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CHIMICA SUPRAMOLECOLARE

Giornata dei Dottorandi

Abstract Book

Rome

CNR – Aula Marconi

24-25 May 2018

Organized by

Istituto di Metodologie Chimiche

Under the patronage of

Società Chimica Italiana Dipartimento Scienze Chimiche

e Tecnologie dei Materiali Consiglio Nazionale delle

Ricerche Società Chimica Italiana

SEZIONE LAZIO

CHIMICA SUPRAMOLECOLARE Giornata dei Dottorandi Boards and Commitees

Conference Chairpersons

Cecilia Bombelli

Stefano Di Stefano

Scientific Committee

Antonella Dalla Cort

Stefano Di Stefano

Cecilia Bombelli

Giovanna Mancini

Organizing Committee

Cecilia Bombelli

Francesca Ceccacci

Antonella Dalla Cort

Stefano Di Stefano

Giorgio Giardini

Giuliana Gigli

Giovanna Mancini

Marco Pastore

Riccardo Salvio

2

CHIMICA SUPRAMOLECOLARE Giornata dei Dottorandi

Programme

3

CHIMICA SUPRAMOLECOLARE Giornata dei Dottorandi Programme

THURSDAY MAY 24

11.00 Registration

14.30 Opening Ceremony

Chairperson: Antonella Dalla Cort

Invited lectures

14.45 - 15.15 “Beyond equilibrium self-assembly”

Alessandro Sorrenti (ETH-Zurich)

Oral Presentations

15.15 – 15.35 “(Hyper)branched highly fluorinated compounds for more sustainable self-assembled

functional material”

Marta Rosati (Politecnico di Milano)

15.35 – 15.55 “Controlling Chemical Reactivity Through Self-Assembly”

Maria A. Cardona (Università di Padova)

15.55 – 16.15 “Selective methylene oxidation of linear alkyl amines with H2O2 catalyzed by a Mn-nonheme

complex guided by supramolecular recognition”

Alessia Barbieri (Università di Roma La Sapienza)

16.15-16.35 Coffee break

Chairperson: Riccardo Salvio

Flash Presentations

16.35 – 17.00 “Reversible energy transfer to lanthanoid ions mediated by calixarenes”

Federica Faroldi (Università di Parma – Curtin University, Perth)

“Direct hydroxylation of benzene and aromatics with H2O2 catalyzed by a self-assembled

iron complex: evidence for a metal-based mechanism”

Giorgio Capocasa (Università di Roma La Sapienza)

“Synthesis and Investigation of Croconates as Smart Organic Coating for Noble Metals

Nanoparticles”

Beatrice Cogliati (Università di Parma)

“Synthesis and characterization of a paramagnetic [2]-rotaxane based on a crown ether-like

wheel incorporating a nitroxide motif”

Cecilia Poderi (Università di Bologna)

“Investigating the Polarity of Silica Nanoparticles”

Elahe Haddadi (Università di Bologna - Shiraz University, Shiraz, Iran)

4


Chairperson: Luigi Mandolini

Oral Presentations

17.00 – 17.20 “Trifunctional calix[4]arene as mimic of DNA topoisomerase I for the promotion of

phosphoryl transfer processes”

Stefano Volpi (Università di Parma)

17.20 – 17.40 “Dodecylcalix[n]arenes: new highly lipophilic members of the calixarene family”

Andrea Magini (Università di Parma)

17.40 – 18.00 “Effect of a non-innocent redox ligand on the reactivity of a [FeFe] hydrogenases mimic”

Andrea Mele (CNRS - CEMCA, Brest)

18.00– 18.20 “Uranyl-salophen complexes: useful platforms to investigate halide-π interactions in solution

and in the solid state”

Luca Leoni (Università di Roma La Sapienza)

20.00 Social Dinner

FRIDAY MAY 25

Chairperson: Stefano Di Stefano

Invited lecture

9.00 – 9.30 “Can we use supramolecular architectures as CHEMICAL INFRASTRUCTURES ?”

Josè Augusto Berrocal (University of Groningen and Eindhoven University of Technology)

Oral Presentations

9.30 – 9.50 “Use of active template approach to the preparation of novel spin-labelled [2]rotaxanes”

Lorenzo Gualandi (Università di Bologna)

9.50 – 10.10 “Efficient active-template synthesis of calix[6]arene-based oriented rotaxanes and

pseudorotaxanes”

Margherita Bazzoni (Università di Parma)

10.10 – 10.30 “Light-powered artificial molecular pumps”

Martina Canton (Università di Bologna)

10.30 – 11.00 Coffee break

Chairperson: Osvaldo Lanzalunga

Oral Presentations

11.00 – 11.20 “Light Harvesting Antennae Based on Silicon Nanocrystals”

Sara Angeloni (Università di Bologna)

5


11.20 – 11.40 “Porphyrinoids as multicomponent light-harvesting systems”

Beatrice Berionni Berna (Università di Roma Tor Vergata)

11.40 – 12.00 “Gold nanoparticles as designer drugs NMR detectors”

Daniele Rosa-Gastaldo (Università di Padova)

12.00 – 12.20 “Formation of Imidazo[1,5‑ a]pyridine Derivatives Due to the Action of Fe2+

on Dynamic

Libraries of Imines”

Simone Albano (Università di Roma La Sapienza)

12.45 Lunch

Chairperson: Francesca Ceccacci

Flash Presentations

14.30 – 15.05 “Protein stabilized nanoformulation of a superfluorinated 19

F-MRI contrast agent”

Nazeeha Ayaz (Politecnico di Milano)

“Luminescent nanoparticles release from biocompatible polymeric fibers”

Liviana Mummolo (Università di Bologna)

“Nanoemulsion: a versatile formulation”

Anna Imbriano (Università di Roma La Sapienza)

“Catanionic mixtures of bile salt derivatives”

Emilia Severoni (Università di Roma La Sapienza)

“Glycosylated liposomes for targeting bacteria”

Stefano Aiello (Università di Roma La Sapienza)

“Self-assembling supramolecular structures as stimuli-responsive systems for sensing pH and

anions in water”

Valeria Caponetti (Università di Bologna)

Chairperson: Cecilia Bombelli

Oral Presentations

15.10 – 15.30 “Antibacterial activity of (+)-usnic acid included in mixed liposomes containing structurally

related L- prolinol derivatives”

Sara Battista (Università dell’ Aquila)

15.30 – 15.50 “Luminescent chemosensors for oxygen”

Benedetta Del Secco (Università di Bologna)

15.50 – 16.10 “Functional liposomes and multi-stimuli responsive polymers encompassing the versatile 2-

(hydroxyimino)aldehyde group”

Martina Nardi (Università di Roma La Sapienza)

16.10 – 16.40 Coffee break

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Chairperson: Giovanna Mancini

Oral Presentations

16.40 – 17.00 “New transparent colloidal TiO2 nano-systems as efficient photocatalysts for environmental

remediation”

Arianna Menichetti (Università di Bologna)

17.00 – 17.20 “Novel CuI-based Metal Organic Frameworks for sensing applications”

Khaled Hassenein (CNR-ISOF Bologna)

17.20 – 17.40 “Carboxylic Acids as Chemical Fuels for a Catenane Based Molecular Switch: Tuning the

Motion Rate”

Chiara Biagini (Università di Roma “La Sapienza”)

17.45 – 18.00 Closing Remarks

7


Invited Lectures

CHIMICA SUPRAMOLECOLARE Giornata dei Dottorandi IL - A.SORRENTI

Beyond equilibrium self-assembly

Alessandro Sorrenti

Institute for Chemical & Bioengineering, Department of Chemistry & Applied Biosciences, ETH Zurich,

Zurich 8093, Switzerland.

Email of presenting author: [email protected].

Over the past decades, supramolecular chemists have

managed to prepare well-ordered and incredibly

sophisticated architectures, many of which have been

engineered to respond to a variety of stimuli, such as pH,

light or ionic strength.1 The overwhelming majority of these

supramolecular systems are thermodynamic equilibrium

states, whose structure is independent of the exact path by

which monomers self-assemble and remains unchanged over

time. Most recently, however, there has been a growing

interest in kinetically trapped structures (non-dissipative

non-equilibrium states) that strongly depend on the

preparation procedure, and where the assembly rates are of

key importance.2 Nevertheless, we are still far from

achieving the functional complexity of living self-assembled

systems, such as microtubules and biomembranes. This is because living systems operate in so-called

dissipative non-equilibrium states, and continuously consume energy to precisely control, in space and time,

their supramolecular structure and their functions.2,3

Mimicking nature, the latest innovation in the field of

molecular self-assembly relies on using (chemical) energy inputs, i.e. energy dissipation, to form and keep

the self-assembled systems away from the thermodynamic equilibrium.4–6

In this talk, I will discuss and give illustrative examples of non-equilibrium supramolecular systems, both

kinetically trapped and dissipative. In the former case, I will show how the control over self-assembly

kinetics (e.g. achieved by controlled reactant diffusion under microfluidic mixing,7 or by hydrodynamic

fields8) may allow to select the desired aggregation pathway(s), ultimately leading to different aggregates

from the same building blocks. In the latter case, I will report on a supramolecular polymer, whose assembly

and disassembly is regulated by enzymatic phosphorylation/dephosphorylation of the building blocks, that

can be kept in various non-equilibrium steady states inside a membrane reactor where the fuel ATP is added

continuously, while waste are removed.6

1. J.-M. Lehn, Supramolecular Chemistry: Concepts and Perspectives. (Wiley, 1995).

2. A. Sorrenti, J. Leira-Iglesias, A. J. Markvoort, T. F. A. de Greef, T. M. Hermans, Chem. Soc. Rev.,

2017, 46, 5476.

3. M. Fialkowski, et al. J. Phys. Chem. B, 2006, 110, 2482.

4. J. Boekhoven, et al. Angew. Chem. Int. Ed. 2010, 49, 4825.

5. J. Boekhoven, W. E. Hendriksen, G. J. Koper, R. Eelkema, J. H. van Esch, Science 2015, 349, 1075.

6. A. Sorrenti, J. Leira-Iglesias, A. Sato, T. M. Hermans, Nat. Commun.2017, 8, 15899.

7. A. Sorrenti, R. Rodriguez-Trujillo, D. B. Amabilino, J. Puigmartí-Luis, J. Am. Chem. Soc. 2016, 138,

6920.

8. A. Sorrenti, Z. El-Hachemi, J. Crusats, J. M. Ribó, Chem. Commun. 2011, 47, 8551.

9

Figure 1. Thermodynamic states in supramolecular

self-assembly.

CHIMICA SUPRAMOLECOLARE Giornata dei Dottorandi IL - J.A.BERROCAL

Can we use supramolecular architectures as “chemical infrastructures”?

José Augusto Berrocal,a, b

G. Henrieke Heideman,b Bas F. M. de Waal,

a E. W. Meijer,

a Ben L. Feringa

b

a Centre for Systems Chemistry, Stratingh Institute for Chemistry and Zernike Institute for Advanced

Materials, Faculty of Mathematics and Natural Sciences, University of Groningen, Nijenborgh 4, 9747 AG

Groningen, the Netherlands; b Institute for Complex Molecular Systems and Laboratory of Macromolecular

and Organic Chemistry, Eindhoven University of Technology, 5600 MB, Eindhoven, the Netherlands.


Designing molecules which self-assemble into a plethora of morphologies is one of the most intriguing

aspects of supramolecular chemistry. The main challenge is the fundamental understanding of the parameters

that control and trigger the self-assembly process. Such knowledge can expand the enormous potential of the

supramolecular field,1 and lead to a sort of molecular “city planning”, namely positioning molecules that

exert a programmed function in a specific area in space.

