Near-edge x-ray absorption fine structure spectra and specific dissociation of small peptoid molecules.

In this study, the total ion yield near-edge x-ray absorption fine structure spectra of four similar peptoid molecules, which differ in the numbers and positions of methyl groups, were investigated experimentally and theoretically. At each excitation energy, the intensity and branching ratio of each ionic product were measured. At a few resonant excitation energies, a specific dissociation of the C-CO bond at the nitrogen and oxygen K-edges and of the N-CO bond at the carbon K-edge was dominant, which correlated well with the predicted destination antibonding orbitals of the core electron excitation. These specific dissociation mechanisms of small peptoid molecules could provide insights into similar phenomena that occur in peptide molecules.

Is the N2A Category Still Necessary for Oral Cancer Patients After Extranodal Extension Upgrade?

BACKGROUND: The presence of single-node metastasis (Ns) sometimes could be encountered in patients with oral squamous cell carcinoma (OSCC). The survival outcome for different Ns should be worthy of discussion. METHODS: Patients diagnosed with OSCC at the National Taiwan University Hospital between January 2007 and December 2018 were reviewed. All patients with Ns were classified into two groups: with and without extranodal extension (ENE). RESULTS: We analyzed 311 OSCC patients with Ns: 77 (24.76%) with and 234 (75.24%) without ENE. Lymph node (LN) >3 cm was the only significant factor associated with ENE (odds ratio 17.21, p < 0.001). The 5-year, disease-free survival of N1/N2A and N3B patients was 60.5% and 49.4%, respectively (p = 0.04), and the 5-year overall survival was 63.1% and 33.6%, respectively (p = 0.0001). Four fifths of Ns patients with LN >3 cm were upgraded to N3B category as ENE+. Postoperative radiotherapy (PORT) could provide significant benefit in regional control for Ns patients with (p = 0.03) and without (p = 0.0004) other adverse features. After multivariant Cox analysis, ENE+ was a modest and significant risk factor for disease-free (p = 0.08) and overall survival (p = 0.001). By contrast, the LN>3cm and N2A category were not significant risk factors for disease-free and overall survival. CONCLUSIONS: For OSCC patients with Ns, the survival outcome between N3B category and N1/N2A category was significantly different. After ENE+ upgrades (>80%), there were fewer N2A patients, and these patients became more comparable to N1 patients. PORT could significantly improve regional control for Ns patients.

A mechanistic study of hydrogen gas sensing by PdO nanoflake thin films at temperatures below 250 °C.

We prepared PdO nanoflake thin films on the SiO2 substrate by reactive sputter deposition, and studied their sensing response to H2 at temperatures between 25 and 250 °C. In addition to the oxygen ionosorption model, which is used to describe the early H2 sensing response over the temperature range studied, the H2 sensing kinetics of the PdO thin films can be separated into three temperature regimes: temperatures below 100 °C, around 150 °C and above 200 °C. At temperatures below 100 °C, PdO reduction is the dominant reaction affecting the H2 sensing behavior. At temperatures around 150 °C, Pd reoxidation kinetically competes with PdO reduction leading to a complicated sensing characteristic. Active PdO reduction by H2 promotes the continuing growth of Pd nanoislands, facilitating dissociative oxygen adsorption and thus the subsequent Pd reoxidation in the H2-dry air gas mixture. The kinetic competition between the PdO reduction and reoxidation at 150 °C leads to the observation of an inverse of the increase in the sensor conductivity. At temperatures above 200 °C, the PdO sensor exhibits a sensor signal monotonically increasing with the H2 concentration, and the H2 sensing behavior is consistent with the Mars-van-Krevelen redox mechanism.

Distribution and hosts of arsenic in a sediment core from the Chianan Plain in SW Taiwan: Implications on arsenic primary source and release mechanisms.

High arsenic abundance of 50-700µg/L in the groundwater from the Chianan Plain in southwestern Taiwan is a well-known environmental hazard. The groundwater-associated sediments, however, have not been geochemically characterized, thus hindering a comprehensive understanding of arsenic cycling in this region. In this study, samples collected from a 250m sediment core at the centre of the Chianan Plain were analyzed for arsenic and TOC concentrations (N=158), constituent minerals (N=25), major element abundances (N=105), and sequential arsenic extraction (N=23). The arsenic data show a prevalence of >10mg/kg with higher concentrations of 20-50mg/kg concentrated at 60-80 and 195-210m. Arsenic was extracted mainly as an adsorbate on clay minerals, as a co-precipitate in amorphous iron oxyhydroxide, and as a structural component in clay minerals. Since the sediments consist mainly of quartz, chlorite, and illite, the correlations between arsenic concentration and abundances of K2O and MgO pinpoint illite and chlorite as the major arsenic hosts. The arsenic-total iron correlation reflects the role of chlorite along with the contribution from amorphous iron oxyhydroxide as indicated by arsenic extraction data. Organic matter is not the dominant arsenic host for low TOC content, low arsenic abundance extracted from it, and a relatively low R(2) of the arsenic-TOC correlation. The major constituent minerals in the sediments are the same as those of the upriver metapelites, establishing a sink-source relationship. Composition data from two deep groundwater samples near the sediment core show Eh values and As(V)/As(III) ratios of reducing environments and high arsenic, K, Mg, and Fe contents necessary for deriving arsenic from sediments by desorption from clay and dissolution of iron oxyhydroxide. Therefore, groundwater arsenic was mainly derived from groundwater-associated sediments with limited contributions from other sources, such as mud volcanoes.