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Polymeric Self-Assembling Units for a Controlled Adsorption and Release at the Nanoscale

Periodic Reporting for period 1 - NANODRIVE (Polymeric Self-Assembling Units for a Controlled Adsorption and Release at the Nanoscale)

Reporting period: 2017-05-02 to 2019-05-01

Selective adsorption and release is an extremely complex topic with a plethora of possible applications. Drug delivery, designing systems able to monitor and track the presence of given substances in gas or in solutions, selective removal of contaminants from solutions (e.g. heavy metals of antibiotics from water), or systems able to selectively release substances with a controlled release path are all different aspects of the same general class of problem: tunable adsorption and release at the nanoscale.

NANODRIVE focuses on the design of functionalisable materials at the nano-scale. In particular NANODRIVE aims at designing macromolecules able to selectively adsorb cargo in crowded solutions, being able to distinguish between different substances in solution and only adsorbing the target ones. Starting from the macromolecular scale, NANODRIVE aims at underpinning the key parameters able to lead to the aimed specific adsorption/release properties.

Polymer science has appeared to be a very promising field in the design and realisation of functionalised macromolecules, opening to countless possibilities to design and manufacture building blocks that, by means of a specific architecture or chemical composition, present tunable and controllable properties both at the single molecule level as well as at the mesoscale.

NANODRIVE focused on understanding how to exploit the flexibility and tunability of both polymeric systems of different chemical or topological architecture and nanocomposites, to selectively adsorb and release material in solution.
In particular, it allowed to design “macromolecules cages” able to recognise and insulate specific target cargos in solutions - e.g. pollutants in water - and to be then able to absorb and release them in a controlled way by tuning a few chemical/physical parameters.

The project addressed such a problem from various perspectives at the nanoscale, both designing “smart” polymeric systems as well as exploiting properties of targeted nanocomposites. NANODRIVE allowed to design macromolecules that were able to selectively capture specific target contaminants in solution. In particular two different systems able to selectively remove different heavy metals from aqueous solutions have been designed theoretically and realised experimentally.
The framework of functionalisable tunable adsorber is a topic that NANODRIVE addressed from a wide perspective; we designed theoretically and realised experimentally polymeric macromolecules that have the ability of selectively adsorbe cargo, with an adsorption process, that can be controlled enthalpically, entropically and geometrically. Starting from the adsorption properties of simple homopolymeric star polymers, we designed a set of macromolecular nanobots able to load cargo and recognise heavy metals in complex and crowded solution by changing either chemical composition of the geometry of the nanoparticles.

We then moved to the realisation of diblock copolymer star polymers, that are characterised by having an inner part that is able to selectively attract cargo, and an outer thermosensible part. The thermosensitivity was added to the original nanoparticles so that once the macromolecules adsorbed the target contaminant from a solution, a slight change in temperature locks the cargo, and allows for its selective removal. The nanoparticles that were designed theoretically and computationally, have been realised and validated experimentally for the selective adsorption of heavy metals in solution.

The close interaction with experimental groups allowed for a slight deviation beyond the original plan of NANODRIVE, extending the project to the design and experimental realisation of functionalised nanocomposites able to selectively capture heavy metal in solution. In particular we intended to understand how to design nanoparticles that would be able to distinguish between diverse metallic pollutants. As we aimed at nanoparticles that could be used on the large scale, and whose toxicological impact could be controlled and analysed, we focused on functionalised Ag Nano Particles (AgNPs)

The results obtained within NANODRIVE have been published - by the end of the project - in 2 peer reviewed publications, 4 papers are currently submitted, and a seventh publication is a scientific dissemination paper on the topic of nanoparticles for sustainable development.
The research topic was presented at 6 international conferences (4 invited talks and 2 contributed talks).
NANODRIVE reached its goal to design particles able to adsorb cargos of different kind, as well as to have control over the selectivity in the adsorption of the cargo.
A strong link with experiments was set up. As a matter of fact, during the project, the interaction with the experimental counterpart was strengthened beyond what was originally planned, becoming paramount in designing the polymeric macromolecules.
All results obtained for single molecules were extended to properties of particles in solution, and tests were performed both theoretically as well as experimentally. Such tests have been conducted for more diversified systems with respect to the ones that were originally planned. Moreover a collaboration with an ecotoxicology group was started with the aim of testing the toxicity and the ecocompatibility of the particles obtained within the NANODRIVE project.


NANODRIVE allowed to start a new research line, and collaborations with groups that are addressing the problem of selective adsorption and release from different perspectives, analysing diverse systems all performing a very similar action. Unveiling the commonalities between the adsorption and release processes in very diverse materials is crucial to highlight the key parameters that drive the whole process at the nanoscale.
Starting from the theoretical macromolecular design and working closely together with experimental groups, the results obtained by NANODRIVE will allow to develop a hybrid theoretical/experimental path able to design and realise materials with very specific tunable functionalities. Such materials have a manifold of potential applications, starting from the water filtering processes at the molecular level up to drug delivery. This research line has a very strong potential impact.

Merging the scientific results obtained by the project and the outcome of the dissemination path in developing countries, will allow to bringing together the research lines started with NANODRIVE with the concept of Sustainable development. In particular, we aim at applying the know-how consolidated within NANODRIVE in the field of selective adsorption framework to the more general water sanitation problem.
Controlled adsorption of colloids within a star polymer.
Selective adsorption of Cd2+ and Hg2+ within tract sets of effective interactions between diverse ex