In this contribution we will present our latest strategy for obtaining well-ordered 3- and 2-dimensional self-

assembled architectures in the solid state and at the solution-surface interface. The strategy consists of

covalently combining cristallinity and thermodynamic incompatibility in the same molecular skeleton. The

synergy of these two characteristics affords sub-10 nm periodical structures with long-range order.2 In the

final part of the talk, we will discuss the recent application of this approach towards controlling the

translation of Feringa’s 3rd

generation unidirectional motors3 on “molecular highways” on surfaces

(Figure 1).

Figure 1. Pictorial representation of the supramolecularly-controlled

translation of Feringa’s unidirectional motors on “molecular highways”.

1. T. Aida; E. W. Meijer, S. I. Stupp, Science 2012, 335, 813–817.

2. J. A. Berrocal; R. H. Zha; B. F. M. de Waal; J. A. M. Lugger; M. Lutz, E. W. Meijer, ACS Nano 2017,

11, 3733-3741.

3. J. C. M. Kistemaker; P. Štacko; D. Roke; A. T. Wolters; G. H. Heideman; M.-C. Chang; P. van der

Meulen; J. Visser; E. Otten; B. L. Feringa, J. Am. Chem. Soc. 2017, 139, 9650–9661.

10

https://pubs.acs.org/author/Kistemaker%2C+Jos+C+M

https://pubs.acs.org/author/%C5%A0tacko%2C+Peter

https://pubs.acs.org/author/Roke%2C+Diederik

https://pubs.acs.org/author/Wolters%2C+Alexander+T

https://pubs.acs.org/author/Heideman%2C+G+Henrieke

https://pubs.acs.org/author/Chang%2C+Mu-Chieh

https://pubs.acs.org/author/van+der+Meulen%2C+Pieter

https://pubs.acs.org/author/van+der+Meulen%2C+Pieter

https://pubs.acs.org/author/Visser%2C+Johan

https://pubs.acs.org/author/Otten%2C+Edwin

https://pubs.acs.org/author/Feringa%2C+Ben+L


Oral Presentations

CHIMICA SUPRAMOLECOLARE Giornata dei Dottorandi OP - M.ROSATI

(Hyper)branched highly fluorinated compounds for more sustainable self-

assembled functional materials

Marta Rosati, Isabel Martinez Espinoza, Valentina Dichiarante, Francesca Baldelli Bombelli, Gabriella

Cavallo, Pierangelo Metrangolo.

Laboratory of Supramolecular and Bio-Nanomaterials (SupraBioNanoLab), Department of Chemistry,

Materials and Chemical Engineering “Giulio Natta”, Politecnico di Milano, Via L. Mancinelli 7, 20131

Milan, Italy.

Email of presenting author: [email protected]; Web-site: www.suprabionano.eu

Perfluorinated materials have found applications in many technological fields thanks to their stability, their

dielectric properties and their water and oil repellency. Moreover, their tendency to form self-assembled

monolayers (SAMs) plays a major role in the achievement of new functional surface properties. Furthermore,

fluorinated molecules can also be applied in 19

F-Magnetic Resonance Imaging analysis (19

F-MRI), an

emerging, powerful noninvasive technique for early disease diagnosis and treatment1.

Due to their bioaccumulative potential, perfluorinated substances with fluorinated long chains have been

banned. The use of short perfluoroalkyl chains (C ≤ 4) reduces the lipophilicity and, consequently, the

bioaccumulation although with a loss in performance2,3

.

Herein we show the synthesis of a new family of fluorinated compounds (see figure 1) characterized by

ultrashort (C1) fluorinated alkyl groups, surrounding a hydrocarbon polar core. This unique design allows to

multiply the number of fluorine atoms in the molecule while the presence of four ether bonds in the core may

hasten molecular degradation in the environment thanks to the cleavage of such bonds in physiological

conditions. Furthermore, the possibility to introduce different active units will open new routes towards self-

assembled nanostructured materials for innovative applications4,5

.

a b

Figure 1. Chemical structures of the branched highly fluorinated molecules under

investigation: a) PERFECTA - a promising contrast agent for 19

F-MRI; b) general

structure of the PERFECTA derivatives.

1. I. Tirotta, V. Dichiarante, C. Pigliacelli, G. Cavallo, G. Terraneo, F. Baldelli Bombelli, P. Metrangolo,

G. Resnati, Chem. Rev., 2015, 115, 1106.

2. Z. Wang, I. T. Cousins, M. Scheringer, K. Hungerbühler, Environment International, 2013, 60, 242.

3. V. Dichiarante, R. Milani, P. Metrangolo, Green Chem., 2018, 20, 13.

4. V. Dichiarante, I. Tirotta, L. Catalano, G. Terraneo, G. Raffaini, M. R. Chierotti, R. Gobetto, F. Baldelli

Bombelli, P. Metrangolo, Chem. Commun., 2017, 53, 621.

5. I. Tirotta, A. Mastropietro, C. Cordiglieri, L. Gazzera, F. Baggi, G. Baselli, M. G. Bruzzone, I. Zucca,

G. Cavallo, G. Terraneo, F. Baldelli Bombelli, P. Metrangolo, G. Resnati, J. Am. Chem. Soc., 2014,

136, 8524.

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mailto:[email protected]

CHIMICA SUPRAMOLECOLARE Giornata dei Dottorandi OP - M.A.CARDONA

Controlling Chemical Reactivity Through Self-Assembly

Maria A. Cardona, Leonard J. Prins.

Dipartimento di Scienze Chimiche, Università di Padova, via Marzolo 1, 35121, Padova.

Email of presenting author: [email protected]

The evolutionary appearance of the cell marks a most important milestone in the history of Earth since it led

to the emergence of life. Research on artificial vesicles has been on the increase lately since vesicles can be

considered models of protocells, and thus can contribute to the understanding of the emergence of life from

inanimate matter. One prominent area of research is the use of self-assembled vesicles as reaction promoters

and regulators. Self-assembly of vesicles gives the system emergent properties, since new functions, which

are absent in the presence of the non-assembled system, emerge only in the aggregated state.1

The aim of this research is to use self-assembled vesicles as a means of controlling the reactivity of chemical

reactions.1 A hydrazone reaction involving hydrophobic reactants proceeded only slowly in the non-

aggregated surfactant but was amplified in the presence of aggregated vesicles. Replacing one of the

reactants with a water-soluble one resulted in preferential hydrazone formation in the non-aggregated state.

Thus, it was possible to preferentially select the product formed by the presence or absence of the aggregated

state.

Adhesion and fusion of membranes are fundamental for cellular function as they mediate important

biological processes like synaptic neurotransmission, endo and exocytosis.2 Aggregation of vesicles is

analogous to adhesion of membranes in biological systems. A system was thus developed whereby negative

vesicles were aggregated in the presence of positive nanoparticles and disaggregated in the presence of a

competing negative competitor, namely ATP. The principles developed could be used to control the

reactivity of a reaction catalysed by the nanoparticles, whereby reactivity was different in the aggregated and

disaggregated state. Both these systems demonstrate that vesicles are able to result in emergent functions

and contribute to the emergence of complexity in synthetic systems.

Figure 1: (a) Figure showing different reactivity in the aggregated and disaggregated states. (b). Figure

showing aggregation and disaggregation using nanoparticles and ATP.

1. P. Walde, H. Umakoshi, P. Stano, F. Mavelli, Chem. Commun., 2014, 50, 10177.

2. S. Himmelein, B.J. Ravoo, Bioinspiration and Biomimicry in Chemistry; John Wiley & Sons, Inc.;

2012, 209.

Acknowledgements: The work is funded by the Marie-Curie ITN Network MULTI-APP (Grant Agreement

642793.

13

(a) (b)

CHIMICA SUPRAMOLECOLARE Giornata dei Dottorandi OP - A.BARBIERI

Selective methylene oxidation of linear alkyl amines with H2O2 catalyzed

by a Mn-nonheme complex guided by supramolecular recognition.

Alessia Barbieri,a Giorgio Olivo,

b Giulio Farinelli,

a Osvaldo Lanzalunga,

a Stefano Di Stefano,

a Miquel

Costas.b

aDipartimento di Chimica, Università di Roma “La Sapienza” and Istituto CNR di Metodologie Chimiche

(IMC-CNR), Sezione Meccanismi di Reazione, Roma. bDepartament de Quimica, Universitat de Girona,

Campus de Montolivi, Spain.


In nature the functionalization of specific C-H bonds is performed with excellent selectivity by many metal

dependent oxygenases such as P450 and nonheme iron dependent proline hydroxylases, thanks to multiple

and specific weak interactions between the aminoacidic residues and/or cofactors within the cavity.

Nevertheless, reproduction of such elaborated architecture that allows optimal substrate-catalyst interactions,

is not so simple in the synthetic systems.

We have synthetized a supramolecular and bioinspired ditopic catalyst containing a Mn-PDP complex as

active site and benzo-18-crown-6 ether as supramolecular receptor which catalyzes regioselectively C-H

hydroxylation of linear protonated primary amines in presence of H2O2 (Figure 1).

Figure 1.

The reversible pre-association substrate-crown ether receptor, directs the site-selectivity of the oxidation on

C8 and C9 methylene positions for a whole series of linear amine substrates, overriding the intrinsic

reactivity of the other C-H bonds. This supramolecular control provides a suitable strategy to predictably

promote selective oxidation of linear amines.

We believe that the interesting potential of this supramolecular approach, would provide a synthetic

attractive way to disclose novel site-selectivities in C-H functionalization reactions.

1. R. Breslow, X. Zhang, Y. Huang, J. Am. Chem. Soc., 1997, 119, 4535.

2. S. Das, C. D. Incarvito, R. H. Crabtree, G. W. Brudvig, Science, 2006, 312, 1941. 3. G. Olivo, G. Farinelli, A. Barbieri, O. Lanzalunga, S. Di Stefano, M. Costas, Angew. Chem. Int. Ed.,

2017, 1, 16347.

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CHIMICA SUPRAMOLECOLARE Giornata dei Dottorandi OP - S.VOLPI

Trifunctional calix[4]arene as mimic of DNA topoisomerase I for the

promotion of phosphoryl transfer processes

Stefano Volpi,a Riccardo Salvio,

b Roberta Cacciapaglia,

b Francesco Sansone,

a Luigi Mandolini,

b Alessandro

Casnati.a

aDipartimento di Scienze Chimiche, della Vita e della Sostenibilità Ambientale, Università degli Studi di

Parma, Viale delle Scienze 17/A, 43124, Parma, Italy; bDipartimento di Chimica e Sezione Meccanismi di

Reazione IMC−CNR, Università La Sapienza, P. le Aldo Moro 5, 00185 Roma, Italy.


The appropriate functionalization of the upper rim of cone-calix[4]arenes has been reported as an effective

strategy for the creation of artificial catalysts able to cleave the phosphodiester function of nucleic acids and

model compounds.1

With the aim to mimic the catalytic triad at the active site of human DNA topoisomerase I,2 it was

synthesized the trifunctional calix[4]arene (1H3)2+

, bearing at the upper rim two guanidinium units and a

phenolic hydroxyl group.3

The diprotonated form of the catalyst (1H2)+

was tested in the cleavage of the DNA model compound bis(p-

nitrophenyl) phosphate (BNPP) in 80% DMSO solution, with rate enhancement of p-nitrophenol liberation,

respect to the background hydrolysis, as high as 6.5 × 104-folds at pH 9.5.

