Interaction between Acetic Acid and Glycerol: A Model for Secondary Reactions during Holocellulose Pyrolysis.

During pyrolysis of holocellulose, secondary reactions of the primary pyrolytic products inevitably occur, affecting the final pyrolytic product distribution. Carboxylic acids from primary pyrolysis process have significant interaction effects on both holocellulose and its pyrolytic products, whereas, the interaction mechanisms are still unclear. In the present study, acetic acid is selected as the typical carboxylic acid product, and glycerol is selected to represent the various hydroxyl-based compounds (both holocellulose and pyrolytic products such as anhydrosugars, etc.). The density functional theory (DFT) method is adopted to investigate the interaction mechanisms between them. Calculation results indicate that acetic acid and glycerol have strong interactions, with acetic acid acting as a catalyst for these interactions in two patterns. (I) Acetic acid enhances the dehydration reactions of glycerol with low energy barriers. (II) Acetic acid and glycerol undergo esterification to form an ester intermediate which then decomposes via various reactions. In addition, the decomposition of acetic acid can also be promoted by the catalysis of glycerol in a certain degree. This study reveals the basic interaction mechanisms between carboxylic acids and hydroxyl-based compounds, providing fundamental information to understand the secondary reactions during pyrolysis of holocellulose.

Theoretical Investigation of the Formation Mechanism of NH3 and HCN during Pyrrole Pyrolysis: The Effect of H2O.

Coal is a major contributor to the global emission of nitrogen oxides (NOx). The NOx formation during coal utilization typically derives from the thermal decomposition of N-containing compounds (e.g., pyrrolic groups). NH3 and HCN are common precursors of NOx from the decomposition of N-containing compounds. The existence of H2O has significant influences on the pyrrole decomposition and NOx formation. In this study, the effects of H2O on pyrrole pyrolysis to form NOx precursors HCN and NH3 are investigated using the density functional theory (DFT) method. The calculation results indicate that the presence of H2O can lead to the formation of both NH3 and HCN during pyrrole pyrolysis, while only HCN is formed in the absence of H2O. The initial interaction between pyrrole and H2O determines the N products. NH3 will be formed when H2O attacks the C2 position of pyrrole with its hydroxyl group. On the contrary, HCN will be generated instead of NH3 when H2O attacks the C3 position of pyrrole with its hydroxyl group. In addition, the DFT calculations clearly indicate that the formation of NH3 will be promoted by H2O, whereas the formation of HCN is inhibited.

Ammonium and phosphate limitation in 1,3-propanediol production by Klebsiella pneumoniae.

Excretion of 1,3-propanediol (1,3-PD) by K. pneumoniae was compared in ammonium- and phosphate-limited chemostat cultures running with an excess of glycerol. 59 and 43% catabolic flux were directed to 1,3-PD in ammonia-limited cultures and phosphate-limited cultures at dilution rate of 0.1 h(-1), respectively. Ammonia-limited fed-batch cultures produced 61 g 1,3-PD l(-1) and a total of 15 g l(-1) organic acid in 36 h. However, phosphate-limited fed-batch cultures excreted 61 g lactate l(-1) and 44 g 1,3-PD l(-1).

MicroRNA-134-5p Regulates Media Degeneration through Inhibiting VSMC Phenotypic Switch and Migration in Thoracic Aortic Dissection.

Abnormal phenotypic switch, migration, and proliferation of vascular smooth muscle cells (VSMCs) are hallmarks for pathogenesis of thoracic aortic dissection (TAD). In the current study, we identified miR-134-5p as a critical regulator controlling human VSMC phenotypic switch and migration to investigate whether miR-134-5p affects human VSMC functions and development of TAD. Using miRNA microarray of aorta specimens from 12 TAD and 12 controls, we identified miR-134-5p, which was significantly downregulated in TAD tissues. With qPCR detection, we found that miR-134-5p was also evidently decreased in human AoSMCs. Ectopic expression of miR-134-5p obviously promoted VSMC differentiation and expression of contractile markers, such as α-SMA, SM22α, and MYH11. miR-134-5p potently inhibited PDGF-BB-induced VSMC phenotypic switch and migration. We further identified STAT5B and ITGB1 as downstream targets of miR-134-5p in human VSMCs and proved them to be mediators in VSMC phenotypic switch and progression of TAD. Finally, Ad-miR-134-5p obviously suppressed the aorta dilatation and vascular media degeneration by 39% in TAD mice after vascular injury induced by Ang II. Our findings revealed that miR-134-5p was a novel regulator in vascular remodeling and pathological progress of TAD via targeting STAT5B/ITGB1 expression. Targeting miR-134-5p or its downstream molecules in VSMCs might develop new avenues in clinical treatment of TAD.

