Diaminodicyanoanthroquinodimethanes: Electrically driven molecular micromotors

Project Information

electorsDDADM

Grant agreement ID: 101063710

DOI

10.3030/101063710

Project closed

EC signature date 9 June 2022

Start date 1 October 2022

End date 30 September 2024

Funded under

• Marie Skłodowska-Curie Actions (MSCA)

Total cost

No data

EU contribution

€ 166 278,72

Coordinated by

VYSOKE UCENI TECHNICKE V BRNE
Czechia

Periodic Reporting for period 1 - electorsDDADM (Diaminodicyanoanthroquinodimethanes: Electrically driven molecular micromotors)

Reporting period: 2022-10-01 to 2024-09-30

Summary of the context and overall objectives of the project

Implementation of microrobots in various biomedical applications is continuously updating day by day and still needs to develop for the sake of humankind's healthy life and environmental remediation. Abnormal acidity changes in the stomach lead to several health issues, including gastroesophageal reflux disease (GERD) and peptic ulcers. Commonly, Proton pump inhibitors (PPIs) and acid-based tablets are employed to treat acid reflexes. Surgeries are recommended for the advanced gastrointestinal illness. In the near future, microrobots will be an efficient alternative for the surgeries. Abnormal gastric acid secretion is the main cause of the gastrointestinal diseases. Gastric acid is a chemical combination of hydrochloric acid, pepsin, and lipase. Gastric acid not only causes disease but also protects from the ingested pathogenic microorganisms from food and plays an important role in good digestion. Among the conventional techniques for monitoring acidity, fluorescent microrobots stand out due to their advantages, such as fluorescence and sensitivity.
Explosive detection is an extremely attention-seeking research area in the twentieth century, and there is a need to develop probes for the different detection environments. Probes for detecting explosives exist mostly as power, crystal, liquid, and paper strips; they are unsuitable for hard-to-reach areas. Picric acid is an extremely dangerous explosive among the other nitro-explosive chemicals, an even stronger explosive than trinitrotoluene (TNT). Excellent solubility, high toxicity at very low concentrations, and wide utilization in several industries like pharmaceuticals, dye industries, and fuel for rockets make them one of the highly influenced pollutants for water bodies and soil.
Tetracycline (Tc) is one of the most widely employed antibiotics due to its high antibacterial activity, cheap and toxic-free. Excessive usage of tetracycline develops antibiotic resistance and pollutes the water and soil bodies and even foods, including milk, eggs, etc. Presently, there are several detection methods for tetracycline, including spectroscopy, immunoassay, and chemotherapy. Among them, fluorescent sensing is outstanding due to its high sensitivity. Fluorescent microrobots are the best candidates for sensing the interest of target pollutants in hard-to-reach areas. Commercial fluorescent dye molecules are suffering from aggregation-caused quenching, which restricts their application. In this project, for the first time, we have developed aggregation-induced emissive (AIE) multi-fluorescent magnetically powered Diaminodicyanoquinodimethanes (DADQs) based microrobots for monitoring intragastric acidity. Extending the application of the fabricated microrobots into other applications was also possible, and then it was implemented to detect picric acid and tetracycline. The electorsDDADM addressed the fabrication of molecular materials-based fluorescent microrobots with excellent AIE fluorescence and their potential in various applications, as discussed above. The results of the project will pave a new path for the fabrication of new types of molecular material-based microrobots and their future applications, which can boost the EU sustainable development goals.
Hence, the overall objectives of electorsDDADM were (i) Synthesis of the derivatives of the Diaminodicyanoquinodimethanes (DADQs), (ii) Fabrication of the molecular materials-based microrobots via simple reprecipitation method, (iii) Actuation of the micromotors are analysed under the magnetic field, (iv) Applications in different fields, including bio-medical field and water cleaning treatments, and (v) Insight into the molecular level interaction that could be behind the fluorescent changes during the application process.