According to the experimental data the three active units cooperate during a reaction sequence (Figure 1) that

involve a phosphoryl transfer process from BNPP to the nucleophilic phenolate moiety of (1H2)+, followed

by the liberation of a second equivalent of p-nitrophenol from the phosphorylated intermediate, thanks to the

electrophilic activation by the neighboring guanidine/guanidinium dyad.

Figure 1. Proposed mechanism for the cleavage of BNPP by (1H2)+.

1. M. Giuliani, I. Morbioli, F. Sansone, A. Casnati, Chem. Commun., 2015, 51, 14140.

2. M. R. Redinbo, L. Stewart, P. Kuhn, J. J. Champoux, W. G. J. Hol, Science, 1998, 279, 1504.

3. R. Salvio, S. Volpi, R. Cacciapaglia, F. Sansone, L. Mandolini, A. Casnati, J. Org. Chem., 2016, 81,

9012.

15

CHIMICA SUPRAMOLECOLARE Giornata dei Dottorandi OP - A.MELE

Effect of a non-innocent redox ligand on the reactivity of a [FeFe]

hydrogenases mimic

Andrea Mele, Catherine Elleouet, Philippe Schollhammer.

UMR CNRS 6521, CEMCA (Laboratoire de Chimie Electrochimie Moléculaires et Chimie Analytique),

Faculté des Sciences et Techniques - 6 Avenue Victor le Gorgeu, CS 9383729238 Brest cedex 3, France


[FeFe] hydrogenases mimics have been extensively used the last years to understand the functioning of the

active site of these enzymes and to mimic their activity towards electrocatalytic H+/H2 conversion.

1

After having developed many different kinds of bridges to connect the two iron atoms, a great effort is now

made to design ligands deeply involved in the redox properties of the whole molecule.

They are able to exercise an important and direct role on the global mechanism of the reaction, acting as an

electron reservoir like the cubane Fe4S4 in the natural active site of the enzyme.2.3

In this communication, the synthesis of two novel complexes [Fe2(CO)4(2-BMI)(µ-pdt)] and [Fe2(CO)4(

2-

BMI)(µ-adtBn

)] (BMI = 2,3-bis(diphenylphosphino)-N-phenylmaleimide) able to electrocatalyze the

production of hydrogen using weak acid sources will be presented and a mechanism will be postulated from

cyclic voltammetry and theoritical calculations studies.

1. W. Weigand, P. Schollhammer, Eds., Bioinspired Catalysis: Metal-Sulfur Complexes,

Wiley-VCH-Verl, Weinheim, 2015

2. Y. Si, K. Charreteur, J.F. Capon, F. Gloaguen, F.Y. Pétillon, P. Schollhammer, J.

Talarmin, J. Inorg. Biochem., 2010, 104, 1038-1042.

3. M.E Carroll, B.E. Barton, T.B. Rauchfuss, P.J. Carroll, J. Am. Chem. Soc., 2012, 134,

18843–18852.

16

CHIMICA SUPRAMOLECOLARE Giornata dei Dottorandi OP - L.LEONI

Uranyl-salophen complexes: useful platforms to investigate halide-π

interactions in solution and in the solid state

Luca Leoni,a Rakesh Puttreddy,

b Cecilia E. Chiaretti,

a Andrea Mele,

a Paolo Mencarelli,

a Kari Rissanen,

b

Antonella Dalla Cort.a

aUniversità di Roma La Sapienza, Piazzale Aldo Moro 5, 00185 Roma (Italy).

bUniversity of Jyväskylä, Department of Chemistry, Nanoscience Center P. O. Box 35, 40014, University of

Jyväskylä (Finland).


Lewis acidic uranyl-salophen [(N,N-phenylene-bis(salicylimine)] receptors are well known to have the fifth

equatorial binding site available for coordination with chemical species endowed with a hard donor site.1 The

presence in the ligand skeleton of an electron-deficient π-acceptor aromatic ring (figure 1), beside the metal

center, favors binding of halides (as tetra-alkylammonium salts) through the interplay of two concerted

interactions, i.e. Lewis acid-base and anion-π interactions.

We measured the enhancement of the binding affinity towards halides in organic solvents, especially for

complexes bearing one or two perfluorophenyl units.2 The same trend is observed in the solid state, Fig 1.

Figure 1. X-Ray crystal structures of uranyl-salophen@Cl- complexes

decorated with one and two perfluorophenyl units.

1. A. Dalla Cort, P. De Bernardin, G. Forte and F. Yafteh Mihan, Chem. Soc. Rev., 2010, 39, 3863–3874.

2. L. Leoni, R. Puttreddy, O. Jurcek, A. Mele, I. Giannicchi, F. Yafteh Mihan, K. Rissanen and A. Dalla

Cort, Chem. Eur.J., 2016, 22, 18714 –18717.

17

CHIMICA SUPRAMOLECOLARE Giornata dei Dottorandi OP - L.GUALANDI

Use of active template approach to the preparation of novel spin-labelled

[2]rotaxanes

Lorenzo Gualandi,a Paola Franchi,

a Elisabetta Mezzina,

a Stephen Goldup,

b Marco Lucarini.

a

a Department of Chemistry “Giacomo Ciamician” University of Bologna, Via San Giacomo 11, 40126

Bologna (Italy).b Chemistry, University of Southampton, Highfield, Southampton SO17 1BJ, UK.


The active template approach to mechanical interlocked molecules (MIM) is based on the facility of metal

ions to both organize precursor fragments for mechanical bond formation and to mediate the final covalent

bond-forming reaction that traps the interlocked structure.1 Since its beginning just a decade ago, this new

metodology has increased rapidly from a single reaction for rotaxane synthesis to a range of metal-mediated

bond formations for the synthesis of complex interlocked molecules.

The active template approach requires the final covalent bond formation to take place through the cavity of

the macrocycle with the functionalized half-axle components positioned on opposite faces of the ring. If

these requirements are met, almost any bond formation can be generated by this reaction. This principle has

been widely demonstrated over the past decade and the active template modification of the well-known

‘click’ reaction was the first example used to prepare an interlocked molecule.2

Here we present the first examples of spin labelled [2]rotaxanes that had been synthesized using active

template methodology. The rotaxane was spin-labelled by the introduction of two nitronyl-nitroxide radicals

at both ends of the thread. Rotaxanation was proved to have a dramatic effect on magnetic interactions

between radical fragments. Analysis of the EPR spectra by a two-jump model,3 allowed us to obtain

structural information on the interlocked structure.

Figure 1. A Bis nitronyl-nitroxide labelled [2]Rotaxane

1. M. Denis, S.M. Goldup, Nat. Rev. Chem. 2017, 1, 61.

2. V. Aucagne, K. D. Hänni, D. A. Leigh, P. J. Lusby, D. B. Walker, J. Am. Chem. Soc. 2006, 128, 2186.

3. F. Romano, R. Manoni, P. Franchi, E. Mezzina, M. Lucarini Chem. Eur. J. 2015, 21, 2775.

18

CHIMICA SUPRAMOLECOLARE Giornata dei Dottorandi OP - M.BAZZONI

Efficient active-template synthesis of calix[6]arene-based oriented

rotaxanes and pseudorotaxanes

Margherita Bazzoni,a Valeria Zanichelli,

a Giulio Ragazzon,

b Guido Orlandini,

a Margherita Venturi,

b Alberto

Credi,c,d

Serena Silvi,b Arturo Arduini,

a Andrea Secchi.

a

a)Dipartimento di Scienze Chimiche, della Vita e della Sostenibilità Ambientale, Università di Parma, Parco

Area delle Scienze 17/A, I-43124 Parma, Italy; b)Dipartimento di Chimica “G. Ciamician”, Università di

Bologna, via Selmi 2,40126 Bologna, Italy; c)Dipartimento di Scienze e Tecnologie Agro-alimentari,

Università di Bologna, viale Fanin 50,40127 Bologna, Italy; d)Istituto per la Sintesi Organica e la

Fotoreattività, Consiglio Nazionale delle Ricerche, via Gobetti 101, 40129 Bologna, Italy;


Mechanically interlocked molecules (MIMs) such as rotaxanes, catenanes and related species, are attracting

great interest in view of their potential application in materials science, information technology, nanoscience,

catalysis and medicine.1 The growing interest in these species is strictly related to the development of simple

and efficient synthetic methodologies that rely on template-directed approaches. The complexation of a guest

molecule inside the cavity of a suitable host results in the modification of the chemical features of the guest,

up to a modification of its reactivity.

Within this context our research group investigate how the engulfment of a positively charged pyridil-

pyridinium-based guest inside the π-rich cavity of a tris-(N-phenylureido)calix[6]arene 2

host affects its

reactivity towards a SN2 reaction.3 We found that the alkylation of the complexed substrates leads to the

formation of oriented pseudorotaxanes and rotaxanes with faster kinetics and higher yields with respect to the

standard SN2reaction. More importantly, the strategy described here expands the range of efficient synthetic

routes for making mechanically interlocked species with a strict control of the mutual orientation of their

nonsymmetric molecular components.4

1. a) C. J. Bruns and J. F. Stoddart, The nature of the mechanical bond: from molecules to machines,

Wiley & Sons, Hoboken, 2017; b) From Non-Covalent Assemblies to Molecular Machines, J.-P.

Sauvage and P. Gaspard, Eds., Wiley-VCH, Weinheim, 2010; c) V. Balzani, A. Credi, M. Venturi,

Molecular devices and machines - Concepts and perspectives for the nanoworld, Wiley-VCH,

Weinheim, 2008.

2. Arduini, G. Orlandini, A. Secchi, A. Credi, S. Silvi and M. Venturi, in Calixarenes and Beyond, eds. P.

Neri, J. L. Sessler and M.-X. Wang, Springer, Cham, 2016, pp. 761–781;

3. G. Orlandini, G. Ragazzon, V. Zanichelli, A. Secchi, S. Silvi, M. Venturi, A. Arduini and A. Credi,

Chem. Commun., 2017, 53, 6172–6174.

4. V. Zanichelli, G. Ragazzon, G. Orlandini, M. Venturi, A. Credi, S. Silvi, A. Arduini, A. Secchi, Org.

Biomol. Chem., 2017, 15, 6753–6763.

19

CHIMICA SUPRAMOLECOLARE Giornata dei Dottorandi OP - M.CANTON

Light-powered artificial molecular pumps

Martina Canton,a,b

Lorenzo Casimiro,a,c

Jessica Groppi,a,b

Stefano Corrà,a,b

Marcello La Rosa,a,b

Christiaan

De Vet,a,b

Massimo Baroncini,a,b,d

Serena Silvi,a,c

Alberto Credi.a,b,d

a CLAN- Center for Light Activeted Nanostructures, Università di Bologna and Consiglio Nazionale delle

ricerche, via Gobetti 101, 40129 Bologna, Italy. b

Dipartimento di Scienze e Tecnologie Agro-alimentari,

Universita` di Bologna, viale Fanin 50, 40129 Bologna, Italy. c

Dipartimento di Chimica “Giacomo

Ciamician”, Universita` di Bologna, via Selmi 2, 40126 Bologna, Italy. d ISOF- Istituto per la Sintesi

Organica e Fotoreattività del CNR, via Gobetti 101, 40129 Bologna, Italy.


