Primitive Photosynthetic Architectures Based on Self‐Organization and Chemical Evolution of Amino Acids and Metal Ions

Abstract

The emergence of light‐energy‐utilizing metabolism is likely to be a critical milestone in prebiotic chemistry and the origin of life. However, how the primitive pigment is spontaneously generated still remains unknown. Herein, a primitive pigment model based on adaptive self‐organization of amino acids (Cystine, Cys) and metal ions (zinc ion, Zn2+) followed by chemical evolution under hydrothermal conditions is developed. The resulting hybrid microspheres are composed of radially aligned cystine/zinc (Cys/Zn) assembly decorated with carbonate‐doped zinc sulfide (C‐ZnS) nanocrystals. The part of C‐ZnS can work as a light‐harvesting antenna to capture ultraviolet and visible light, and use it in various photochemical reactions, including hydrogen (H2) evolution, carbon dioxide (CO2) photoreduction, and reduction of nicotinamide adenine dinucleotide (NAD+) to nicotinamide adenine dinucleotide hydride (NADH). Additionally, guest molecules (e.g., glutamate dehydrogenase, GDH) can be encapsulated within the hierarchical Cys/Zn framework, which facilitates sustainable photoenzymatic synthesis of glutamate. This study helps deepen insight into the emergent functionality (conversion of light energy) and complexity (hierarchical architecture) from interaction and reaction of prebiotic molecules. The primitive pigment model is also promising to work as an artificial photosynthetic microreactor.

Transforming a Fluorochrome to an Efficient Photocatalyst for Oxidative Hydroxylation: A Supramolecular Dimerization Strategy Based on Host‐Enhanced Charge Transfer

“…[9][10][11][12][13][14] To fabricate efficient photosensitizers and photocatalysts through non-covalent synthesis is drawing increasing interests for its convenient construction manners beyond molecular level. [15][16][17][18][19][20][21][22][23][24][25] Benefiting from the dynamic nature of non-covalent interactions, the fabrication of functional p-conjugates with dynamicity, stimuli-responsibility, adaptivity, is expected. The development of non-covalent synthetic strategy is vital for the supramolecular engineering of functional p-conjugates.…”

Visible-light photooxidation in water by 1O2-generating supramolecular hydrogels

“…These hydrogel photocatalysts were used for the oxidation of iodide, 30 hydrogen production, 31 polymer crosslinking, 32 and articial photosynthesis. 33,34 There remain, however, several drawbacks with hydrogel photocatalysts, including the limited control of positioning and accessibility of photoactive sites and the possibility of dissociation of non-covalently bound photoactive sites from the gel. We propose that by making the catalyst an integral and inseparable component of the gelator itself, supramolecular photocatalysts could be produced with increased number of photoactive sites and enhanced stability.…”

Artificial Organelles for Energy Regeneration

“…In addition to these two examples, which demonstrated light‐driven NAD + regeneration in compartments, there are large number of similar studies showing mainly light‐driven NADH regeneration in the bulk with a help of different photosensitizers (e.g., graphitic carbon nitride thioflavin T‐amyloid nanofibers), porphyrin on biomimetic synthetic wood (SW), or porhirine on peptide nanotubes in combination with Pt nanoparticles . All these methods demonstrate regeneration of enzymatically active NADH form and it can be envisaged that some of them could be implemented in the compartments.…”

“…Most NAD + regeneration strategies considered lipid vesicles as compartments . The NAD + regeneration was driven by light by chemical energy or electrochemically and regeneration of both oxidized and reduced forms of NAD + was demonstrated. In the examples with light‐driven NAD + regeneration, TiO 2 was used as a photosensitizer.…”