Review of Herbal Traditional Chinese Medicine for the Treatment of Diabetic Nephropathy.

Diabetic nephropathy (DN) is the most serious chronic complications of diabetes; 20-40% of diabetic patients develop into end stage renal disease (ESRD). However, exact pathogenesis of DN is not fully clear and we have great difficulties in curing DN; poor treatment of DN led to high chances of mortality worldwide. A lot of western medicines such as ACEI and ARB have been demonstrated to protect renal function of DN but are not enough to delay or retard the progression of DN; therefore, exploring exact and feasible drug is current research hotspot in medicine. Traditional Chinese medicine (TCM) has been widely used to treat and control diabetes and its complications such as DN in a lot of scientific researches, which will give insights into the mechanism of DN, but they are not enough to reveal all the details. In this paper, we summarize the applications of herbal TCM preparations, single herbal TCM, and/or monomers from herbal TCM in the treatment of DN in the recent 10 years, depicting the renal protective effects and the corresponding mechanism, through which we shed light on the renal protective roles of TCM in DN with a particular focus on the molecular basis of the effect and provide a beneficial supplement to the drug therapy for DN.

Catalytic fast pyrolysis of cellulose and biomass to produce levoglucosenone using magnetic SO4(2-)/TiO2-Fe3O4.

Magnetic superacid (SO4(2-)/TiO2-Fe3O4) was prepared for catalytic fast pyrolysis of cellulose and poplar wood to produce levoglucosenone (LGO). Its catalytic activity was evaluated via pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS) experiments, and compared with the non-magnetic SO4(2-)/TiO2, phosphoric acid (H3PO4) and sulfur acid (H2SO4) catalysts. Moreover, the LGO yield was quantitatively determined. The results indicated that the magnetic SO4(2-)/TiO2-Fe3O4 was effective to selectively produce LGO from both cellulose and poplar wood. Its catalytic capability was a little better than the non-magnetic SO4(2-)/TiO2 and H3PO4, and much better than the H2SO4. The maximal LGO yields from both cellulose and poplar wood were obtained at 300 °C with the feedstock/catalyst ratio of 1/1, reaching as high as 15.43 wt% from cellulose and 7.06 wt% from poplar wood, respectively.

Theoretical study on the mechanisms of cellulose dissolution and precipitation in the phosphoric acid-acetone process.

Phosphoric acid-acetone fractionation was applied to pretreat lignocellulose for production of cellulosic ethanol. Cellulose solubility properties in H(2)O, H(3)PO(4) and CH(3)COCH(3) were simulated. Atomic geometry and electronic properties were computed using density functional theory with local-density approximation. H(3)PO(4) molecule is adsorbed between two cellulose segments, forming four hydrogen bonds with E(B) of -1.61 eV. Density of state for cellulose in H(3)PO(4)-cellulose system delocalizes without obvious peak. E(gap) of 4.46 eV is much smaller than that in other systems. Molecular dynamics simulation indicates that fragments of double glucose rings separate in the cellulose-H(3)PO(4) interaction system. Icy CH(3)COCH(3) addition leads to re-gathering of separated fragments. Reaction energy of cellulose in three solvents is around 3.5 eV, implying that cellulose is chemically stable. Moreover, theoretical results correspond to the experiments we have performed, showing that cellulose dissolves in H(3)PO(4), flocculates after CH(3)COCH(3) addition, and finally becomes more liable to be hydrolyzed into glucoses.