LEAPS, “Light Effected autonomous molecular pumps: Towards active transporters and actuating materials"

is a research project, funded by an European Research Council Advanced Grant, whose goal is to develop

supramolecular systems capable of performing directed and autonomous translational movements activated

by light energy and use them for transporting molecular substrates in a variety of set-ups. The system that we

are developing is a pseudorotaxane assembly

in which a molecular ring passes

unidirectionally through a molecular axle in

response to photochemical and chemical

stimulation. It is composed of a molecular ring

(1) and a non-symmetric molecular axle that

comprises: a cyclopentyl unit as passive

pseudo-stopper (2) at one end, an ammonium

cation as central recognition site for the ring

and an azobenzene stopper as bistable

photoswitchable unit (3) at the other end. The

ring should enter exclusively from the E-

azobenzene side of the axle for kinetic

reasons, affording a pseudorotaxane in which

the macrocycle encircles the recognition site

on account of hydrogen-bonding interactions between the oxygen atoms and the ammonium centre and,

possibly, π-stacking forces involving the naphthalene and azobenzene units. Subsequently, light irradiation

converts the E-azobenzene unit into the bulkier Z form, a process that causes a destabilization of the

supramolecular complex and dethreading of the components (Figure 1a). The next step will be to develop a

“second generation pump” by replacing the cyclopentyl pseudostopper with an appropriately substituted

phenyl unit, that is easier to functionalize (Figure 1b), in order to add further components to the

system.Another option is to append an alkyl chain of suitable length at the pseudostopper side, which can act

as a reservoir for collecting molecular rings, pumped by light. A nanodevice of this kind is of high interest

because it would convert the energy of the incident photons into chemical energy in the form of molecular

rings stored under a non-equilibrium condition.

1. Ragazzon, G. Baroncini, M. Silvi, S. Venturi, M. Credi, A. Nature Nanotechnology 10, 70–

75 (2015)

2. Ragazzon, G. Baroncini, M. Silvi, S. Venturi, M. Credi, A. Beilstein J. Nanotechnol 6, 2096–

2104 (2015)

20

OMe

Figure 1. a) Schematic representation of the relative

unidirectional translations of the ring and axle components

triggered by light. b) candidate subunits for the role of

pseudostopper in the axle component.

b

a

3 2

1

CHIMICA SUPRAMOLECOLARE Giornata dei Dottorandi OP - S.ANGELONI

Light Harvesting Antennae Based on Silicon Nanocrystals

Sara Angeloni,a Francesco Romano,

a Raffaello Mazzaro,

b Paola Ceroni.

a

a Departement of Chemistry, University of Bologna "G. Ciamician", Via Selmi 2, 40126 Bologna, Italy;

b Departement of Technology, University of Luleå , 971 87, Luleå, Sweden.


Silicon (Si) is an extraordinarily useful semiconductor, earth-abundant and non-toxic, but it exhibits no

significant luminescence at room temperature because of its indirect band gap. Si nanocrystals (SiNCs) -or

quantum dots- on the other hand can be efficient light emitters, with emission wavelength that can be tuned

by size from the near infrared (NIR) into the visible range, but they are weak light absorbers as a result of

their indirect band gap. To enhance the optical absorption of SiNCs, they can be employed as scaffolds for

light harvesting molecular antennae, which are made of many donors, the chromophores, and an acceptor, the

SiNC itself. These chromophores should be strong light absorbers and should have an efficient energy

transfer to the SiNCs, in order to enhance the SiNCs’ molar absorption coefficient and thus their brightness.1

Light harvesting molecular antennae were realized by applying two different synthetic methods. The first

synthetic rout allowed us to covalently attach the di-phenyl-anthracene (DPA) units onto the 3 nm diameter

SiNCs surface (Fig. 1a). The energy transfer efficiency was studied and approved. All the optical properties

of SiNCs were preserved. SiNCs functionalized with DPA will be used in order to improve the properties of

luminescence solar concentrators (LSC). In the second synthetic method, through the nanoprecipitation

technique,2 DPA units and 3 nm or 5 nm diameter SiNCs were both physically encapsulated inside polymer

nanoparticles (Fig. 1b). Exciting this system, the excitation energy transfer (EET) between the DPA

encapsulated units takes place until the interaction with an encapsulated SiNC. The energy transfer efficiency

was approved. The nanoprecipitation technique will be tested again with different organic dyes and different

polymer nanoparticles.

Figure 1. Schematic representation of a molecular antenna obtained with the covalent

method (a) and the non-covalent method (b).

1. F. Romano, Y. Yu, B. Korgel, G. Bergamini, P. Ceroni, Topics in Current Chemistry, 2016, 374, 89; R.

Mazzaro, F. Romano, P. Ceroni, Physical Chemistry Chemical Physics, 2017, 19, 26507.

2. A. Reisch and A. S. Klymchenko, Small, 2016, 12, 1968; A. Reisch, P. Didier, L. Richert, S. Oncul, Y.

Arntz, Y. Mèly and A. S. Klymchenko, Nature Communication, 2014, 5, 4089.

Acknowledgements: This work was funded by European Research Council (ERC), a starting grant (PhotoSi).

21

CHIMICA SUPRAMOLECOLARE Giornata dei Dottorandi OP - B.BERIONNI BERNA

Porphyrinoids as multicomponent light-harvesting systems

Beatrice Berionni Berna,a Benedikt Platzer,

b Pierluca Galloni,

a Sara Nardis,

a Dirk M. Guldi,

b Tomás Torres,

c

Roberto Paolesse.a

aDepartment of Chemical Science and Technology, University of Rome Tor Vergata, Italy

bDepartment of Chemistry and Pharmacy, Friedrich Alexander University Erlangen-Nuremberg, Germany

cDepartment of Organic Chemistry, Universidad Autónoma de Madrid, Cantoblanco, Spain


Preparation and study of bio-inspired artificial photosynthetic systems have given rise to remarkable interest

in the last few decades, and several kinds of electron donor−acceptor (D−A) ensembles exhibiting

photoinduced charge separation have been explored.1-4

We have focused our efforts on the synthesis of a dyad, where high energy light is absorbed by one dye

(corrole), then shuttled through the next dye (phthalocyanine).

In these models phthalocyanines are conjugated to different corroles by different means of linkages.

First, we have examined the substituent effect on the meso positions of arylcorroles, and then studied their

energy/electron transfer ability toward an electron-withdrawing phthalocyanine.

Also, different kinds of derivatives (fullerene, subphthalocyanine) were linked to the corrole-phthalocyanine

dyad through a supramolecular approach, showing an appropriate redox gradient to facilitate the ultimate

charge separation from the donor to the acceptor after photoexcitation.

1. M. Wolf, C. Villegas, O. Trukhina, J. L. Delgado, T. Torres, N. Martín, T. Clark and D. M. Guldi, J.

Am. Chem. Soc., 2017, 139, 17474–17483

2. Liu, C.; Colón, B. C.; Ziesack, M.; Silver, P. A.; Nocera, D. G. Science 2016, 352, 1210-1213

3. J. D. Megiatto, A. Antoniuk-Pablant, B. D. Sherman, G. Kodis, M. Gervaldo, T. A. Moore, A. L. Moore

and D. Gust, Proc. Natl. Acad. Sci., 2012, 109, 15578–15583

4. O. Trukhina, M. Rudolf, G. Bottari, T. Akasaka, L. Echegoyen, T. Torres and D. M. Guldi, J. Am.

Chem. Soc., 2015, 137, 12914–12922.

22

CHIMICA SUPRAMOLECOLARE Giornata dei Dottorandi OP - D.ROSA-GASTALDO

Gold nanoparticles as designer drugs NMR detectors

Daniele Rosa-Gastaldo, Luca Gabrielli, Federico Rastrelli, Fabrizio Mancin.

Department of Chemistry., University of Padova, via Marzolo 1, 35131, Padova, Italy.


Amphetamine and methamphetamine derivatives are well-known psychotropic substances used for

recreational purposes. Many “designer drugs”, obtained from simple modifications of existing drugs,

appear on the market every year.

These drugs avoid both the

classification as illicit substance and

their identification by standard

analytical methods. We manage to

successfully identify them using gold

nanoparticles coated with different

thiols to selectively transfer the

magnetization from the nanoparticle

to the drug interacting with the thiol

monolayer.

This approach called “NMR

chemosensing” relies on the

difference in diffusion rate between

the 2nm gold nanoparticles and the

molecules in solution and it allows

us to extract the spectrum of the

interacting drug from the mixture.

By modifying the composition of the

monolayer it is possible to tune the

selectivity of the system, detect and

propose a structure for new

phenethylamines, in micromolar

concentration without any

preliminary purification.

Figure 1. NOE pumping-CPMGz spectra of eleven mixtures

containing different drug analogs. Only the signals of the

interacting analyte are visible.

Figure 2. Recognition of

amphiphilic “designer

drugs” by a gold

nanoparticle coated with

amphiphilic thiols with

complementary charge.

1. L.Gabrielli, D. Rosa-Gastaldo, M.-V. Salvia, F. Rastrelli, F. Mancin, submitted., 2018

2. B. Perrone, S. Springhetti, F. Ramadori, F. Rastrelli, F. Mancin, J. Am. Chem. Soc. 2013, 135, 11768

3. F. Mancin et al. Patent: WO2017017245A1 2017

Acknowledgments: this work was founded by the ERC starting grant MOSAIC (Grant 259014) and Progetto

Strategico dell’Università di Padova NAMECA.

23

CHIMICA SUPRAMOLECOLARE Giornata dei Dottorandi OP - S.ALBANO

Formation of Imidazo[1,5‑ a]pyridine Derivatives Due to the Action of Fe2+

on Dynamic Libraries of Imines

Simone Albano,a Giorgio Olivo,

a Luigi Mandolini,

a Chiara Massera,

b Franco Ugozzoli,

b Stefano Di Stefano.

a

a-

, Piazzale Aldo Moro 5, 00185

Roma, Italy; b

, Viale delle Scienze 17/a, 43124 Parma, Italy.


A renewal of interest in imine chemistry is witnessed by the large number of papers published in recent

years. The main reason for this is the reversible character of most of the reactions involving imines, which

qualifies them as attractive functionalities in the fields of supramolecular and dynamic combinatorial

chemistry, organic synthesis and materials science.1

With the aim of investigating the possibility to exploit simultaneous transamination/transimination (TATI)

reactions2 for synthetic applications, an imidazo[1,5-a]pyridine derivative was unexpectedly obtained

through the action of Fe2+

on a dynamic combinatorial library3 of imines generated in situ via condensation

of benzaldehyde and 2-picolylamine under TATI conditions. This reaction product was easily isolated as the

only nitrogen-containing product eluted from the chromatographic column (Figure 1). A reaction mechanism

has been proposed, and either the importance of the nature of the added metal cation and the influence of

different substituents on the aromatic aldehyde have been analysed.

Figure 1. Schematic description of the investigated reaction leading to

novel imidazo[1,5-a]pyridine derivatives.

1. See for example: (a) M. E. Belowich, J. F. Stoddart, Chem. Soc. Rev., 2012, 41, 2003; (b) M. Ciaccia, S.

Di Stefano, Org. Biomol. Chem., 2015, 13, 646.

2. m, Chem. - Eur. J., 2015, 21, 9776.

3. P. T. Corbett, J. Leclaire, L. Vial, K. R. West, J.-L. Wietor, J. K. M. Sanders, S. Otto, Chem. Rev.,

2006, 106, 3652.

Acknowledgments: thanks are due to the Ministero dell’Istr e della Ricerca (MIUR,

PRIN 2010CX2TLM).

(Progetti di Ricerca 2014).

24

CHIMICA SUPRAMOLECOLARE Giornata dei Dottorandi OP - S.BATTISTA

Antibacterial activity of (+)-usnic acid included in mixed liposomes

containing structurally related L- prolinol derivatives

Sara Battista,a Luisa Giansanti,

a Francesca Ceccacci.

b

a Dipartimento di Scienze Fisiche e Chimiche, Università degli Studi dell’Aquila, Via Vetoio 10, 67010

Coppito (AQ) (Italy); b CNR-IMC Istituto di Metodologie Chimiche Sezione Meccanismi di Reazione,

Università di Roma “Sapienza” P. le Aldo Moro 5, 00185 Rome, Italy.