Work performed from the beginning of the project to the end of the period covered by the report and main results achieved so far

Magnetically steered multi-fluorescent microrobots have been developed for different applications, including intragastric acidity, detection of picric acid, and tetracycline. Initially, 7,7-bis(2-(2-aminoethyl)pyridino)−8,8-dicyanoquinodimethane is synthesized and characterized using NMR and SCXRD studies. For the first time, Fe3O4 nanoparticles decorated molecular materials based fluorescent microrobots are fabricated using simple reprecipitation techniques, and their actuation was studied under different magnetic field frequencies. Microrobots with multi-fluorescence were achieved by adopting different reaction conditions. The fluorescence memory of the microrobots at different pH ranges was studied and employed in observing pH changes in gastric acid. Molecular-level modifications in the microrobots at different pH conditions that cause fluorescence changes of gastric acid were investigated using FTIR analysis. Molecular material-based micromotors are suitable for biomedical applications, as they are toxic-free and easy to handle. Later, soft tissue models were devised to demonstrate the pH changes of the gastric acid in real-life applications. Fabricated microrobots were injected into the dead mouse and explored their capability of bio-medical applications.
One of the main advantages of designing molecular materials is their simple structural tailorability, which allows us to expand the applications of microrobots. We designed different dicyanoquinodimethane derivatives with free amino functional groups for detecting picric acid and tetracycline. We synthesised 7-pyrrolidino-7-(1(3-aminopropyl)imidazole-8,8 dicyanoquinodimethanes by a two-step synthetic process. Synthesised materials were employed for the fabrication of the microrobots with Fe3O4 nanoparticles using a simple reprecipitation method. The magnetically moved microrobots are employed to detect picric acid and tetracycline. For the first time, the selective sensing of the microrobots for picric acid from other nitro aromatics is investigated. The detection limit of microrobots for picric acid and tetracycline was found to be 0.1 and 0.3 μM, respectively. The molecular interactions between the moelcuales of the microrobots and pollutants were analysed using various analyses, including FTIR, FESEM, and fluorescence microscopic analysis. A fluidic channel was employed to exhibit their capability in real life sensing applications in hard-to-reach areas. By tuning the functionality of microrobots, it can be employed for water treatment applications like the removal of micro- and nanoplastic particles and microorganisms from aquatic environments.

Progress beyond the state of the art and expected potential impact (including the socio-economic impact and the wider societal implications of the project so far)

The project, electorsDDADM, has developed a general concept for the fabrication of fluorescent molecular material based microrobots for different applications as follows: 1. Monitoring intragastric acidity and 2. Detection of picric acid and tetracycline. In the proposal, we set the goal to fabricate molecular material based microrobots with different fancy morphological structures and discussed application possibilities in different fields. The first work of the electorsDDADM deals with the fabrication of the multi-fluorescent molecular material based microrobots using a simple reprecipitation method as discussed in the proposal and applied in monitoring intragastric acidity, which is beyond state of the art. This will open a new path for the fabrication of a new class of molecular material based microrobots for different biomedical applications. Next work is developed with different functional group substituted dimainodicyanoquinodimethanes, 7-pyrrolidino-7-(1(3-aminopropyl) imidazole-8,8 dicyanoquinodimethanes for picric acid and tetracycline sensing, which is completely beyond our proposal plan. Noteworthy, this project addressed the following EU sustainable development goals: 1. Good health and well-being; and 2. Water treatment. These findings enlighten the capability of microrobots in a wide range of applications, including the removal of micro/nano plastics, which is one of the serious risks to living organisms. The developed protocols for the fabrication of molecular materials based microrobots are cheaper than classical metal based microrobots with gold or platinum coatings, which is economically helpful to the microrobots research community. The project established the capability of the microrobots in different application fields and will likely have a favorable impact among the material research community. Biomedical applications and selective detection of nitro explosives and antibiotics by using fluorescent microrobots are believed to have a high impact on the medical and environmental remediation fields in the near future.

project-2.png

project-1.jpg