Novel Method of Constructing Two-Dimensional Correlation Spectroscopy without Subtracting a Reference Spectrum

In this study, we propose a new approach to generate two-dimension spectra to enhance the intensity of cross peaks relevant to intermolecular interaction. We investigate intermolecular interaction between two solutes (denoted as P and Q, where P has a characteristic peak at <i>X</i>_P) dissolved in the same solvent via the near diagonal cross peaks around the coordinate (<i>X</i>_P, <i>X</i>_P) in a two-dimensional (2D) asynchronous spectrum of generalized spectroscopy. Because of physical constrains in many cases, the variation ranges of the initial concentrations of P or Q must be kept very narrow, leading to very weak cross peak intensities. The weak cross peaks vulnerable to noise bring about difficulty in the investigation of subtle intermolecular interaction. Herein, we propose a new of way constructing a 2D asynchronous spectrum without the subtraction of the average spectrum often used as a reference spectrum. Mathematical analysis and computer simulation demonstrate that the near diagonal cross peaks around the coordinate (<i>X</i>_P, <i>X</i>_P) in the 2D asynchronous spectrum using the new approach possess two characteristics: (1) they can still reflect an intermolecular interaction reliably; 2) the absolute intensities of the cross peaks are significantly stronger than those generated by the conventional method. We incorporate the novel method with the DAOSD (double asynchronous orthogonal sample design scheme) approach and applied the modified DAOSD approach to study hydrogen bonding behavior in diethyl either/methanol/THF system. The new approach made the weak cross peaks, which are not observable in 2D asynchronous spectrum generated using conventional approach, become observable. The appearance of the cross peak demonstrate that When a small amount of THF is introduced into diethyl solution containing low amount of methanol, THF breaks the methanol–diethyl ether complex and forms methanol-THF complex via new hydrogen bond. This process takes place in spite of the fact that the content of diethyl ether is overwhelmingly larger than that of THF. The above result demonstrates that the new approach described in this article is applicable to enhance intensity of cross peaks in real chemical systems

DataSheet1_Granular activated carbon enhances volatile fatty acid production in the anaerobic fermentation of garden wastes.docx

Garden waste, one type of lignocellulosic biomass, holds significant potential for the production of volatile fatty acids (VFAs) through anaerobic fermentation. However, the hydrolysis efficiency of garden waste is limited by the inherent recalcitrance, which further influences VFA production. Granular activated carbon (GAC) could promote hydrolysis and acidogenesis efficiency during anaerobic fermentation. This study developed a strategy to use GAC to enhance the anaerobic fermentation of garden waste without any complex pretreatments and extra enzymes. The results showed that GAC addition could improve VFA production, especially acetate, and reach the maximum total VFA yield of 191.55 mg/g VSadded, which increased by 27.35% compared to the control group. The highest VFA/sCOD value of 70.01% was attained in the GAC-amended group, whereas the control group only reached 49.35%, indicating a better hydrolysis and acidogenesis capacity attributed to the addition of GAC. Microbial community results revealed that GAC addition promoted the enrichment of Caproiciproducens and Clostridium, which are crucial for anaerobic VFA production. In addition, only the GAC-amended group showed the presence of Sphaerochaeta and Oscillibacter genera, which are associated with electron transfer processes. Metagenomics analysis indicated that GAC addition improved the abundance of glycoside hydrolases (GHs) and key functional enzymes related to hydrolysis and acidogenesis. Furthermore, the assessment of major genera influencing functional genes in both groups indicated that Sphaerochaeta, Clostridium, and Caproicibacter were the primary contributors to upregulated genes. These findings underscored the significance of employing GAC to enhance the anaerobic fermentation of garden waste, offering a promising approach for sustainable biomass conversion and VFA production.</p