The Role of the Mannich Reaction in Nitrogen Migration during the Co-Hydrothermal Carbonization of Bovine Serum Albumin and Lignin with Various Forms of Acid-Alcohol Assistance.

Co-hydrothermal carbonization (co-HTC) of N-rich and lignocellulosic biomass is a potential way to produce hydrochar with high yield and quality, but the nitrogen will also enrich in a solid product. In this study, a novel co-HTC with acid-alcohol assistance is proposed, and the model compounds bovine serum albumin (BSA) and lignin were used to investigate the role of the acid-alcohol-enhanced Mannich reaction in nitrogen migration. The results showed that the acid-alcohol mixture could inhibit nitrogen enrichment in solids and the order of the denitrification rate was acetic acid > oxalic acid > citric acid. Acetic acid promoted solid-N hydrolysis to NH4+ while oxalic acid preferred to convert it to oil-N. More tertiary amines and phenols were generated with oxalic acid-ethanol addition and then formed quaternary-N and N-containing aromatic compounds through the Mannich reaction. In the citric acid-ethanol-water solution, NH4+ and amino acids were captured to form diazoxide derivatives in oil and pyrroles in solids through both nucleophilic substitution and the Mannich reaction. The results are able to guide biomass hydrochar production with the targeted regulation of nitrogen content and species.

Gas-pressurized torrefaction of lignocellulosic solid wastes: Low-temperature deoxygenation and chemical structure evolution mechanisms.

A novel gas-pressurized (GP) torrefaction realizes deeper deoxygenation of lignocellulosic solid wastes (LSW) to as high as 79% compared to traditional torrefaction (AP) with the oxygen removal of 40% at the same temperature. However, the deoxygenation and chemical structure evolution mechanisms of LSW during GP torrefaction are currently unclear. In this work, the reaction process and mechanism of GP torrefaction were studied through follow-up analysis of the three-phase products. Results demonstrate gas pressure causes over 90.4% of cellulose decomposition and the conversion of volatile matter to fixed carbon through secondary polymerization reactions. Above phenomena are completely absent during AP torrefaction. A deoxygenation and structure evolution mechanism model is developed through analysis of fingerprint molecule and C structure. This model not only provides theoretical guidance for optimization of the GP torrefaction, but also contributes to the mechanism understanding of pressurized thermal conversion processes of solid fuel, such as coal and biomass.

Catalytic pyrolysis of biomass wastes over Org-CaO/Nano-ZSM-5 to produce aromatics: Influence of catalyst properties.

Catalytic pyrolysis of biomass wastes is a promising way to produce aromatics. Based on the conventional CaO/ZSM-5 system, this study aims to improve the aromatics yields by developing an upgraded system which combined nanosized ZSM-5 with CaO from organic calcium precursors (Org-CaO/NZSM-5). The results showed that the aromatics proportion in bio-oil from pyrolysis of Jatropha de-oiled cake with Org-CaO/NZSM-5 increased to 93%. The corresponding yield of BTX (benzene, toluene and xylene) and naphthalene was around 70% which was almost twice than that with conventional CaO/ZSM-5. Org-CaO showed better thermal cracking ability and deoxygenation with more hydrocarbons intermediates and higher H/Ceff of vapors, contributing to enhanced formation of BTX over NZSM-5. NZSM-5 contained much more mesopores and acid sites on external surface, promoting higher conversion of bulky molecules into naphthalenes. Compared with peanut shell, corncob and bagasse pyrolysis, Jatropha de-oiled cake pyrolysis produced much higher aromatics with Org-CaO/NZSM-5.

Correlations between hydrochar properties and chemical constitution of orange peel waste during hydrothermal carbonization.

For efficient hydrothermal treatment of biomass, this study aims to figure out the correlations between complex chemical constitution of orange peel (OraPeel) as typical bio-waste and the physicochemical structure of its derived hydrochar, which could be utilized to adjust hydrochar properties for specific applications (e.g., adsorbent, fuel) by regulating respective proportions of each component in bio-waste. Cellulose, hemicellulose and lignin were used as the control variables of feedstocks composition in this work. After hydrothermal process, lignin added feedstock produced more hydrochar, which contained rougher surface with nearly doubled BET areas and more benzene rings. Hemicellulose-aided hydrochar possessed higher density of carbonaceous microspheres and richer hydroxyl. This char was simultaneously covered by more esters or lactones with more aromatic oxygen-containing groups inside. Similar to hemicellulose, cellulose improved the formation of diverse oxygenous groups but reduced the size of microspheres on hydrochar.

Retrograde facilitation of verbal memory by trihexyphenidyl in healthy elderly with and without the APOE epsilon4 allele.

Retrograde facilitation (RF) of information learned prior to acute oral administration of trihexyphenidyl, a preferential muscarinic M1 receptor antagonist which impairs new learning, was studied in 24 healthy elderly subjects. The relationship between the RF induced by this anticholinergic drug and the APOE epsilon4 allele was also examined. Acute adverse performance effects of trihexyphenidyl (1- and 2mg) were determined using the Buschke Selective Reminding Test administered pre-drug and at 1, 2.5, and 5h post-drug. Recall of pre-drug words at the end of the fifth hour neuropsychological assessment (end-of-session recall) was of primary interest. Words studied before drug administration were better recalled following 2mg trihexyphenidyl compared to placebo, and this RF effect was not affected by the APOE epsilon4 allele. Better recall of pre-drug words following 2-mg trihexyphenidyl was associated with a greater amnestic effect of this dose. Our findings demonstrated that RF induced by trihexyphenidyl was related to anterograde amnestic effects of the drug and resulted in part from drug-induced reduction of retroactive interference.

Do rats represent time logarithmically or linearly?

This study examined two possible psychophysical time scales, a logarithmic representation of time with constant variability and a linear representation of time with scalar variability. Twenty-four rats were tested on a modified temporal bisection procedure in which multiple responses could occur in a 10-s time window after the termination of a stimulus. The number of "long" or "short" responses was used as a measure of the rats' certainty of the duration of the presented interval. Data were analyzed with signal detection theory, and straight lines were fit to the zROC curves with the assumptions of a logarithmic representation of time with constant variability and a linear representation of time with scalar variability. The logarithmic representation of time with constant variability provided a better fit to the data than the linear representation of time with scalar variability.

Applications of timing theories to a peak procedure.

This article describes applications of scalar expectancy theory (SET), learning-to-time theory (LeT), and Packet theory to data from a peak procedure. Twelve rats were trained in a multiple cued-interval procedure with two fixed intervals (60 and 120 s) signaled by houselight and white noise. Twenty-five percent of the cycles were nonfood cycles, which were 360 s long and had no reinforcement. Mean and individual response rates on nonfood cycles were fitted with explicit solutions of SET, LeT and Packet theory. Applications of the three timing theories were compared in terms of goodness of fit and complexity.

Effects of repeated acquisitions and extinctions on response rate and pattern.

The procedure developed by R. A. Rescorla (2002) was used to study the effects of repeated acquisitions and extinctions of head entry responses into a food cup by rats. In each of 4 20-session phases, food was delivered at the end of particular 30-s auditory and visual stimuli, but not at the end of different 30-s auditory and visual stimuli. Based on response rates to individual stimuli and compound stimuli, the increase in response rate in acquisition occurred more rapidly than the decrease in extinction. Acquisition, but not extinction, occurred faster after successive transitions between acquisition and extinction. Temporal gradients of responding developed during acquisition and remained during extinction. Conclusions based on mean response rate, temporal gradients, and transfer tests were consistent.