摘要：SummaryPrecision remodeling of glycans in their native environments is pivotal for understanding glycan-mediated biological events and has important biotechnological implications in fields of clinical diagnosis, glyco-immune checkpoint therapy, and so forth. However, the influence of aglycone-steric diversity on the selectivity of glycan remodeling has been largely overlooked, limiting the application in complex biological scenarios. Here, we report the achievement of aglycone sterics-selective enzymatic glycan remodeling by controlled grafting of functional polymers from glycoenzyme. Through tuning polymer length, a series of enzyme-polymer composites with varying substrate permeability are prepared, which afford an activity pattern-based differentiation strategy for aglycone sterics. This leads to the implementation of glycolipid’s partner screening, and aglycone sterics-selective glycan remodeling in a complex biological environment. We further orchestrate the polymer length adjustment with external cues to regulate aglycone-steric selectivity in a multi-faceted fashion, resulting in an unexpected enhancement of glycolipid remodeling, and temporal control of glycan remodeling on live cells.Graphical abstractDisplay OmittedHighlights•Functional polymer is used to tune the glycan remodeling activity of a glycoenzyme•Glycoenzyme-polymer composites display an aglycone sterics-dependent activity•The composites enable aglycone sterics-selective glycan remodeling in complex media•Temporal and two-dimensional regulation of glycan remodeling is achieved, respectivelyBiological sciences; Biochemistry; Glycobiology; Enzyme engineering
