We present detailed electrochemical investigations into the role of dissolved O2 in electrolyte solutions in scavenging photoactivated electrons from a uniform photosystem I (PS I) monolayer assembled on alkanethiolate SAM (self-assembled monolayer)/Au surfaces while using methyl viologen (MV(2+)) as the redox mediator. To this end, we report results for direct measurements of light induced photocurrent from uniform monolayer assemblies of PS I on C9 alkanethiolate SAM/Au surfaces. These measurements, apart from demonstrating the ability of dissolved O2 in the electrolyte medium to act as an electron scavenger, also reveal its essential role in driving the solution-phase methyl viologen to initiate light-induced directional electron transfer from an electron donor surface (Au) via surface assembled PS I trimers. Specifically, our systematic electrochemical measurements have revealed that the dissolved O2 in aqueous electrolyte solutions form a complex intermediate species with MV that plays the essential role in mediating redox pathways for unidirectional electron transfer processes. This critical insight into the redox-mediated electron transfer pathways allows for rational design of electron scavengers through systematic tuning of mediator combinations that promote such intermediate formation. Our current findings facilitate the incorporation of PS I-based bio-hybrid constructs as photo-anodes in future photoelectrochemical cells and bio-electronic devices.
We investigate the phase transition stages for detergent-mediated liposome solubilization of bio-mimetic membranes with the motivation of integrating membrane-bound Photosystem I into bio-hybrid opto-electronic devices. To this end, the interaction of two non-ionic detergents n-dodecyl-β-D-maltoside (DDM) and Triton X-100 (TX-100) with two types of phospholipids, namely DPhPC (1,2-diphytanoyl-sn-glycero-3-phosphocholine) and DPPG (1,2-dipalmitoyl-sn-glycero-3-phospho-(1'-rac-glycerol)), are examined. Specifically, solubilization processes for large unilamellar liposomes are studied with the aid of turbidity measurements, dynamic light scattering, and cryo-transmission electron microscopy imaging. Our results indicate that the solubilization process is well depicted by a three-stage model, wherein the lamellar-to-micellar transitions for DPhPC liposomes are dictated by the critical detergent/phospholipid ratios. The solubilization of DPhPC by DDM is devoid of formation of a "gel-like" phase. Furthermore, our results indicate that DDM is a stable candidate for DPhPC solubilization and proteoliposome formation. Finally, although the solubilization of DPPG with DDM indicated the familiar three-stage process, the same process with TX-100 indicate structural deformation of vesicles into complex network of kinetically trapped micro- and nanostructured arrangements of lipid bilayers.
To produce desired aggregate structures of copolymers, the copolymer is usually first dissolved in a common solvent that dissolves all the blocks. However, a solvent having the exact same solubility to all the blocks of a copolymer is rare. Hence, it is extremely important to know whether the block copolymer forms micelle in a common solvent, and if it does, to know the micelle's structure. In this study, we used polystyrene-b-poly(4-vinylpyridine) (PS-b-P4VP) dissolved in dimethyl formamide (DMF) as a model system to address block copolymer micelle formation and its structure in a solvent good for all the blocks as DMF dissolves both PS and P4VP. Our atomic force microscopy (AFM) and cryogenic-transmission electron microscopy (cryo-TEM) results clearly demonstrated that PS-b-P4VP with a wide range of molecular weight and P4VP composition in DMF forms a spherical micelle. Furthermore, contact angle measurements and TEM results clearly show that the micelle has a PS core and a P4VP corona. In comparing the dry micelle and the micelle in DMF, we discovered that the micelle core is significantly swelled by DMF. Our findings suggest that soft-core micelles widely exist for block copolymers in solvents good for all the blocks but with significant selectivity between different blocks.
The role of natural thylakoid membrane housing of Photosystem I (PSI), the transmembrane photosynthetic protein, in its robust photoactivated charge separation with near unity quantum efficiency is not fundamentally understood. To this end, incorporation of suitable protein scaffolds for PSI incorporation is of great scientific and device manufacturing interest. Areas of interest include solid state bioelectronics, and photoelectrochemical devices that require bio-abio interfaces that do not compromise the photoactivity and photostability of PSI. Therefore, the surfactant-induced membrane solubilization of a negatively charged phospholipid (DPhPG) with the motivation of creating biomimetic reconstructs of PSI reconstitution in DPhPG liposomes is studied. Specifically, a simple yet elegant method for incorporation of PSI trimeric complexes into DPhPG bilayer membranes that mimic the natural thylakoid membrane housing of PSI is introduced. The efficacy of this method is demonstrated via absorption and fluorescence spectroscopy measurements as well as direct visualization using atomic force microscopy. This study provides direct evidence that PSI confinements in synthetic lipid scaffolds can be used for tuning the photoexcitation characteristics of PSI. Hence, it paves the way for development of fundamental understanding of microenvironment alterations on photochemical response of light activated membrane proteins.
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