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Iron-sulfur cluster and apoferritin complex and preparation method and application thereof

A technology of apoferritin and iron-sulfur clusters, which is applied in chemical instruments and methods, organic compound/hydride/coordination complex catalysts, chemical/physical processes, etc. Poor water solubility and other problems, to achieve the effect of enhancing catalytic hydrogen production efficiency, good biocompatibility, and strong stability

Active Publication Date: 2018-03-13
NANJING UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Although the natural enzymes have high activity, good selectivity, and good application value, it is still a challenge to use these enzymes directly in the hydrogen production plant because of the difficulty of isolating them and their poor performance in air. is also bad and thus limited in practical applications
In contrast, iron-sulfur cluster catalysts are simple to prepare, have high stability, and relatively low cost. However, most iron-sulfur cluster catalysts have poor water solubility, and it is necessary to find a suitable method to improve their water solubility so that they can be used in water It exerts its high-efficiency performance in catalytic hydrogen production in the
[0004] At present, it has been reported in the literature that some hydrophilic groups have been modified on iron-sulfur cluster hydrogenase, but due to the complicated chemical modification process, the stability is ultimately limited.
In addition, some scholars try to covalently link iron-sulfur cluster catalysts with some carriers, such as chitosan, cytochrome c, etc. This method is also not easy to control the optimal ratio between the two, and the operability is difficult.

Method used

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  • Iron-sulfur cluster and apoferritin complex and preparation method and application thereof
  • Iron-sulfur cluster and apoferritin complex and preparation method and application thereof
  • Iron-sulfur cluster and apoferritin complex and preparation method and application thereof

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preparation example Construction

[0072] The preparation method comprises the following steps:

[0073] (1) Synthesis of 1,10-phenanthroline-5,6-dione:

[0074] First synthesize 1,10-phenanthroline-5,6-dione, prepare a mixed acid solution containing 20mL of concentrated sulfuric acid and 10mL of concentrated nitric acid, and add 2.0g of 1,10-phenanthroline and potassium bromide 2.0 in the mixture of g. Heat in an oil bath at 130°C for 3 hours. After cooling to room temperature, it was added to 250 mL of deionized water at 4 °C, and the pH was neutralized to 6-7 with 80 mL of 10 M NaOH. Then use CHCl 3 Extracted 3 times, 100 mL each time, finally treated with anhydrous sodium sulfate and dried in a vacuum oven to obtain 1.8 g of a bright yellow solid product.

[0075] (2) Synthesis of ruthenium complex ligand (dpqp):

[0076] Weigh 0.084g of 1,10-phenanthroline-5,6-dione and dissolve it in 20mL of methanol. After boiling, quickly add 0.044g of 2,3-diaminopiperazine and reflux for 3 hours. The resulting so...

Embodiment 1

[0085] Adjust the pH of the apoferritin aqueous solution to be 2, add the ruthenium complex to the apoferritin solution, the feeding ratio of the ruthenium complex to the apoferritin nanoparticles is 300:1, after stirring, for example, using a magnetic stirrer, the The pH of the solution was adjusted to 10, so that the apoferritin was assembled back into a complete protein cage, and allowed to stand for a period of time. Dialyze with PBS aqueous solution (1mM) containing 10% acetonitrile solvent by volume for 48 hours, and use PBS aqueous solution without acetonitrile for the last dialysis; filter the sample obtained after the above dialysis with a 0.22 μm water filter head, and then use PD-10 After post-processing the desalting column, the apoferritin complex loaded with ruthenium complexes can be obtained; subsequently, the complex obtained above is blended with the iron-sulfur cluster catalyst, wherein the feed of the iron-sulfur cluster catalyst and the apoferritin nanopart...

Embodiment 2

[0088] Adjust the pH of the apoferritin aqueous solution to be 2, add the ruthenium complex to the apoferritin solution, the feeding ratio of the ruthenium complex to the apoferritin nanoparticles is 300:1, and after stirring with a magnetic stirrer, adjust the pH of the solution to 10. Allow the apoferritin to assemble back into a complete protein cage and let it stand for a period of time. Dialyze with PBS aqueous solution (1mM) containing 5% acetonitrile solvent by volume for 48h; filter the sample obtained after the above dialysis with a 0.22μm water filter head, and then use a PD-10 desalting column for post-treatment to obtain the loaded ruthenium complex apoferritin complex; then, the complex obtained above was blended with an iron-sulfur cluster catalyst, wherein the feeding ratio of the iron-sulfur cluster catalyst to apoferritin nanoparticles was 400:1, and after standing still, a 0.22 μm Filter the water system filter head, and then use the PD-10 desalting column fo...

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Abstract

The invention discloses an iron-sulfur cluster and apoferritin complex and a preparation method and application thereof; the iron-sulfur cluster and apoferritin complex includes apoferritin and a ruthenium compound and iron-sulfur cluster catalyst loaded therein, wherein the ruthenium compound has an entrapment ratio of 5-15% and the iron-sulfur cluster catalyst has an entrapment ratio of 10-30%.The photosensitizer ruthenium compound and water-insoluble iron-sulfur cluster catalyst molecules are functionally assembled in a protein molecule by means of non-covalent assembly, a working environment in nature is provided for the iron-sulfur cluster catalyst, and an aqueous photo-driven hydrogen production system is constructed; wide application of the iron-sulfur cluster catalyst catalytic system in an aqueous solution is achieved; the system has good stability; when the system is applied to hydrogen production by photocatalytic decomposition, the use of ascorbic acid as a proton source and electron sacrificial donor under light condition enables hydrogen production efficiency of the system to be enhanced.

Description

technical field [0001] The invention belongs to the field of composite nanomaterials, and in particular relates to an iron-sulfur cluster-apoferritin composite, a preparation method thereof and its application in hydrogen production by photocatalytic hydrolysis. Background technique [0002] Non-renewable resources such as coal, oil, and natural gas, which are depleted day by day, are the main energy sources that human beings rely on at present. At the same time, the combustion of these traditional fossil energy sources will cause great pollution to the environment. Environmental pollution and energy shortage are two key issues that plague the development of human beings today and in the future. Therefore, it is of great practical significance to find and develop green and renewable new energy sources. As a fuel that does not involve carbon elements at all, hydrogen is undoubtedly an ideal clean alternative energy source. The photolysis of water technology can directly con...

Claims

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Application Information

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IPC IPC(8): B01J31/22C01B3/04
CPCC01B3/042B01J31/003B01J31/063B01J31/183B01J31/226B01J2531/842B01J2531/821B01J35/39B01J35/23Y02E60/36
Inventor 冯福德陈炜健
Owner NANJING UNIV
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