RESUMO
Hydroxybenzylammonium compounds can undergo a reversible 1,4- or 1,6-elimination to afford quinone methide intermediates after release of the amine. These molecules are useful for the reversible conjugation of payloads to amines. We hypothesized that aromaticity could be used to alter the rate of reversibility as a distinct thermodynamic driving force. We describe the use of density functional theory (DFT) calculations to determine the effect of aromaticity on the rate of release of the amine from hydroxybenzylammonium compounds. Namely, the aromatic scaffold affects the dearomatization reaction to reduce the kinetic barrier and prevent the reversibility of the amine elimination. We consequently synthesized a small library of polycyclic hydroxybenzylammoniums, which resulted in a range of release half-lives from 18 minutes to 350 hours. The novel mechanistic insight provided herein significantly expands the range of release rates amenable to hydroxybenzylammonium-containing compounds. This work provides another way to affect the rate of payload release in hydroxybenzylammoniums.
RESUMO
Bioconversion of lignocellulosic biomass is a highly promising alternative to rapidly reduce reliance on fossil fuels and greenhouse gas emissions. However, the use of lignocellulosic biomass is limited by the challenges of efficient degradation strategies. Given this need, Bacillus tropicus (B. tropicus) with cellulose degradation ability was isolated and screened from rotten dahlia. The strain efficiently utilized coconut oil cake (COC) to secrete 167.3 U/mL of cellulase activity. Electron microscopy results showed significant changes in the structure and properties of cellulose after treatment with B. tropicus, which increased the surface accessibility and the efficiency of the hydrolysis process. The functional group modification observed by Fourier transform infrared spectroscopy indicated the successful depolymerization of COC. The X-ray diffraction pattern showed that the crystallinity index increased from 44.8% to 48.2% due to the hydrolysis of the amorphous region in COC. The results of colorimetry also reveal an efficient hydrolysis process. A co-culture of B. tropicus and Saccharomyces cerevisiae was used to produce ethanol from COC waste, and the maximum ethanol yield was 4.2 g/L. The results of this work show that B. tropicus can be used to prepare biotechnology value-added products such as biofuels from lignocellulosic biomass, suggesting promising utility in biotechnology applications.
RESUMO
Agricultural ditches are significant methane (CH4) sources since substantial nutrient inputs stimulate CH4 production and emission. However, few studies have quantified the role of diffusion and ebullition pathways in total CH4 emission from agricultural ditches. This study measured the spatiotemporal variations of diffusive and ebullitive CH4 fluxes from a multi-level ditch system in a typical temperate agriculture area, and assessed their contributions to the total CH4 emission. Results illustrated that the mean annual CH4 flux in the ditch system reached 1475.1 mg m-2 d-1, among which 1376.7 mg m-2 d-1 was emitted via diffusion and 98.5 mg m-2 d-1 via ebullition. Both diffusive and ebullitive fluxes varied significantly across different types of ditches and seasons, with diffusion dominating CH4 emission in middle-size ditches and ebullition dominating in large-size ditches. Diffusion was primarily driven by large nutrient inputs from adjacent farmlands, while hydrological factors like water temperature and depth controlled ebullition. Overall, CH4 emission accounted for 86 % of the global warming potential across the ditch system, with 81 % attributed to diffusion and 5 % to ebullition. This study highlights the importance of agricultural ditches as hotspots for CH4 emissions, particularly the dominant role of the diffusion pathway.