19 HZSM-5 extrudates, its two constituents (HZSM-5 zeolite and alumina binder), and SiC for 20 reference were tested after steam treatment for the upgrading of wheat straw fast pyrolysis (FP) 21 vapors from an ablative bench scale system. In addition, mesoporosity was added to the HZSM-5 crystals of the zeolite/Al 2 O 3 extrudates by desilication, which decreased the microporous volume 23 and led to enhanced weak acidity and less strong acidity compared to the parent extrudates. For 24 increasing biomass-to-catalyst ratios (w/w, B:C), oils were collected and analyzed for elemental 25 composition, total acid number (TAN), moisture, molecular weight, evaporation characteristics, 26 and chemical composition by gas chromatography mass spectrometry with flame ionization 27 detection (GC-MS/FID), 1 H nuclear magnetic resonance (NMR), 13 C NMR, and two-dimensional 28 heteronuclear single-quantum correlation (2D HSQC) NMR. Compared to Al 2 O 3 , catalysts 29 containing HZSM-5 promoted aromatization and limited the coke formation due to its shape 30 selective micropores. Nevertheless, Al 2 O 3 was effective in deoxygenation. At B:C ~7, 23 wt-% 31 carbon/25 % energy recovery in the oil fraction was obtained while reducing the oxygen content 32 by 45 % relative to a thermal reference oil fraction obtained over a SiC bed. As such, Al 2 O 3 offers 33 certain benefits compared to HZSM-5 based catalysts due to its lower cost and better hydrothermal 34 stability with respect to acidity. At a catalyst temperature of 500 °C, the introduction of mesopores 35 to HZSM-5 extrudates led to higher energy recovery as oil compared to the parent HZSM-5 36 extrudates. At B:C = 6.3, 23 wt-% carbon/26% energy recovery in the oil phase was achieved 37 while removing 45% of the oxygen functionalities relative to the thermal reference bio-oil.38 Compared to deep deoxygenation for direct hydrocarbon production, mild deoxygenation 39 improved the energy recoveries of the oil fractions and appears viable for pretreating pyrolysis 40 vapors before co-processing bio-oils with fossil oil in refineries.
Capsular polysaccharides (CPS) are crucial virulence factors of Streptococcus pneumoniae. The previously unknown CPS structures of the pneumococcal serogroup 16 (serotypes 16F and 16A) were thoroughly elucidated by nuclear magnetic resonance (NMR) spectroscopy and verified by chemical analysis. The following repeat unit structures were determined: 16F, -3)-α-l-Rhap-[4-P-1-Gro]-(1-3)-α-d-Glcp-[(6-P-1)-Gro]-(1-3)-β-l-Rhap-[2-OAc]-(1-4)-β-d-Glcp-(1-; 16A, -3)-β-d-Galf-[2-OAc (70%)]-(1-3)-α-l-Rhap-(1-2)-α-l-Rhap-(1-3)-α-d-Galp-[(6-P-1)-Gro]-(1-3)-β-d-Galp-(1-4)-β-d-Glcp-(1- (OAc, O-acetyl substitution; P-1-Gro, glycerol-1-phosphate substitution). A further analysis of CPS biosynthesis of serotypes 16F and 16A, in conjunction with published cps gene bioinformatics analysis and structures of related serotypes, revealed presumable specific function of glycosyltransferase, acetyltransferase, phosphotransferase, and polymerase. The functions of glycosyltransferases WcxN and WcxT were proposed for the first time, and they were assigned to catalyze linkage of α-l-Rhap-(1-3)-α-d-Glcp and α-l-Rhap-(1-2)-α-l-Rhap, respectively. Furthermore, since serotype 16F was genetically close to serogroup 28, cross-reactions between serogroup 16 and serogroup 28 were studied using diagnostic antisera, which provided further understanding of antigenic properties of CPS and diagnostic antisera. Interestingly, serotype 16F cross-reacted with factor antisera 28b and 11c. Meanwhile, serotype 16A cross-reacted with factor antiserum 11c. IMPORTANCE The vaccine pressure against Streptococcus pneumoniae could result in a change of prevalence in carriage and invasive serotypes. As such, it is necessary to monitor the distribution to achieve successful vaccination of the population, and similarly, it is important to increase the knowledge of even the currently less prevalent serotypes. The CPS are vital for the virulence of the pathogen, and antigenic properties of CPS are based on the structure. Consequently, a better understanding of the structure, biosynthesis, and serology of the capsular polysaccharides can be of great importance toward developing future diagnostic tools and vaccines.
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