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Photosynthesis Research

, Volume 142, Issue 2, pp 169–180 | Cite as

A photosynthesis-inspired supramolecular system: caging photosensitizer and photocatalyst in apoferritin

  • Weijian Chen
  • Xuetong Cai
  • Luyang Ji
  • Xiao Li
  • Xuewei Wang
  • Xiaoran Zhang
  • Yajing Gao
  • Fude FengEmail author
Original Article
  • 217 Downloads

Abstract

Inspired by the bioinorganic structure of natural [FeFe]-hydrogenase ([FeFe]-H2ase) that possesses iron sulfur clusters to catalyze proton reduction to hydrogen (H2), we design a supramolecular photosystem by sequentially integrating hydrophobic ruthenium complex (as a photosensitizer) and diiron dithiolate complex (as a photocatalyst) into the inner surface or cavity of apoferritin via noncovalent interactions. This platform allows photosensitizer and catalyst to localize in a close proximity and short-distance electron transfer process to occur within a confined space. The resulted uniform core–shell nanocomposites were stable and well dispersed in water, and showed enhanced H2 generation activity in acidic solution as compared to the homogenous system without apoferritin participation.

Graphic abstract

Keywords

Supramolecular assembly Photocatalytic hydrogen evolution Apoferritin Protein cage Artificial photosynthesis 

Abbreviations

apo-HSF

Horse spleen apoferritin

[FeFe]-H2ase

[FeFe]-hydrogenase

PSI

Photosystem I

PS

Photosensitizer

Fe–S

Iron–Sulfur

β- and γ-CD

β- and γ-Cyclodextrin

EY

Eosin Y

RB

Rose bengal

Rudpqp

[Ru(bpy)2(dpqp)]2+ (bpy = 2,2′-bipyridnedpqp = pyrazino[2′,3′5,6]pyrazino[2,3-f][1,10]phenanthroline)

dppz

Dipyrido[3,2-a:2′,3′-c]phenazine

FeFe–COOH

[Fe2{(μ-SC2H4)(μ-SCH)(CH2)4COOH}(CO)6]

MLCT

Metal to ligand charge transfer

CD

Circular dichroism

FT-IR

Fourier transform infrared

DLS

Dynamic light scattering

TEM

Transmission electron microscopy

GC

Gas chromatography

ICP-OES

Inductively coupled plasma optical emission spectroscopy

TON

Turnover number

NP

Nanoparticle of apoferritin encapsulating Ru photosensitizer and FeFe–COOH

Notes

Acknowledgements

We are grateful to Prof. Wei Wang (Nanjing University) for help with DLS measurements. We thank the National Basic Research Program of China (No. 2015CB856300), Nanjing University Innovation and Creative Program for PhD candidate (No. CXCY18-17), Interdisciplinary Training for Graduate Students of Nanjing University (No. 2016CL11), the Innovative Training Program for Undergraduate Students of Nanjing University (No. G201910284101), and the Program for Changjiang Scholars and Innovative Research Team in University for financial support.

Compliance with ethical standards

Conflicts of interest

The authors declare no competing financial interests.

Supplementary material

11120_2019_671_MOESM1_ESM.docx (130 kb)
Supplementary material (DOCX 130 kb)

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Copyright information

© Springer Nature B.V. 2019

Authors and Affiliations

  1. 1.Key Laboratory of High Performance Polymer Material and Technology of Ministry of Education, Department of Polymer Science & Engineering, School of Chemistry & Chemical EngineeringNanjing UniversityNanjingPeople’s Republic of China

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