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The high quantum efficiency of natural photosynthesis has inspired chemists for solar fuel synthesis. In photosynthesis, charge recombination in photosystems is minimized by efficient charge separation across the thylakoid membrane. Building on our previous bioelectrochemical studies of electron transfer between a light-harvesting nanoparticle (LHNP) and the decahaem subunit MtrC, we demonstrate photo-induced electron transfer through the full transmembrane MtrCAB complex in liposome membranes. Successful photoelectron transfer is demonstrated by the decomposition of a redox dye, Reactive Red 120 (RR120), encapsulated in MtrCAB proteoliposomes. The photoreduction rates are found to be dependent on the identity of the external LHNPs, specifically, dye-sensitized TiO2, amorphous carbon dots (a-CD) and graphitic carbon dots with core nitrogen doping (g-N-CDs). Agglomeration or aggregation of TiO2 NPs likely reduces the kinetics of RR120 reductive decomposition. In contrast, with the dispersed a-CD and g-N-CDs, the kinetics of the RR120 reductive decomposition are observed to be faster with the MtrCAB proteoliposomes and we propose that this is due to enhancement in the charge-separated state. Thus, we show a proof-of-concept for using MtrCAB as a lipid membrane-spanning building block for compartmentalised photocatalysis that mimics photosynthesis. Future work is focused on incorporation of fuel generating redox catalysts in the MtrCAB proteoliposome lumen. [ABSTRACT FROM AUTHOR]

The decahaem cytochrome MtrC from Shewanella oneidensis MR-1 was employed as a protein electron conduit between a porous indium tin oxide electrode and redox enzymes. Using a hydrogenase and a fumarate reductase, MtrC was shown as a suitable and efficient diode to shuttle electrons to and from the electrode with the MtrC redox activity regulating the direction of the enzymatic reactions. [ABSTRACT FROM AUTHOR]

In the present study, we report on the carbonic anhydrase (CA)-assisted formation of biomineralized calcium carbonate crystalline composites (CCCCs). Ellipsoidal CCCCs, such as calcite polymorphism, in a micro-size range catalyzed by CA were successfully synthesized with polyethylene glycol and magnetic nanoparticles in the constant CO2 pressure controlled chamber, for the first time. CA-assisted CCCCs characterized by X-ray diffraction, transmission electron microscopy, scanning electron microscopy, and dynamic light scattering, showed their crystalline phase with mesoporous property according to Fourier transform infrared and Brunauer–Emmett–Teller area. These CCCCs retained about 43% of free CA esterase activity. Furthermore, the magnet-based separation was also successful for the reuse of the CCCCs. As a result, the CCCCs produced preserved their catalytic activity even after its ten repeated usages, and were stable for more than 50 days under room temperature. The reported method paves the way for novel biomineralization via CA for the formation of functional CA containing nanocomposites and biocatalyst technology applications. [ABSTRACT FROM AUTHOR]

Subtilisin Carlsberg (SC) was immobilized and stabilized on magnetically-separable mesoporous silica (Mag-MSU-F) in the form of nanoscale enzyme reactors (NERs) based on the ship-in-a-bottle mechanism. Stabilized NERs of SC (NER-SC) were freeze-dried and successfully used for the transesterification of N-acetyl-l-phenylalanine ethyl ester with n-propanol in isooctane. Magnetic separation of Mag-MSU-F facilitated the repeated usages of stable NER-SC. This is the first demonstration for the use of stable and magnetically-separable NERs in an organic solvent, which has the potential for environmentally-friendly synthesis using enzymes in organic solvents. [ABSTRACT FROM AUTHOR]

In this study, we report the structure and shape of new polymeric nanofibers entrapped with QDs, which were prepared by electrospinning a homogenous mixture of polymers and QDs. Uniformly distributed QDs within the polymer matrix seem to induce the high degree of compactness and shape rigidity in the nanofibers, and resulted in the efficient enzyme immobilization. After immobilization, the esterase enzymes coated on the QDs–nanofibers showed good stability with no loss of enzyme activity even after being recycled for more than ten times. The present study demonstrates the successful application of shape reformable polymeric nanofibers entrapped with QDs for enzyme immobilization for the first time, and so it is anticipated that this technology can be employed in various enzyme applications due to its facile shape control feature in the fabrication of the nanofibers. [ABSTRACT FROM AUTHOR]

In this study, the formation of protein microspheres through lysosomal enzyme-assisted biomineralized crystallization was demonstrated. Spherical micro-sized hybrid CaCO 3 constructs were synthesized and characterized using field-emission scanning electron microscopy equipped with energy-dispersive X-ray spectroscopy, X-ray diffraction, Fourier-transform infrared spectroscopy, and particle size analysis. Additionally, parameters such as the Brunauer-Emmett-Teller surface area and single-point total pore volume, and adsorption/desorption analysis were used to investigate the mesoporous properties, which are advantageous for lysosomal enzyme (LE) loading. A LE can be used as an organic template, not only as a morphological controller but also for entrapping LE during the crystallization pathway. The hybrid protein microspheres accommodated 2.3 mg of LE with a 57% encapsulation efficiency and 5.1 wt% loading. The peroxidase activity of the microspheres was calculated and found to be approximately 0.0238 mM -1 min -1 . pH-responsive release of the LE from CaCO 3 was observed, suggesting potential biomedical and cosmetic applications in acidic environments. The hybrid LE microsphere treatment significantly alleviated melanin production in a dose-dependent manner and further downregulated the mRNA expression of MITF, tyrosinase, TYRP-1, and TYRP-2. These results indicate skin-whitening effects by inhibiting melanin without inducing cytotoxicity. The data provide the first evidence of the potential use of a LE for obtaining hybrid minerals and the effectiveness of biomineralization-based sustainable delivery of enzyme-based vehicles based on organelle-extract-assisted biomineralization.

The decahaem cytochrome MtrC from Shewanella oneidensis MR-1 was employed as a protein electron conduit between a porous indium tin oxide electrode and redox enzymes. Using a hydrogenase and a fumarate reductase, MtrC was shown as a suitable and efficient diode to shuttle electrons to and from the electrode with the MtrC redox activity regulating the direction of the enzymatic reactions.