Elucidating the mechanism and active site of the cyclohexanol dehydrogenation on copper-based catalysts: A density functional theory study

Abstract The dehydrogenation of cyclohexanol to cyclohexanone is very important in the manufacture of nylon. Copper-based catalysts are the most popular catalysts for this reaction, and on these catalysts the reaction mechanism and active site are in debate. In order to elucidate the mechanism and active site of the cyclohexanol dehydrogenation on copper-based catalysts, density functional theory with dispersion corrections were performed on up to six facets of copper in two different oxidation states: monovalent copper and metallic copper. By calculating the surface energies of these facets, Cu(111) and Cu2O(111) were found to be the most stable facets for metallic copper and for monovalent copper, respectively. On these two facets, all the possible elementary steps in the dehydrogenation pathway of cyclohexanol were calculated, including the adsorption, dehydrogenation, hydrogen coupling and desorption. Two different reaction pathways for dehydrogenation were considered on both surfaces. It was revealed that the dehydrogenation mechanisms are different on these two surfaces: on Cu(111) the hydrogen belonging to the hydroxyl is removed first, then the hydrogen belonging to the carbon is subtracted, while on Cu2O(111) the hydrogen belonging to the carbon is removed followed by the subtraction of the hydrogen in the hydroxyl group. Furthermore, by comparing the energy profiles of these two surfaces, Cu2O(111) was found to be more active for cyclohexanol dehydrogenation than Cu(111). In addition, we found that the coordinatively unsaturated copper sites on Cu2O(111) are the reaction sites for all the steps. Therefore, the coordinatively unsaturated copper site on Cu2O(111) is likely to be the active site for cyclohexanol dehydrogenation on the copper-based catalysts.

LL-37 Degradation by GCF: A Role for Porphyromonas gingivalis Proteinases?

Background: LL-37, composed of 37 amino acid residues, is an innate host defence peptide of the cathelicidin family. It is expressed by neutrophils, monocytes and epithelial cells and exhibits both anti-bacterial and immunomodulatory properties. LL-37 is however prone to proteolytic degradation by proteinases, thus potentially limiting its inherent host defence properties in the inflammatory milieu. Objectives: The present study was designed to determine whether LL-37 was degraded by components of gingival crevicular fluid (GCF) from healthy subjects or those with periodontitis. In addition, we aimed to deduce whether degradation of the peptide was accelerated in GCF samples which were determined to be positive for the periodontopathic bacterium Porphyromonas gingivalis. Methods: GCF and bacterial plaque samples, pre- and post non-surgical periodontal treatment, were collected from 4 individual sites in patients presenting with advanced periodontitis. In healthy subjects, GCF samples only were collected. Plaque samples were analysed by QPCR for the presence or absence of P. gingivalis. Pooled GCF samples from healthy sites; periodontitis sites which were P. gingivalis negative (Pg-); or periodontitis sites which were P. gingivalis positive (Pg+), were incubated with synthetic LL-37 for 0 – 180 min. The degradation products were then analysed by matrix-assisted laser desorption/ionisation time of flight mass spectrometry (MALDI-TOF MS). Results: LL-37 was not degraded when incubated with GCF from healthy subjects. In contrast, LL-37 was degraded after 30 min when incubated with Pg- GCF. However degradation of LL-37 was apparent after only 2 min incubation with Pg+ GCF and the parent molecule was almost completely degraded after 30 min. Conclusions: The rapid degradation of LL-37, particularly in Pg+ sites, highlights the limited role which this host defence peptide may play in the presence of biologically active proteinases. It also underscores a potent virulence mechanism of P. gingivalis used to circumvent innate host responses.

ALMA-resolved salt emission traces the chemical footprint and inner wind morphology of VY Canis Majoris

(abreviated) We aim to study the inner-wind structure (R<250 Rstar) of the well-known red supergiant VY CMa. We analyse high spatial resolution (~0".24x0".13) ALMA Science Verification (SV) data in band 7 in which four thermal emission lines of gaseous sodium chloride (NaCl) are present at high signal-to-noise ratio. For the first time, the NaCl emission in the inner wind region of VY CMa is spatially resolved. The ALMA observations reveal the contribution of up to four different spatial regions. The NaCl emission pattern is different compared to the dust continuum and TiO2 emission already analysed from the ALMA SV data. The emission can be reconciled with an axisymmetric geometry, where the lower density polar/rotation axis has a position angle of ~50 degrees measured from north to east. However, this picture can not capture the full morphological diversity, and discrete mass ejection events need to be invoked to explain localized higher-density regions. The velocity traced by the gaseous NaCl line profiles is significantly lower than the average wind terminal velocity, and much slower than some of the fastest mass ejections, signalling a wide range of characteristic speeds for the mass loss. Gaseous NaCl is detected far beyond the main dust condensation region. Realising the refractory nature of this metal halide, this hints at a chemical process preventing all NaCl from condensing onto dust grains. We show that in the case of the ratio of the surface binding temperature to the grain temperature being ~50, only some 10% of NaCl remains in gaseous form, while for lower values of this ratio thermal desorption efficiently evaporates NaCl. Photodesorption by stellar photons seems not to be a viable explanation for the detection of gaseous NaCl at 220 Rstar from the central star, and instead, we propose shock-induced sputtering driven by localized mass ejection events as alternative.