(+)-Usnic acid (UA, Figure 1a) is a solid yellowish cortical pigment produced by secondary metabolism of

many lichens. It has antibacterial,1 antiproliferative,

2 antifungean,

3 antiviral

4 and anti-inflammatory

5

properties, but its low solubility in water and its relative hepatotoxicity6 limit its use. Based on these

premises the potentiality of mixed liposomes containing a natural saturated or unsaturated phospholipid and a

synthetic surfactant derived from L-prolinol (1-4, Figure 1b) as UA delivery system was investigated.

Antibacterial activity of these formulations was also evaluated on a strain of Gram-positive bacteria,

Staphylococcus aureus subsp. Aureus (ATCC® 29213™), at the aim of correlating their physicochemical

properties and their delivering efficacy to their composition. The obtained results show that also subtle

variations of the molecular structure of liposome components can induce significant differences in their

physicochemical and biological behavior.

Figure 1. a. (+)-usnic acid; b. L-prolinol derivatives

1. M. Lauterwein, M. Oethinger, Antimicrob. Agents Chemother., 1995, 39,2541.

2. K. C. Kumar, K. Muller, J. Nat. Prod., 1999, 62, 821.

3. R. H. Pires, Antimicrob. Agents Chemother., 2012, 56, 595.

4. N. B. Perry, M.H. Benn, Lichenologist, 1999, 31, 627.

5. K. Ingólfsdóttir, Photochemistry 2002, 61, 729.

6. P. Pramyothin, W. Janthasoota, J. Ethnopharmacol, 2004, 90, 381.

25

https://www.cambridge.org/core/search?filters%5BauthorTerms%5D=Michael%20H.%20Benn&eventCode=SE-AU

CHIMICA SUPRAMOLECOLARE Giornata dei Dottorandi OP - B.DEL SECCO

Luminescent chemosensors for oxigen

Benedetta Del Secco,a Luca Prodi,

a Enrico Rampazzo,

a Sergei Vinogradov,

b Nelsi Zaccheroni.

a

a Department of Chemistry “G. Ciamician”, University of Bologna, Via Selmi 2, Bologna

b Department of Chemistry, School of Arts and Sciences, University of Pennsylvania, Philadelphia, United

States.


The development of nanotechnologies in the field of medicine has opened the design of synergic tools where

therapeutic and diagnostic features can be combined in an assembled nanostructure. Systems like

nanoparticles with a polymeric soft shell and a dye-doped silica hard core (PluS NPs, patented in 2011 by

L.Prodi et al), have very good properties for fluorescence bioimaging applications, due to their elevated

brightness, strong photostability and negligible in vivo cytotoxicity1.The aim of this work is the synthesis and

chemical and photochemical characterization of new nanostructured systems based on these NPs for

diagnostic application. In particular, a NP able to act as a chemosensor for molecular oxygen has been

developed, based on the encapsulation of new porphyrins inside the NP core, in collaboration with the group

of professor S.Vinogradov at the University of Philadelphia. The synthesis involves a micellar assisted

method, forming a water-soluble structure with a diameter around 25 nm. The emission property of these

nanostructures can be modulated using different silane derivatized fluorophores in order to obtain materials

emitting in the UV-visible-NIR range of the spectrum 2.

Figure 1 schematic representation of the chemosensors their dimentional

characterization (TEM) and emission quantum yield variations with O2 levels

A chemosensor is a species which interacts with a specific system inducing a detectable change in one of its

properties. The quenching of small molecule luminescence by O2 is a simple, non-invasive method for its

imaging in vivo. In collaboration with the group of professor S.Vinogradov has been synthetized four

different porphyrins that are able to switch on their luminescence when level of O2 is very low. Starting from

previous synthetic protocols, they has been modified in order to insert these porphyrins, that are known to be

insoluble in the aqueous media, in the NPs core (Fig.1). Due to the shielding effect of the silica matrix on the

emitting species the starting emission of the porphyrins in the NPs in water is higher with respect to the free

porphyrins in solution. Despite of this, they show a significant increase in the emission intensity when

increasingly degassed. TEM (Fig.1) and DLS analysis were performed to study their shape and dimension,

then several photophysical characterizations were conducted in the presence or absence of O2.

1. S.Bonacchi, M.Montalti, L.Prodi, N.Zaccheroni, R.Juris, D.Genovese, E. Rampazzo. Patent N. EP

2627360 A1, 2013

2. S.Biffi, L.Petrizza, E.Rampazzo, R.Voltan, M.Sgarzi, C.Garrovo, L.Prodi, L.Andolfi, C.Agnoletto,

G.Zaulia, P.Secchiero. RSC Adv., 2014, 4, 18278.

26

CHIMICA SUPRAMOLECOLARE Giornata dei Dottorandi OP - M.NARDI

Functional liposomes and multi-stimuli responsive polymers encompassing

the versatile 2-(hydroxyimino)aldehyde group

Martina Nardi,a,b

Francesca D’Acunzo,a,b

Alessandro Pinna,a Patrizia Gentili.

a,b

aDepartment of Chemistry, University of Rome “La Sapienza”, P.le A.Moro,5, 00185, Rome, Italy;

bCNR,

Institute of Chemical Methodologies, Sezione Meccanismi di Reazione at Department of Chemistry,

University of Rome “La Sapienza”, P.le A.Moro 5, 00185, Rome, Italy.


2-(hydroxyimino)aldehydes (HIA, Figure 1) are a class of highly versatile organic molecules that have been

incorporated in a wide variety of structures in our laboratory. Specifically, we have obtained HIA-substituted

small molecules, amphiphilic polymetacrylates1 and a HIA-containing lipid (Figure 2).

Oxime acidity,

isomerism, photochemical behavior, redox properties, metal binding ability and self-assembly in solution are

the main properties of interest with these compounds.2,3

Furthermore, the aldehyde group provides a handle

for binding bioactive molecules.

Figure 1. 2-(hydroxyimino)aldehydes (HIAs)

Figure 2. Liposomes (top) and multi-stimuli responsive polymers (bottom)

bearing HIA group

Our results demonstrate that the HIA group can be incorporated into self-assembling systems to which it can

impart its multi-functional properties.

1. M. Nardi, F. D’Acunzo, M. Clemente, G. Proietti, P. Gentili, Polym. Chem., 2017, 8, 4233

2. P. Gentili and S. Pedetti, Chem. Commun., 2012, 48, 5358.

3. P. Gentili, M. Nardi, I. Antignano, P. Cambise, M. D’Abramo, F. D’Acunzo, A. Pinna, E. Ussia,

Submitted to Chemistry-A European Journal

27

CHIMICA SUPRAMOLECOLARE Giornata dei Dottorandi OP - A.MENICHETTI

New transparent colloidal TiO2 nano-systems as efficient photocatalysts for

environmental remediation

Arianna Menichetti, Gloria Guidetti, Matteo Calvaresi, Francesco Zerbetto, Giuseppe Falini, Marco Montalti.

Department of Chemistry G.Ciamician, University of Bologna, via Francesco Selmi 2, 40126, Bologna, Italy


During the last decade, the study of sun light driven photocatalytic (PC) reactions to degrade

organic/inorganic pollutants by means of new photocatalytic nano-materials (PNMs) attracted a lot of

interest. Powder of anatase TiO2 is the most common PNM in industry because it has: good UV light

absorption (bandgap ≈ 3 eV)1, non-toxicity and low cost (1.9K USD/Ton at 2016 prices

2)

3. Nevertheless, the

PC performances of commercial powders of TiO2 are limited because they are made of aggregates of

nanoparticles that can be badly dispersed in water with high torbidity and low suspension stablity4. For these

reasons, the production of the photo-generated electron-hole pairs3 and the light activation of TiO2 as PC are

inhibited. Here, we successfully report the synthesis and characterization of colloidal TiO2 nanoparticles

(NPs) by using common ionic (Sodium Cholate, CTAB) and non-ionic (Triton X-100, Pluronic F-127)

surfactants5. TEM and optical characterizations revealed stable and transparent dispersions of 5-7 nm size

anatase/brookite core-shell TiO2 NPs. The PC activity was tested by monitoring the degradation of an

organic pollutant (Rhodamine B dye-RhB) in aqueous solution after a 15-minutes UV light irradiation. The

best PC performance was achieved in the case of NPs with CTAB and Triton X-100 giving respectively an

enhancement of +203%, +158% compared to commercial TiO2 (Fig.1). The high transparency, stability and

PC activity of these synthesized TiO2 NPs can be exploited as alternative to the TiO2 commercial powders, in

order to develop highly PC transparent materials in the future.

Figure 1. Decrease of the normalized absorbance of RhB in aqueous solution and in presence of the colloidal

TiO2 samples, compared to TiO2 AHP 200, during 15-minute UV irradiation (313 nm).

1. Salinaro, A. et al. Pure and Applied Chemistry, 1999, 71, 321.

2. http://www.cnchemicals.com/

3. Zhang, Q.; et al. Nanoscale, 2015, 7, 14002.

4. Zhang X. et al. Carbon,2005, 43, 1700.

5. Baldi, G. et al., US Patent 8,431,621 B2, 2013.

Acknowledgments: Funding from the European Union Seventh Framework Program under grant agreement

no. 604391 Graphene Flagship.

28

CHIMICA SUPRAMOLECOLARE Giornata dei Dottorandi OP - K.HASSENEIN

Novel CuI-based Metal Organic Frameworks for sensing applications

Khaled Hassanein,a Chiara Cappuccino,

b Lucia Maini,

b Barbara Ventura.

a

a 1 Istituto per la Sintesi Organica e la Fotoreattività (ISOF) - CNR; Via Gobetti, 101 - 40129 Bologna,

Italy; b Dipartimento di Chimica “G. Ciamician”, Via Selmi 2 - 40126 Bologna, Italy:


Traditional applications of metal organic frameworks (MOFs), also known as porous coordination polymers,

are focused on gas storage and separation, which take advantage of the inherent porosity and high surface

area of these materials.1 The application of MOFs as chemical sensors require signal transduction based on

the dynamics of the analyte interacting with the MOF network.2, 3

The main objective of our project is to design multifunctional (combination of optical and electrical signals)

and dynamic Stimuli-Responsive Metal Organic Frameworks (SR-MOFs) with enhanced selectivity and

sensitivity towards harmful volatile organic compounds (VOCs), to be integrated into sensory devices.

We have selected building units that offer extensive connectivity, flexibility, tunable porosity and

functionalization of the inner surface of the network with groups interacting with the analytes by means of -

interactions or hydrogen bonds. Therefore, we envisage that the new chemical sensors will show increased

selectivity and sensitivity towards VOCs with respect to the state-of-the-art, thanks to supramolecular

interactions between the MOF network and the guest molecule (VOCs).

Figure 1. Scheme of the proposed methodology.

1. P. Silva, S. M. F. Vilela, J. P. C. Tomébc, F. A. Almeida Paz, Chem. Soc. Rev, 2015, 44, 6774.

2. I. Stassen, N. Burtch, A. Talin, P. Falcaro, M. Allendorf, R. Ameloot, Chem. Soc. Rev, 2017, 46, 3185.

3. M. G. Campbell; S. F. Liu, T. M. Swager, M. Dincă, J. Am. Chem. Soc, 2015 137, 13780.

The work is supported by the H2020-MSCA-IF-2016-751175 project “SmartMOFs”.

