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Nanostack printing for materials research

Periodic Reporting for period 3 - NANOSTACKS (Nanostack printing for materials research)

Reporting period: 2023-02-01 to 2024-07-31

Man-made fuel cells have a bad energy-efficiency, i.e. they waste two thirds of the energy as heat when they convert hydrogen to electrical energy. Moreover, they need expensive palladium-based catalysts because all the other catalysts are irreversibly poisoned by molecules in ambient air. Hydrogenases that are Nature’s fuel cells convert chemical energy very efficiently into electrical energy, and they do that with cheap iron oxide-based catalysts. We want to find out if we can manufacture a fuel cell that is as efficient as Nature’s fuel cells, and that uses a cheap catalyst.
That is important for society, because regenerative electrical energy is generated when the wind blows or when the sun shines, but two thirds of that energy is lost, when stored with the help of a state-of-the-art fuel cell. Batteries are much more efficient in storing electrical energy, and by now fuel costs for an electrical car are cheaper than costs for diesel fuel because also a diesel engine wastes 70% of the chemical energy that drives the car. But batteries have a problem with their energy-density: electric cars are quite heavy due to their battery, which is even worse in a truck, a ship, an airplane, or when storing energy from a wind park.
An energy-efficient fuel cell would solve these problems: if combined with a small battery an energy efficient fuel cell would outperform a gasoline powered car or airplane.
Building a fuel cell that mimics Nature’s principles is difficult, though. Energy converting enzymes all use the same basic trick: similar to a marble run, they fast lead electrons down a predetermined pathway of redox centres, and, thereby, prevent electrons from recombining with their left-behind proton which would dissipate the electron’s energy as heat.
We use a recently invented multi material nano3D printer to print such layers as nanostacks. Thereby, we want to do materials evolution: printing many different nanostack variants, and selecting improved solar cells or fuel cells.
nano3D printer:
We advanced our nano3D printer to an estimated TRL8. The machine is used since 2023 by KIT’ & dkfz’ spin off company PEPperPRINT to manufacture peptide arrays for its customers. Currently, PEPperPRINT manufactures / advances several accessory machines that allow the needed throughput (automated wet chemistry processing, semi-automated metering of donor slides). Customer demand is unexpected high.
nano3D printable materials:
a. Polymers that serve as “solid solvents”, i.e. when melted by heat or solvent vapour they support a chemical reaction just like a normal solvent does. We identified many suitable solid solvents that work in solid-materials-based chemistry.
b. Amino acids that are embedded within “solid solvents”. These are used to first structure an acceptor slide with >20 different amino acids as solid materials, and then simply by melting elongate growing peptides in the array format to synthesize peptide arrays. We identified many additional post translational modified amino acid building blocks that now – first time – can be incorporated into peptide arrays.
c. Other chemical building blocks embedded within solid solvents that similar to peptide synthesis are used to synthesize many different light absorbing molecules.
d. OLED materials, e.g. emitter materials, electron transport materials, hole transport materials that can be used to nano3D print diodes, LEDs, batteries, solar cells or similar. Unexpectedly, we found out that 75% of tried out solid materials could be nano3D printed.
e. Finally, we found out that nanoparticles could be printed with our nano3D printer. SME TECNAN will try to commercialize corresponding inks.

Microstructured materials:
Another line of experiments successfully manufactured ITO-microstructured acceptor arrays together with a readout device. That brings down hands-on work to nano3D printing several nanolayers, and then directly analyzing printed nanostacks for function.

Functioning nanostacks:
Indeed, we managed to identify functioning nanostacks. A corresponding publication & patent application is currently written. It will be the basis to commercialize these activities.
High density peptide arrays:
Meanwhile, in 2024, nano3D printed peptide arrays by SME PEPperPRINT are manufactured for customers. When compared to peptide arrays that are produced with the peptide-laser-printer, these arrays have an estimated 5-fold higher density of synthesized peptides, and they are an estimated 10-fold cheaper per synthesized peptide. Unexpectedly, their quality is higher, obviously due to the nano3D printer’s novel printing mode. To our knowledge, this type of peptide arrays is unrivalled. Even more interesting, first-time-available, affordable high density peptide arrays with post translational modified amino acids should allow customers to find out what signals these post translational modifications convey to the organism. These first-time-possible experiments together with the high quality of arrays (due to the printing mechanism that ensures defect free nanolayers) explains unexpected high customer demand. The impact of these novel peptide arrays might be high. We, and customers use them to eventually find hints to the causes of hitherto unexplainable diseases, e.g. diabetes type 1. This achievement was not foreseen in the NANOSTACKS proposal.

Chemical synthesis in array format:
Another achievement that was not foreseen in the NANOSTACKS proposal was the finding that we can synthesise up to 50.000 different chemicals per glass slide beyond peptide synthesis. A publication that describes this novel chemical synthesis method is currently written. If advanced further, it would allow us to better understand the rules that govern chemical synthesis.

nano3D printed nanoscale materials in array format:
At the core of the NANOSTACKS project is nano3D printing materials. Unexpectedly, we found a surprisingly high percentage of nano3D printable materials. Moreover, when using a donor-heating-device we can obviously nano3D print materials that couldn’t be printed at room temperature. We had some problems in stacking these nanolayers, though. That should be solvable by using a specialized carrier material.
Meanwhile, in 2024, we managed to identify functioning nanostacks. A corresponding publication & patent application is currently written. It should be feasible to find energy efficient and platinum free fuel cells. If advanced further, the impact of that new technology might be immense.
Assembled nano3D printer