QENS and FTIR studies on binding states of benzene molecules adsorbed in zeolite HZSM-5 at room temperature

Fourier-transform infrared (FTIR) spectroscopy and quasi-elastic neutron scattering (QENS) were employed for monitoring of the binding states of benzene molecules, adsorbed in HZSM-5 zeolite at 300 K and for loadings of 0.6 to 7 molecules per unit cell. While the in-plane combination C-C and C-H stretching bands of adsorbed benzene remained una.ected, a splitting was observed in the out-of-plane C-H bending vibrational bands, a feature reported for the transformation of benzene from liquid to solid phase. Also, the intensity ratio of the in-plane C-C stretching band (ν19 of adsorbed benzene at 1479 cm-1 and the bands in the region ) 3100-3035 cm-1 due to fundamentals and combination C-C and C-H stretching vibrations indicated a trend observed typically for a condensed phase of benzene. No shift was observed in the frequency of the above-mentioned IR bands when zeolite samples exchanged with Na+ or Ca2+ were employed. QENS results suggest that the benzene molecules occluded in zeolitic pores (~3 molecules per unit cell) undergo a 6-fold rotation but their translation motion is too slow. Also, a high residence time of 16.5 ps was observed for the benzene entrapped in HZSM-5, compared to a time of ~2.5 ps reported for the liquid and ~19 ps for the solid state of benzene. These results reveal again the compression of the benzene molecules on adsorption in zeolitic pores. It is suggested that the benzene molecules confined in cavities experience a strong intermolecular interaction, giving rise eventually to their clustered state depending on the loading. In the clustered state, benzene molecules are packed with their plane parallel to zeolitic walls and interact with each other through p-electron clouds. No electronic bonding is envisaged between these clusters and the framework or the extra-framework zeolitic sites

β2→ 1-fructans modulate the immune system in vivo by direct interaction with the mucosa in a microbiota-independent fashion

It has been shown in vitro that only specific dietary fibers contribute to immunity, but studies in vivo are not conclusive. Here, we investigated degree of polymerization (DP) dependent effects of beta2-->1-fructans on immunity via microbiota-dependent and -independent effects. To this end, conventional or germ-free mice received short- or long-chain beta2-->1-fructan for 5 days. Immune cell populations in the spleen, mesenteric lymph nodes (MLNs), and Peyer's patches (PPs) were analyzed with flow cytometry, genome-wide gene expression in the ileum was measured with microarray, and gut microbiota composition was analyzed with 16S rRNA sequencing of fecal samples. We found that beta2-->1-fructans modulated immunity by both microbiota and microbiota-independent effects. Moreover, effects were dependent on the chain-length of the beta2-->1-fructans type polymer. Both short- and long-chain beta2-->1-fructans enhanced T-helper 1 cells in PPs, whereas only short-chain beta2-->1-fructans increased regulatory T cells and CD11b-CD103- dendritic cells (DCs) in the MLN. A common feature after short- and long-chain beta2-->1-fructan treatment was enhanced 2-alpha-l-fucosyltransferase 2 expression and other IL-22-dependent genes in the ileum of conventional mice. These effects were not associated with shifts in gut microbiota composition, or altered production of short-chain fatty acids. Both short- and long-chain beta2-->1-fructans also induced immune effects in germ-free animals, demonstrating direct effect independent from the gut microbiota. Also, these effects were dependent on the chain-length of the beta2-->1-fructans. Short-chain beta2-->1-fructan induced lower CD80 expression by CD11b-CD103- DCs in PPs, whereas long-chain beta2-->1-fructan specifically modulated B cell responses in germ-free mice. In conclusion, support of immunity is determined by the chemical structure of beta2-->1-fructans and is partially microbiota independent

Oral Antimicrobial Peptides and Biological Control of Caries

The presence of antimicrobial peptides (AMPs) in saliva may be a biological factor that contributes to susceptibility or resistance to caries. This manuscript will review AMPs in saliva, consider their antimicrobial and immunomodulatory functions, and evaluate their potential role in the oral cavity for protection of the tooth surface as well as the oral mucosa. These AMPs are made in salivary gland and duct cells and have broad antimicrobial activity. Alpha-defensins and LL37 are also released by neutrophils into the gingival crevicular fluid. Both sources may account for their presence in saliva. A recent study in middle school children aimed to determine a possible correlation between caries prevalence in children and salivary concentrations of the antimicrobial peptides human beta-defensin-3 (hBD-3), the cathelicidin, LL37, and the alpha-defensins. The levels of these AMPs were highly variable in the population. While levels of LL37 and hBD-3 did not correlate with caries experience, the mean alpha-defensin level was significantly higher in children with no caries than in children with caries (p < 0.005). We conclude that several types of AMPs that may have a role in oral health are present in unstimulated saliva. Low salivary levels of alpha-defensin may represent a biological factor that contributes to caries susceptibility. Our observation could lead to new ways to prevent caries and to a new tool for caries risk assessment

Structures of (5′S)-8,5′-Cyclo-2′-deoxyguanosine Mismatched with dA or dT

pubs.acs.org/cr