29

CHIMICA SUPRAMOLECOLARE Giornata dei Dottorandi OP - C.BIAGINI

Carboxylic Acids as Chemical Fuels for a Catenane Based Molecular

Switch: Tuning the Motion Rate

Chiara Biagini,a Simone Albano,

a José Augusto Berrocal,

b Luigi Mandolini,

a Stefano Di Stefano.

a

aDipartimento di Chimica and Istituto CNR di Metodologie Chimiche-IMC, Sezione Meccanismi di Reazione

c/o Dipartimento di Chimica, Università degli Studi di Roma “La Sapienza”, P.le A. Moro 5, 00185 Rome,

Italy; bInstitute for Complex Molecular Systems, Eindhoven University of Technology, P.O. Box 513, 5600

MB Eindhoven (The Netherlands).


In this work, activated carboxylic acids are presented as new chemical fuels for a catenane based chemical

switch composed of two identical macrocycles incorporating a 1,10-phenanthroline unit. While the transition

between two different states of a molecular switch has often been made possible by the sequential addition of

a fuel and a proper antifuel,1 here one only chemical species, 2-cyano-2-phenylpropanoic acid 1, is employed

to drive the whole cyclic operation (Figure 1).

Decarboxylation of acid 1 is fast and quantitative when carried out in the presence of 1 molar equivalent of

the chemical switch and, when decarboxylation is over, all of the catenane molecules have experienced large-

amplitude motions from state A (neutral) to state B (protonated), then to state A again.2

In this communication, the principle at the basis of the above system will be illustrated. Furthermore, it will

be shown that is possible to control the rate of the back and forth motion of the switch (ranging from 100 s to

100 h timescale) by a fine tuning of the fuel chemical structure.3

Figure 1: Cyclic operation of the catenane-based switch 2 coupled to decarboxylation of fuel 1.

1. E. R. Kay, D.A. Leigh, and F. Zerbetto, Angew. Chem. Int. Ed. 2007, 46, 72.

2. J. A. Berrocal, C. Biagini, L. Mandolini, and S. Di Stefano, Angew. Chem. Int. Ed. 2016, 55, 6997.

3. C. Biagini, S. Albano, R. Caruso, L. Mandolini, J. A. Berrocal, S. Di Stefano, Chem. Sci., 2018, 9, 181.

30


Flash Presentations

31

CHIMICA SUPRAMOLECOLARE Giornata dei Dottorandi FP - F.FAROLDI

Reversible energy transfer to lanthanoid ions mediated by calixarenes

Federica Faroldi,a,b

Laura Baldini,a Massimiliano Massi,

b Mauro Mocerino,

b Francesco Sansone.

a

a Department of Chemistry, Life Sciences and Environmental Sustainability, University of Parma, Parco

Area delle Scienze 17/A, 43124, Parma, Italy; b Department of Chemistry, Curtin University, GPO Box

U1987, Perth, 6845, AUSTRALIA.


The near infrared emission of lanthanoid ions is highly sought after for a number of applications including

biological imaging and sensing, night vision displays as well as telecommunication signalling.1 Previous

work in this area investigated the binding and sensitisation of visible emitters such as trivalent Eu, Tb, and

Sm to calix[4]arene scaffolds functionalised on the lower rim by three amide groups.2 The sensitisation

originated from electronic transitions occurring on the aromatic rings of the calix[4]arene structure.

However, the process was found to be inefficient due to an energy mismatch between the triplet excited state

of the ligand and the 4f* accepting state of the lanthanoid ions.3 Furthermore, very limited energy transfer

was observed for complexes formed with near-infrared emitting lanthanoid ions, such as Er, Nd, and Yb.

We report here our work towards improving the near infrared emission of calix[4]arene/lanthanoid ion

complexes by covalently grafting a suitable antenna to the lower or upper rim of the calix[4]arene systems.

Possible antennae include naphthalimide (Figure 1) and flavin-based components.4

Figure 1. Generic calix[4]arene-based system for the

binding and sensitisation of lanthanoid ions.

1. J.-C. G. Bünzli, Chem. Rev., 2010, 110, 2729.

2. C. R. Driscoll, B. L. Reid, M. J. McIldowie, S. Muzzioli, G. L. Nealon, B. W. Skelton, S. Stagni, D. H.

Brown, M. Massi, M. I. Ogden, Chem. Commun., 2011, 3876.

3. D. D’Alessio, S. Muzzioli, B. W. Skelton, S. Stagni, M. Massi, M. I. Ogden, Dalton Trans, 2012, 41,

4736.

4. J. Yeow, A. Kaur, M. D. Anscomb, E. J. New, Chem. Commun., 2014, 50, 8181.

32

CHIMICA SUPRAMOLECOLARE Giornata dei Dottorandi FP - G.CAPOCASA

Direct hydroxylation of benzene and aromatics with H2O2 catalyzed by a

self-assembled iron complex: evidence for a metal-based mechanism

Giorgio Capocasa, Giorgio Olivo, Alessia Barbieri, Osvaldo Lanzalunga, Stefano Di Stefano.

Dipartimento di Chimica Università di Roma “La Sapienza”, edificio Cannizzaro. Piazzale Aldo Moro, 5

00185 Roma (RM) Italy.


The hydroxylation of aromatics is a notoriously challenging transformation presenting both regio- and

chemo-selectivity problems: strong oxidants often produce large amounts of quinones and, in the presence of

alkyl chains on the ring, the major products are those arising from benzylic oxidation1,2

.

Figure 1: possible products deriving from the oxidation of strong oxidants

Furthermore, when the reaction is catalyzed by iron-based complexes, the phenols produced poison the

catalyst due to their binding to the iron-center. This reduces the turnover number and overall yield of the

reaction.3

We present an imine-based iron catalyst that is able to oxidize aromatics with surprising chemo- and

regio-selectivity. The catalyst self-assembles in situ from inexpensive and readily available commercial

products (Iron (II) trifluoromethanesulfonate, 2-(amminomethyl)pyridine and 2-pyridinecarboxaldehyde) 4.

Typical yields in phenols are relatively high for a direct hydroxylation of aromatic compounds while over-

oxidation to quinones is limited with yields in the single percent digit and, where alkyl chains are present,

benzyl oxidation is not prevalent.

Mechanistic studies point towards a metal-based oxidation pathway via an SEAr mechanism.

1. J.P. Hage, A. Llobet, D.T. Sawyer, Bioorganic Med. Chem, 1995, 3, 1383.

2. C. Yuan, Y. Liang, T. Hernandez, A. Berriochoa, K., N. Houk, D. Siegel, Nature, 2013, 499, 192.

3. A. Thibon, V. Jollet, C. Dibal, K. Sénéchal-David, L. Billon, A.B. Sorokin, F. Banse, Chem.–Eur. J.,

2012, 18, 2715.

4. G. Capocasa, G. Olivo, A. Barbieri, O. Lanzalunga, S. Di Stefano, Catal. Sci. Technol., 2017,7, 5677.

33

CHIMICA SUPRAMOLECOLARE Giornata dei Dottorandi FP - B.COGLIATI

Synthesis and Investigation of Croconates as Smart Organic Coating for

Noble Metals Nanoparticles

B.Cogliati, A.Arduini, A.Secchi.

Department of Chemistry, Life Sciences an Enviromental Sustainability – COFI unit – Parco Area delle

Scienze 17/A. I-43124 Parma, Italy.


Croconic acid is a cyclic organic molecule, belonging to a particular family of compounds called oxo-carbon

acids. This molecule properly functionalized exhibit an absorption in NIR region and this property can be

exploited in the design of NIR-harvesting materials obtained with a hybridization of a nano-material,

characterized by a NIR absorption, with this organic molecule.

The purpose of this research is to combine a particular type of gold nanoparticles, called nanorods (AuNRs),

with a specific aspect ratio (AR) in order to have an absorption in NIR region (900-1100 nm), with a

croconic acid. This latter must be properly functionalized with an alkyl spacer (for example thiol-ending) in

order to allow the anchoring to the AuNRs.

Croconic acid absorption in the IR region can be tuned by varying donor moieties. Some experiments

reported in the literature have revealed that increasing the conjugation in the donor part of the croconic unit

leads to a red shift in NIR region (~1000 nm).

Croconic acid is synthetized following the method reported by Fatiadi et al. 1. For the synthesis of gold

nanorods the Seed-Mediated Growth method 2 is followed.

1. A. Fatiadi, H. Isbell, W. Sager, Journal of Research of the national Bureau of Standards- A. Physics

and Chemistry, 1962, 67A, 153.

2. B. Nikoobakht, M. A. El-Sayed, Chem. Mater. 2002, 15, 1957.

34

CHIMICA SUPRAMOLECOLARE Giornata dei Dottorandi FP - C.PODERI

Synthesis and characterization of a paramagnetic [2]-rotaxane based on a

crown ether-like wheel incorporating a nitroxide motif

Valentina Bleve,a Cecilia Poderi,

a Paola Franchi,

a Evangelia Konstanteli,

a,b Lorenzo Gualandi,

a Stephen M.

Goldup,c

Elisabetta Mezzina,a

Marco Lucarini.a

a Department of Chemistry, University of Bologna, Via S. Giacomo 11, 40126, Bologna, Italy;

b Department

of Chemistry, National and Kapodistrian University of Athens, 15772, Athens, Greece; c Department of

Chemistry, University of Southampton, SO17 1BJ, Southampton, UK;


In the last decade, different works involving the synthesis of supramolecular systems (rotaxanes) containing

persistent nitroxide radicals have been reported.1 However, in most of these works the interaction between

the radical motifs was only used to probe the shuttling process of the macrocycle and it was not employed in

the recognition process. Starting from this, we decided to investigate the synthesis of a new crown ether

macrocycle containing a dialkyl nitroxide radical and to use it as spin-probe and as recognition site in a [2]-

rotaxane system incorporating 4,4’-bipyridinium (BPY2+

) and dialkylammonium (NH2+) stations (Figure 1).

2

The synthesis of the macrocycle was afforded by adapting the original procedure proposed in 1983 by Keana

et al.3 to yield the preferred cis-stereoisomer of the desired nitroxide crown ether. The paramagnetic rotaxane

was then prepared by following the conventional threading-stoppering synthetic pathway and its formation

was verified by ESI-MS, UV-visible and EPR spectroscopy. We were able to probe the displacement of the

macrocycle between the two recognition sites of the [2]-rotaxane by measuring the nitrogen hyperfine

splitting in the EPR spectrum, before and after treatment with a base. In addition, we performed the study of

the reduction kinetics comparing the [2]-rotaxane and the macrocycle behaviour by means of EPR

spectroscopy. In conclusion, this work represented the first example of a rotaxane system in which the

paramagnetic unit on the wheel acts as recognition site during the threading process.4 The future work will be

focused on the design of new mechanically interlocked molecules containing paramagnetic groups, in view

of interesting applications in the field of radical molecular machines.

Figure 1. Ring displacement upon treatment with acid/base in the [2]-rotaxane system.

1. M. Lucarini, E. Mezzina, Electron Paramagnetic Resonance: Specialist Periodical Reports, 2010, 22,

41.

2. P. R. Ashton, R. Ballardini, V. Balzani, I. Baxter, A. Credi, M. Fyfe, M. Gandolfi, M. Gûmez-Lûpez,

M. Martinez, A. Piersanti, N. Spencer, J. F. Stoddart, M. Venturi, A. J. P. White, D. J. Williams, J. Am

.Chem. Soc. 1998, 120, 11932.

