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[Display omitted] • A new synergistic emulsification mechanism of O/W Pickering HIPEs was proposed. • A green and eco-friendly hydrogel with hyperbranched imprinted sites was designed. • The sorbents exhibit rapid capture kinetics, high absorption capacity and excellent selectivity. • A lasting adsorption stability were realized in practical samples. Hyperbranched sorbents has attracted extensive concern from scholars at home and abroad owing to its rich surface termination recognition units and hyperbranched crosslinking structure. In this work, a new kind of porous hyperbranched boronate affinity molecularly imprinted hydrogel (PHs@CNCs@Y-Br-MIPs) were prepared via Pickering emulsion template method for selective separation and purification of flavonoids in complex agricultural wastewater. The novel multi-response hyperbranched Pickering particles based on cellulose nanocrystals (CNCs) can effectively enhanced the biocompatibility, hydrophilic, and interface stability of the emulsion system. Meanwhile, the introduction of dipentaerythritol hexyl (3-mercaptopropionic acid) (DH) in CNCs@SH@Y-Br could provide abundant hyperbranched anchor groups for immobilizing template molecules, resulting in the formation of more specific binding sites. In addition, the 4-formyl-1,2 phenylbis (2-bromo-2-methyl protocarbamate) (Y-shaped initiator) can precisely regulate the distribution of imprinted site and imprinted efficiency via atomic radical polymerization (ATRP). As expected, the resulting PHs@CNCs@Y-Br-MIPs showed fast adsorption kinetics (360 min) for NRG under pH = 7.4 and the excellent NRG adsorption capacity (Q max = 42.28 μmol g−1). Compared to non-imprinted polymer, the PHs@CNCs@Y-Br-MIPs exhibited the promising imprinting factors (IF = 2.74) owing to the abundant boronate affinity sites numbers of 46.81 μmol g−1 and the high-affnity binding site density of 0.56 μmol/m2 on PHs@CNCs@Y-Br-MIPs. The adsorption–desorption cycles proved excellent regenerability (only 6.79 % loss) after six adsorption–desorption cycles. Furthermore, the NRG extraction rate of PHs@CNCs@Y-Br-MIPs increased to 93.61 %. The purified NRG had good antibacterial properties against Staphylococcus aureus (13.17 mm of antibacterial bands). As such, the ability to hyperbranched imprinted polymers-regulate the recognition site density and selectivity highlights their significance in functioning as smart porous imprinted sorbents for separation and purification of targeted flavonoid molecules. [ABSTRACT FROM AUTHOR]

• An innovative emulsion interfacial assembly imprinted strategy was designed. • The optimized adsorbent has excellent biocompatibility and mechanical ability. • Hyperbranched imprinted sites facilitate NRG adsorption at multicomponent extract. • The outstanding adsorption selectivity in practical natural products can be enabled. Hydrogel-based molecular imprinted materials have attracted much attention in separation science and technology. However, traditional hydrogel imprinting sorbents face the limited number of imprinting sites, resulting in low adsorption capacity. Herein, a novel hyperbranched boronate affinity imprinted hydrogel (APOH-BA-MIPs) was prepared based on emulsion microreactors for the specific separation of flavoniods. Interestingly, the new Pickering particles (CNCs@GMA@SH-A-CD) with hyperbranched anchor groups and suitable hydrophilic properties were fabricated, which significantly grafted the specific recognizing sites. Meanwhile, the cellulose nanocrystals (CNCs) and cyclodextrins (CDs) composite can effectively enhance the emulsion stability. The addition of functioned CNCs solid emulsifier would effectively enhance the mechanical stability of micro-nano imprinting assembly sorbents during the adsorption process. The mechanical properties of the resulting APOH-BA-MIPs were also improved (Young's moduli 1.73 MPa). The results of adsorption experiments of APOH-BA-MIPs show fast adsorption kinetics (300 min) for NRG under pH = 7.4. The APOH-BA-MIPs still exhibited a significant adsorption capacity (56.03 μmol g−1 at 308 K) for NRG compared to other structural analogues, such as CC, RT, QRCT, ARS and LTL. The imprinting factor (IF) of 3.24 was observed for APOH-BA-MIPs compared to their non-imprinted counterpart. The high affinity site number of APOH-BA-MIPs were calculated to be as high as 53.11 μmol g−1. The regeneration performance of APOH-BA-MIPs still remained at 93.75 % after seven adsorption–desorption cycles. Additionally, the purity can be extracted from agricultural waste pomelo peel to 91.37 %. The purified NRG exhibited excellent antibacterial properties against Staphylococcus aureus. This work provides a new strategy for the fabrication of micr-nano imprinted sorbents with abundant and uniform recognition sites for specific capture flavonoid molecules from agricultural waste. [ABSTRACT FROM AUTHOR]