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Natural ecosystems can be conceptually thought of as interconnected environmental and metabolic systems. Humans and their activities affect and are a part of these ecosystems. Considering a more applied perspective of human activities within ecosystems, it is important to gain an understanding of natural ecology and its metabolic processes in various environments. From this perspective, biomass production is at the forefront of current research. Here we show, our challenges of solution/solid-state NMR analysis for molecular complexity toward biomass. The first challenge is macromolecular complexity to analyze structure and composition of polysaccharides. The second challenge is biomass degrading microbial complexity, namely concerning their metabolic activity. The third challenge is integrating molecular and microbial complexity, by using heterogeneous analytical approach. Our approach provides a foundation for evaluation of systemic effects of input polysaccharides toward output digested–catabolized metabolites by environmental microbiota, including animal symbionts.

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