3. J. F. W. Keana, J. Cuomo, L. Lex, S. E. Seyedrezai, J. Org. Chem. 1983, 48, 2647.

4. V. Bleve, P. Franchi, E. Konstanteli, L. Gualandi, S. M. Goldup, E. Mezzina, M. Lucarini, Chem. Eur.

J. 2018, 24, 1198.

35

CHIMICA SUPRAMOLECOLARE Giornata dei Dottorandi FP - E.HADDADI

Investigating the Polarity of Silica Nanoparticles

Elahe Haddadi,a,b

Damiano Genovese,a Andrey Klymchenko,

c Luca Prodi

a

a) Department of Chemistry “G. Ciamician”, University of Bologna, via Selmi 2, 40126, Bologna, Italy.

b) Department of Chemistry, College of Sciences, Shiraz University, Shiraz, 71467-13565, Iran

c) UMR 7213 CNRS, Faculté de Pharmacie, Université de Strasbourg, 74 route du Rhin, 67401 Illkirch

Cedex, France.


Nanomaterials represent a rich potential because they can include several environments featuring very

different polarities, resulting in different physical and chemical properties at the distance of a few

nanometers, in a single structure. Identification of polarity inside nanomaterials is essential to capture their

potential as nanoreactors, as catalysts or in drug delivery applications. 1

To address this issue and explore the polarity of nanostructures, we have used solvatochromic dyes

covalently bound to the nanoparticles. In particular, we used a silane derivative of Nile Red (NR) that binds

to core-shell silica-PEG nanoparticles during their formation.

We have so investigated the emission features of NR binding to different nanoparticles, obtained by

condensation of different organosilanes with a well-established method. The method is based on the

preparation of micelles of Pluronic F127 in water. This surfactant is a nonionic triblock copolymer

terminating in primary hydroxy groups with a poly(ethylene glycol)–poly(propylene oxide)–poly(ethylene

glycol) structure (PEG-PPO-PEG; MW 12 600).2

The final material is a versatile multicompartment system characterized by high water solubility, excellent

monodispersity, stability, and brightness. We investigated the photophysical and morphological properties of

the resulting NR-doped organosilica nanostructures, elucidating the heterogeneous polarity typical of these

peculiar nanomaterials.

1. E. Rampazzo, S. Bonacchi, D. Genovese, R. Juris, M. Montalti, V. Paterlini, N. Zaccheroni, C. Dumas-

Verdes, G. Clavier, R. Méallet-Renault, L. Prodi, J. Phys. Chem. C, 2014, 118 (17), pp 9261–9267.

2. S. Bonacchi, D. Genovese, R. Juris, M. Montalti, L. Prodi, E. Rampazzo, N. Zaccheroni, Angew. Chem.

2011, 50, 4056 – 4066

36

https://pubs.acs.org/author/Rampazzo%2C+Enrico

https://pubs.acs.org/author/Bonacchi%2C+Sara

https://pubs.acs.org/author/Genovese%2C+Damiano

https://pubs.acs.org/author/Juris%2C+Riccardo

https://pubs.acs.org/author/Montalti%2C+Marco

https://pubs.acs.org/author/Paterlini%2C+Veronica

https://pubs.acs.org/author/Zaccheroni%2C+Nelsi

https://pubs.acs.org/author/Dumas-Verdes%2C+C%C3%A9cile

https://pubs.acs.org/author/Dumas-Verdes%2C+C%C3%A9cile

https://pubs.acs.org/author/Clavier%2C+Gilles

https://pubs.acs.org/author/M%C3%A9allet-Renault%2C+Rachel

https://pubs.acs.org/author/Prodi%2C+Luca

CHIMICA SUPRAMOLECOLARE Giornata dei Dottorandi FP - N.AYAZ

Protein stabilized nanoformulation of a superfluorinated 19

F-MRI contrast

agent

Nazeeha Ayaz, Jacopo Repossi, Lara Gazzera, Daniele Maiolo, Valentina Dichiarante, Pierangelo

Metrangolo, Francesca Baldelli Bombelli.

Laboratory of Supramolecular and Bio-Nanomaterials (SupraBioNanoLab), Department of Chemistry,

Materials and Chemical Engineering “Giulio Natta”,Politecnico di Milano, via L. Mancinelli 7,20131

Milano, Italy.

Email of presenting author: [email protected]; Web-site: www.suprabionano.eu

19F-Magnetic Resonance Imaging (MRI) is a powerful complementary tool to be coupled with other

diagnostic imaging techniques such as 1H-MRI and ultrasound imaging (US), in order to overcome their

present shortcomings, particularly in terms of sensitivity. 19

F-MRI has indeed emerged as one of the most

promising diagnostic tools providing hot spot imaging. Here, we report a unique fluorinated imaging agent

PERFECTA [1] bearing 36 equivalent 19

F atoms and therefore showing a single, intense resonance peak.

Most of the superfluorinated contrast agents are highly hydrophobic, which makes their use difficult in

biological environment. In this work, an ampiphilic protein, hydrophobin (HFBII), which is a natural

biosurfactant with filming properties, was used to disperse PERFECTA in aqueous solutions. We optimized

a protocol to obtain colloidally stable formulations of PERFECTA. The obtained formulations were

characterized by NMR, DLS and 19

F-MRI. The results showed that these formulations were composed of

monodispersed PERFECTA nanoparticles coated by a HFBII shell and have good NMR relaxation times to

be used as 19

F-MRI contrast agents [Figure 1]. Cytotoxicity and cellular uptake studies in HeLa cells also

demonstrated nanoparticle biocompatibility. Thus, the obtained nanoparticles represent a versatile theranostic

platform that could be further used to deliver therapeutic drugs and nucleic acids.

Figure 1. Nanoparticle of the superfluorinated contrast agent PERFECTA coated with a HFBII shell.

1. I. Tirotta, A. Mastropietro, C. Cordiglieri, L. Gazzera, F. Baggi, G. Baselli, M. G. Bruzzone, I. Zucca,

G. Cavallo, G. Terraneo, F. Baldelli Bombelli, P. Metrangolo, G. Resnati, J. Am. Chem. Soc., 2014,

136, 8524.

37

CHIMICA SUPRAMOLECOLARE Giornata dei Dottorandi FP - L.MUMMOLO

Luminescent nanoparticles release from biocompatible polymeric fibers

Liviana Mummolo, Benedetta Del Secco, Maria Letizia Focarete, Andrea Merlettini, Luca Prodi, Nelsi

Zaccheroni.

Department of Chemistry “G. Ciamician”, University of Bologna, via Selmi 2, 40126, Bologna, Italy.


Nanomedicine and in particular the area of drug delivery has gained increasing interest in last decades. The

controlled release of a drug at the therapeutically optimal rate and dose is a major concern, and new carriers

are needed for a sustained release. Among many approaches proposed to reach this aim, polymeric

nanofibers represent a promising tool. Indeed, they can be easily produced by a cost-effective and scalable

electrospinning process in the form of non-woven mats, which can be eventually implanted in the human

body to release in-situ the embedded therapeutics.

We decided to take advantage of the synergistic action of the above-mentioned polymeric nanofibers with

‘drug’ luminescent silica core/PEG shell nanoparticles (NPs), that have been studying since a few years as

imaging agent1, carriers

2 and lately as theranostic materials.

Firstly, we decorated the shell of the NPs with a peptide sequence known to be able to selectively recognize a

sequence over-expressed by the hepatic cancer cells. Suspensions of core-shell luminescent silica NPs in a

polymeric solution of poly(lactide-co-glycolide) copolymer (PLGA 50:50 w/w) were electrospun and two

different nanofibers mats was obtained: the first one embedding NPs without superficial derivatizations and

the second one functionalized with the peptide.

The release of the NPs in PBS at 37 °C from the nanofibers mats was studied and followed by

spectrofluorimetric measurements. The release profiles were compared and each of them was correlated

with fiber degradation profiles in the same phisiological conditions. The obtained data demonstrate the

possibility to design and control the release kinetics of non-cytotoxic NPs3 from a bioresorbable nanofibrous

mat, opening up a wide number of potential biomedical application.

Figure 1 schematic representation of synthesis and of the luminescent

label entrapped in a random polymer

1. E.Rampazzo et al. “Multicolor core/shell silica nanoparticles for in vivo and ex vivo imaging”,

Nanoscale, 4, 2012, 824.

2. N.Zaccheroni et al. “A fluorescent ratiometric nanosized system for the determination of Pd(II) in

water”, Chem. Commun., 50, 2014 , 15259.

3. L.Prodi et al. “Proper design of silica nanoparticles combines high brightness, lack of cytotoxicity and

efficient cell endocytosis”, Nanoscale, 5, 2013, 7897.

38

CHIMICA SUPRAMOLECOLARE Giornata dei Dottorandi FP - A.IMBRIANO

Nanoemulsion: a versatile formulation.

A.Imbriano,a P.N.Hanieh,

a F.Rinaldi,

b C.Marianecci,

a M.Carafa.

a

a Department of Drug Chemistry and Technologies, Sapienza University of Rome, Rome, Italy

b Center for Life Nano Science@Sapienza, Istituto Italiano di Tecnologia (ITT), Rome, Italy


Nanoscience and nanotechnology concern the study and the application of extremely small things all over

different science fields, such as chemistry, biology, physics, materials science, engineering, pharmaceutics

and restoration1. Nanocarriers and nanomaterials can act as excellent and versatile vehicle for new or

extensively used active compounds. Among the different nanocarriers, Nanoemulsions (NEs) have attracted

great attention. NEs are colloidal systems that consist of two liquid phase, an oil phase (O) and an aqueous

phase (W), one of them finely dispersed (O/W – W/O) with droplet size ranging from 50 to 500 nm. They are

thermodynamically unstable but kinetically stable. The stability of NEs is a function of droplet size and

monodispersity, which implies that they can be diluted without changing the size distribution of the drops2.

These properties make them a attractive candidates for applications in food and cosmetic field and in drug

delivery. NEs are commonly stabilized by surfactants. NEs can act as drug delivery systems owing to their

solubilizing capacity of non-polar compounds. Furthermore, NEs can be formulated to be administered by

different routes such as topical, ocular, intravenous, intranasal and oral3.

These formulations can be used in the food industry to improve solubility of hydrophobic ingredients, e.g.

essential oils that can act as preservative ingredients4. NEs can be applied in the field of artwork cleaning, in

fact these systems have shown several advantages compared to conventional systems; many studies have

demonstrated that the cleaning process with NEs allows a controlled cleaning action of the works of art

surface. In our study we have characterized NEs from different oil such as Neem, Almond and Carnation oils

and different surfactants in order to take advantage of each component in different fields. For example,

Brij®72 (Polyoxyethylene Stearyl Ether) seem to be useful in the topical delivery of active compounds for the

treatment of many skin diseases, as it could enhance the skin permeation and increase residence time of the

drugs in the stratum corneum (SC)6.

Figure 1. Schematic of O/W and W/O nanoemulsions.

1. F. Rinaldi, P. N. Hanieh, C. Longhi, S. Carradori, D. Secci, G. Zengin, M. G. Ammendolia, E. Mattia,

E. Del Favero, C. Marianecci, M. Carafa, Journal of Enzyme Inhibition and Medicinal Chemistry, 2017,

32, 1265–1273.

2. M. L. Zambrano-Zaragoza, R. González-Reza, N. Mendoza-Muñoz, V. Miranda-Linares, T. F.

Bernal-Couoh, S. Mendoza-Elvira, D. Quintanar-Guerrero, International Journal of Molecular

Sciences, 2018, 19, 705.

