modifications to consonant articulatio

Coincident energy and angular distributions in xenon 4d_5/2 inner-shell double photoionization

We report on measurements of the triply differential cross section for the 4d(5/2) inner-shell photoionization in xenon followed by N(5)O(2,3)O(2,3) Auger decay using electron-electron coincidence spectroscopy. The experimental setup made it possible to obtain the first coincident angular distributions for the (1D2) and (3P2) final states at a photon energy of 97.45 eV. Relative amplitudes and phases describing the photoionization were estimated from these angular distributions

Complementary grazing systems for beef cattle production

Pasture productivity in Iowa often is limited by the low yield of cool-season grasses in the summer. This project considers whether uneven seasonal distribution in pastures could be improved by including species that perform better under higher temperatures

Angle-resolved two-dimensional mapping of electron emission from the inner-shell 2p excitations in Cl₂

Angle-resolved Auger and valence photoelectron spectra were measured over a 14-eV photon energy range across the Cl2 2p ionization thresholds. The measurements were carried out using highly efficient time-of-flight spectrometers coupled with photons from the Atomic and Molecular undulator beamline of the Advanced Light Source and an advanced data-acquisition system. Auger-electron spectra of 2→pσ* and 2→pnl resonances were analyzed and the evolution of the resonant Auger to the normal Auger decay distorted by postcollision interaction was examined. We find that valence photoionization channels do not resonate strongly at the photon energies of the core-to-Rydberg excitation, in contrast to the strongly resonating ones observed in the HCl molecule. Auger decay spectra of the 2p−1σ* resonances showed no evidence of atomic transitions in Cl*, also in contrast to HCl. In addition, angular distribution of the photoelectron and Auger-electron lines was derived

Radiocarbon dating wooden carvings and skeletal remains from Pitch Lake, Trinidad

Since the mid 19th century, rare prehistoric wooden carvings and human skeletal remains have been dredged from Pitch Lake, Trinidad, during commercial asphalt mining. Establishing a chronology for these objects is challenging, due to both a lack of stratigraphic and contextual information and the necessity to completely remove any pitch to ensure accurate radiocarbon dates. A range of solvent extraction protocols was tested to identify the most suitable one for pretreating the Pitch Lake artefacts, and then applied to ten wooden objects and a human cranium recovered from the lake. Several of these objects yielded earlier dates than expected, raising concerns that pitch had remained after pretreatment and had affected the dates. Pyrolysis-GC/MS and optical microscopy techniques were applied to material from the human cranium, a weaving tool, and a small bowl. These techniques, as well as routinely applied laboratory quality assurance procedures, indicated that there was no residual pitch within the cranium or the weaving tool after pretreatment, giving confidence to the dates. However, the small bowl was observed to still be contaminated with pitch after extensive pretreatment, indicating that the date is too old and can only be considered as a terminus post quem