Aquatic humic substances (AHS) isolated from two characteristic seasons of the Negro river, winter and summer corresponding to floody and dry periods, were structurally characterized by 13C nuclear magnetic ressonance. Subsequently, AHS aqueous solutions were irradiated with a polychromatic lamp (290-475 nm) and monitored by its total organic carbon (TOC) content, ultraviolet-visible (UV-vis) absorbance, fluorescence, and Fourier transformed infrared spectroscopy (FTIR). As a result, a photobleaching up to 80% after irradiation of 48 h was observed. Conformational rearrangements and formation of low molecular complexity structures were formed during the irradiation, as deduced from the pH decrement and the fluorescence shifting to lower wavelengths. Additionally a significant mineralization with the formation of CO2, CO, and inorganic carbon compounds was registered, as assumed by TOC losses of up to 70%. The differences in photodegradation between samples expressed by photobleaching efficiency were enhanced in the summer sample and related to its elevated aromatic content. Aromatic structures are assumed to have high autosensitization capacity effects mediated by the free radical generation from quinone and phenolic moieties.
-This work presents a kinetic study of the enzymatic hydrolysis of three cellulosic substrates: filter paper (FP), used as a low recalcitrance substrate model; steam exploded sugarcane bagasse (SB); and weak acid pretreated SB (1:20 dry bagasse:H 2 SO 4 solution 1% w/w), the last two delignified with 4% NaOH (w/w). The influence of substrate concentration was assessed in hydrolysis experiments in a shaker, using Accellerase® 1500, at pH 4.8, in 50 mM sodium citrate buffer. Cellulose loads (weight substrate /weight total ) were changed between 0.5%-13% (for FP) and 0.99%-9.09% (for SB). For FP and low loads of steam exploded SB, it was possible to fit pseudo-homogeneous Michaelis-Menten models (with inhibition). For FP and higher loads of steam exploded SB, modified Michaelis-Menten models were fitted. Besides, it was observed that, after retuning of the model parameters, it is possible to apply a model fitted for one situation to a different case. Chrastil models were also fitted and they were the only feasible approach for the highly recalcitrant acid-treated SB.
The enzymatic cocktail of cellulases is one of the most costly inputs affecting the economic viability of the biochemical route for biomass conversion into biofuels and other chemicals. Here, the influence of liquid hot water, dilute acid, alkali, and combined acid/alkali pretreatments on sugarcane bagasse (SCB) used for cellulase production was investigated by means of spectroscopic and imaging techniques. Chemical composition and structural characteristics, such as crystallinity (determined by X-ray diffraction), functional groups (Fourier transform infrared spectroscopy), and microstructure (scanning electron microscopy), were used to correlate SCB pretreatments with enzymatic biosynthesis by a strain of the filamentous fungus Aspergillus niger under solid-state fermentation. The combined acid/alkali pretreatment resulted in a SCB with higher cellulose content (86.7%). However, the high crystallinity (74%) of the resulting biomass was detrimental to microbial uptake and enzyme production. SCB pretreated with liquid hot water yielded the highest filter paper cellulase (FPase), carboxymethyl cellulase (CMCase), and xylanase activities (0.4, 14.9, and 26.1 U g(-1), respectively). The results showed that a suitable pretreatment for SCB to be used as a substrate for cellulase production should avoid severe conditions in order to preserve amorphous cellulose and to enhance the physical properties that assist microbial access.
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