3. A. Gupta, H. B. Eral, T. A. Hatton and P. S. Doyle, Soft Matter, 2016.

4. J. Rodriguez, M. J. Martin, M. A. Ruiz and B. Clares, Food Res. Int., 2016, 83, 41–59.

5. P. Baglioni, D. Berti, M. Bonini, E. Carretti, L. Dei, E. Fratini, R. Giorgi, Advances in Colloid and

Interface Science, 2014, 205, 361–371.

6. M. Gupta, B. Vaidya, N. Mishra, S. P. Vyas, Artificial Cells, Blood Substitutes, and Biotechnology,

2011, 39 (6), 376–384.

39

CHIMICA SUPRAMOLECOLARE Giornata dei Dottorandi FP - E.SEVERONI

Catanionic mixtures of bile salt derivatives

Maria Chiara di Gregorio,a Emilia Severoni,

a Leana Travaglini,

a Marta Gubitosi,

a Simona Sennato,

b

Francesco Mura,c Carlos Redondo-Gómez,

d Aida Jover,

e Nicolae Viorel Pavel,

a Luciano Galantini.

a*

a Department of Chemistry, ‘‘Sapienza University of Rome”, P. le A. Moro 5, 00185 Roma, Italy;

bCNR-ISC UOS Sapienza and Physics Department Sapienza “Sapienza University of Rome”,P. le A. Moro 5,

00185 Roma, Italy; cCNIS, Research Center for the Nanotechnologies Applied to Engineering, “University of

Rome”,P. le A. Moro 5, 00185 Roma; d

Escuela de Química, Centro de Investigación en Electroquímica y

Energía Química (CELEQ), Universidad de Costa Rica, San José, Costa Rica; e Departamento de Química

Física, Facultad de Ciencias, Universidad de Santiago de Compostela, Avda. Alfonso X El Sabio s/n, 27002

Lugo, Spain.


Three-dimensional structures with nanoscopic dimensions, yielded by self-assembly of lipids and surfactants,

are particularly interesting for their applications in nanoscience. In these applications the possibility of

controlling and modifying the charge of the particles allows the regulation of fundamental aspects such as the

ability of the particle to load molecules (drugs, DNA, proteins, etc.), to aggregate and to penetrate

membranes.Due to a rigid and unconventional amphiphilic structure, anionic and cationic derivatives

obtained by chemical modifications of the steroidal surfactants bile salts (BS) have proven to provide

uncommon ordered catanionic supramolecular structures in catanionic mixtures.1,2

They also allowed for a

fine tune of the aggregate charge by changing the mixture composition.

In this context this work found its relevance by reporting about the co-assembly of new oppositely charged

BS based derivatives bearing hydrophobic rigid groups on the steroid rigid skeleton. Results demonstrate that

catanionic aggregates with different morphologies and charge can be prepared by properly tuning the mixture

stoichiometry, thus promotingthese mixtures to versatile systems for preparations of supramolecular

nanostructures.

Figura 1. Aggregates of a) negatively charged BS derivate, c) positively charged BS

derivate, b) catanionic mixture.

1. Manghisi, N.; Leggio, C.; Jover, A.; Meijide, F.; Pavel, N. V.; Soto Tellini, V. H.; Vázquez Tato, J.;

Agostino, R. G.; Galantini, L. Angew. Chem. Int. Ed. 2010, 49, 6604-6607

2. Di Gregorio, M. C.; Pavel, N.V.; Miragaya, J.; Jover, A.; Meijide, F.; Tato, J. V.; Soto Tellini, V. H.;

Galantini, L. Langmuir 2013, 29, 12342−12351

40

a) b) c)

CHIMICA SUPRAMOLECOLARE Giornata dei Dottorandi FP - S.AIELLO

Glycosylated liposomes for targeting bacteria

Stefano Aiello,a Cecilia Bombelli,

c Michela Picano,

a Beatrice Simonis,

a Livia Pagano,

a Sara Ugolini,

a

Giovanna Mancini.b

a Dipartimento di Chimica, Università di Roma “Sapienza” P. le Aldo Moro 5, 00185 Rome, Italy.

b CNR-IMC Istituto di Metodologie Chimiche, via Salaria km 29.300, 00016 Monterotondo Scalo RM, Italy.

c CNR-IMC Istituto di Metodologie Chimiche Sezione Meccanismi di Reazione, Università di Roma

“Sapienza” P. le Aldo Moro 5, 00185 Rome, Italy.

E-mail of presenting author: [email protected]

Biofilm associated bacterial infections are one of the most relevant health problem due to the high antibiotic

resistance of biofilm infections. In fact, bacterial cells are embedded in a complex polymeric matrix that,

from the one hand protects the cells from external agents and, from the other confers to bacteria new

powerful tools to survive, such as for example the ability to communicate among them by “Quorum

Sensing”, a system of stimuli and responses correlated to their proliferation that exploits specific signal

molecules2,3

. Several molecules, such as ferulic acid, gallic acid and arbutin, resveratrol have been shown to

inhibit Quorum Sensing in in vitro studies4

but an optimal formulation for their targeted delivery in living

organisms has not been developed yet.

We have designed and prepared cationic glycosylated liposomes for the encapsulation of some of the most

promising Quorum Sensing inhibitors. Sugar moieties (glucose, mannose, galactose) should in fact interact

with specific proteins expressed on bacterial surface, lectins, that bear binding sites for specific

monosaccharides.

Figure 1: functionalized double layer Figure 2: trans-resveratrol

Here we report on the synthesis of two new glycosylated lipids containing mannose and galactose moieties

and on the agglutination of glycosilated liposomes mediated by Concanavalin A, a commercial plant lectin

used as a model. Further, loading of resveratrol into the glycosylated liposomes has been explored.

1. J. W. Costerton, G. G. Geesey, K.-J. Cheng, Scientific American, 1978, 238, 86

2. N. M. Vega, J. Gore, Current opinion in microbiology, 2014, 21, 28

3. A. R. Stacy, S. P. Diggle, M. Whiteley, Current opinion in microbiology, 2012, 15, 155

4. A. Borges , M. J. Saavedra, M. Simões, Biofouling 2012, 28:7, 755

41

CHIMICA SUPRAMOLECOLARE Giornata dei Dottorandi FP - V.CAPONETTI

Self-assembling supramolecular structures as stimuli-responsive systems

for sensing pH and anions in water

Valeria Caponetti,a Marco Montalti.

b

a b Department of Chemistry “Giacomo Ciamician”, University of Bologna, via Selmi 2, 40126, Bologna,

Italy.


Multi-stimuli responsive materials are finding increasing importance in fields of high social and economic

impact that include drug delivery, diagnostics, tissue engineering and ‘smart’ optical systems, as well as

microelectronics, biosensors, microelectromechanical systems, coatings and textiles1. _ENREF_2_ENREF_3

Although different design approaches have been proposed, the self-assembly of molecular or nanostructured

building blocks is, without any doubt, one of the most versatile, straightforward and powerful strategy to

achieve stimuli-responsive materials2. The response of these materials, either to environmental or external

solicitation, can be, in fact, achieved by exploiting the same inter-components interactions that brings to their

assembly.

Here we demonstrate that aggregation of properly designed perylene bisimide amino derivate can be

controlled by pH in water solution 3,4

.

As shown in the figure the dye

molecules (a) aggregate in water

because of p-p stacking interaction

(b), causing fluorescence quenching.

The system can be disaggregated and

the fluorescence switched on by

protonation exploiting the

electrostatic repulsion between the

positive cations (c).Even more

interestingly we observed that the

protonated system can be re-

assembled by increasing the

concentration of anion that partially

shield the positive charge of the

ammonium substituents. Finally, our

molecules show a unique response to

protonation and anion concentration

in water. These features make them

very promising tools for ion sensing in view of biological and environmental applications.

1. S. Mura, J. Nicolas, Nature Materials, 2013, 12, 991-1003;

2. F. Würthner, C. R. Saha-Möller, Chemical Reviews, 2016, 116, 962-1052;

3. M. Montalti, G. Battistelli, Chemical Communications, 2014, 50, 5326-5329;

4. G. Battistelli, M. Montalti, Wiley Interdisciplinary Reviews: Nanomedicine and Nanobiotechnology,

2016, 8, 139-150;

42

Fig. 1. Aggregation of perylene bisimide controlled by pH.


List of Participants

CHIMICA SUPRAMOLECOLARE Giornata dei Dottorandi List of Participants

1 Aiello Stefano Università di Roma “Sapienza”

[email protected]

2 Albano Simone Università di Roma “Sapienza”

[email protected]

3 Angeloni Sara Università di Bologna

[email protected]

4 Ayaz Nazeeha Politecnico di Milano

[email protected]

5 Barbieri Alessia Università di Roma “Sapienza”

[email protected]

6 Battista Sara Università degli studi dell’Aquila

[email protected]

7 Bazzoni Margherita Università di Parma

[email protected]

8 Berionni Berna Beatrice Università di Roma “Sapienza”

[email protected]

9 Berrocal Josè Augusto University of Groningen - University of Technology Eindhoven, the Netherlands

[email protected]

10 Biagini Chiara Università di Roma “Sapienza”

[email protected]

11 Bombelli Cecilia CNR –IMC – sez. Meccanismi di Reazione, Roma

[email protected]

12 Canton Martina Università di Bologna

[email protected]

13 Capocasa Giorgio Università di Roma “Sapienza”

[email protected]

14 Caponetti Valeria Università di Bologna

[email protected]

15 Cardona Maria A. Università di Padova

[email protected]

16 Ceccacci Francesca CNR –IMC – sez. Meccanismi di Reazione, Roma

[email protected]

17 Cogliati Beatrice Università di Parma

[email protected]

18 Dalla Cort Antonella Università di Roma “Sapienza”

[email protected]

19 Del Secco Benedetta Università di Bologna

[email protected]

20 Di Stefano Stefano Università di Roma “Sapienza”

[email protected]

21 Faroldi Federica Università di Parma – Curtin University, Perth, Australia

[email protected]

44

CHIMICA SUPRAMOLECOLARE Giornata dei Dottorandi List of Participants

22 Giardini Giorgio CNR – IMC – Monterotondo (RM)

[email protected]

23 Gigli Giuliana CNR –IMC – sez. Meccanismi di Reazione, Roma

[email protected]

24 Gualandi Lorenzo Università di Bologna

[email protected]

25 Elahe Haddadi Università di Bologna - Shiraz University, Shiraz, Iran

[email protected]

26 Hassanein Khaled ISOF – CNR -Bologna

[email protected]

27 Imbriano Anna Università di Roma “Sapienza”

[email protected]

28 Lanzalunga Osvaldo Università di Roma “Sapienza”

[email protected]

29 Leoni Luca Università di Roma “Sapienza”

[email protected]

30 Magini Andrea Università di Parma

[email protected]

31 Mancini Giovanna CNR – IMC – Monterotondo (RM)

[email protected]

32 Mele Andrea CNRS - CEMCA – Brest- France

[email protected]

33 Menichetti Arianna Università di Bologna

[email protected]

34 Mummolo Liviana Università di Bologna

[email protected]

35 Nardi Martina Università di Roma “Sapienza”

[email protected]

36 Pastore Marco CNR – IMC – sez. Meccanismi di Reazione, Roma

[email protected]

37 Poderi Cecilia Università di Bologna

[email protected]

38 Rosa-Gastaldo Daniele Università di Padova

[email protected]

39 Rosati Marta Politecnico di Milano

[email protected]; Web-site: www.suprabionano.eu

40 Salvio Riccardo Università di Roma “Sapienza”

[email protected]

41 Severoni Emilia Università di Roma “Sapienza”

[email protected]

42 Sorrenti Alessandro ETH Zurich

[email protected].

43 Volpi Stefano Università di Padova

[email protected]

45

mailto:[email protected]

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