Supramolecularly Assembled Nanocomposites as Biomimetic Chloroplasts for Enhancement of Photophosphorylation.

Prototypes of natural biosystems provide opportunities for artificial biomimetic systems to break the limits of natural reactions and achieve output control. However, mimicking unique natural structures and ingenious functions remains a challenge. Now, multiple biochemical reactions were integrated into artificially designed compartments via molecular assembly. First, multicompartmental silica nanoparticles with hierarchical structures that mimic the chloroplasts were obtained by a templated synthesis. Then, photoacid generators and ATPase-liposomes were assembled inside and outside of silica compartments, respectively. Upon light illumination, protons produced by a photoacid generator in the confined space can drive the liposome-embedded enzyme ATPase towards ATP synthesis, which mimics the photophosphorylation process in vitro. The method enables fabrication of bioinspired nanoreactors for photobiocatalysis and provides insight for understanding sophisticated biochemical reactions.

Freezing-triggered gelation of quaternized chitosan reinforced with microfibrillated cellulose for highly efficient removal of bilirubin.

The highly efficient removal of bilirubin from blood by hemoperfusion for liver failure therapy remains a challenge in the clinical field due to the low adsorption capacity and poor hemocompatibility of currently used carbon-based adsorbents. Polysaccharide-based cryogels seem to be promising candidates for hemoperfusion adsorbents owing to their inherited excellent hemocompatibility. However, the weak mechanical strength and relatively low adsorption capacity of polysaccharide-based cryogels limited their application in bilirubin adsorption. In this work, we presented a freezing-triggered strategy to fabricate QCS/MFC cryogels, which were formed by quaternized chitosan (QCS) crosslinked with divinylsulfonyl methane (BVSM) and reinforced with microfibrillated cellulose (MFC). Ice crystal exclusions triggered the chemical crosslinking to generate the cryogels with dense pore walls. The obtained QCS/MFC cryogels were characterized by FTIR, SEM, stress-strain test, and hemocompatibility assay, which exhibited interconnected macroporous structures, excellent shape-recovery and mechanical performance, and outstanding blood compatibility. Due to the quaternary ammonium functionalization of chitosan, the QCS/MFC showed a high adsorption capacity of 250 mg g-1 and a short adsorption equilibrium time of 3 h. More importantly, the QCS/MFC still exhibited high adsorption efficiency (over 49.7%) in the presence of 40 g L-1 albumin. Furthermore, the QCS/MFC could also maintain high dynamic adsorption efficiency in self-made hemoperfusion devices. This facile approach provides a new avenue to develop high-performance hemoperfusion adsorbents for bilirubin removal, showing great promise for the translational therapy of hyperbilirubinemia.

Shapeable and underwater super-elastic cellulose nanofiber/alginate cryogels by freezing-induced oxa-Michael reaction for efficient protein purification.

Construction of monolithic cryogels that can efficiently adsorb proteins is of great significance in biotechnological and pharmaceutical industries. Herein, a novel approach is presented to fabricate microfibrillated cellulose (MFC)/sodium alginate (SA) cryogels by using freezing-induced oxa-Michael reaction at -12 °C. Thanks to the controllable reactiveness of divinyl sulfone (DVS), cryo-concentrated pH increase activates the oxa-Michael reaction between DVS and hydroxyl groups of MFCs and SAs. The obtained composite cryogel exhibits outstanding underwater shape recovery and excellent fatigue resistance. Moreover, the MFC/SAs reveal a high lysozyme adsorption capacity of 294.12 mg/g, surpassing most of absorbent materials previously reported. Furthermore, the cryogel-packed column can purify lysozyme continuously from chicken egg white, highlighting its outstanding practical application performance. Reuse experiments indicated that over 90% of lysozyme extraction capacity was retained after 6 cycles. This work provides a new avenue to design and develop next-generation chromatographic media of natural polysaccharide-based cryogel for protein purification.

Facile fabrication of robust polydopamine microcapsules for insulin delivery.

Inspired by the composition of adhesive proteins in mussel, a facile, low-cost, and green approach to construct robust polydopamine (PDA) microcapsules as carriers for insulin delivery is developed. The morphology and shell thickness of the capsules could be tuned by varying the concentration of dopamine or the pH of Tris-HCl buffer. The PDA capsules are stable enough for long-term storage and transportation in practical application. The fluorescent property of PDA capsules labeled with FITC is beneficial in monitoring the safety and efficacy of drug carriers. Furthermore, the PDA shell coated insulin particles exhibit pH-responsive release behavior, making them promising for the oral administration of insulin in diabetic patients.