DANIELE DEL GIUDICE

Dottore di ricerca

ciclo: XXXV


supervisore: Stefano Di Stefano

Titolo della tesi: Activated Carboxylic Acids for the Operation of pH-Responsive Supramolecular Systems

This thesis illustrates the results of the research I carried out during my PhD, which was focused on the employment of Activated Carboxylic Acids (ACAs) as chemical fuels for the dissipative operation of pH responsive supramolecular systems. This particular topic is part of a wider research field, which aims to artificially reproduce the characteristic features of living systems. Part A of the thesis gives an overview about recent advancements in this field. In particular, Chapter 1 briefly describes some examples found in Nature from which scientists took inspiration for the design of artificial systems with life like properties, such as adaptation and self regulation. Two main characteristics can be envisaged in this context: the high dynamicity and the ability to harness energy from the environment to accomplish fundamental tasks. Chapter 2 shows how supramolecular chemistry has been used so far to develop structures and systems that achieved, at least in part, the high dynamicity, recognition ability and selectivity of their natural counterparts. On the other hand, some of the strategies employed so far to design systems able to dissipate energy in order to provide a certain output, e.g. self assembly, catalysis, or a mechanical movement, are presented in Chapter 3, with particular focus on the employed chemical fuels. Among these, ACAs have been conveniently used to trigger transient pH variation, thus allowing to control pH responsive supramolecular systems, as described in Part B. Here, the state of the art of the ACAs topic is presented, drawing the attention on their mechanisms of operation, weaknesses, and strengths. During my PhD, I focused my research on broadening the field of application of ACAs, employing them to trigger the dissipative operation of other pH responsive supramolecular systems. Chapter 5 presents the results, obtained in collaboration with Casnati and Baldini’s group, and concerning the first application of an ACA, namely 2 cyano 2 phenilpropanoic acid, to control in a dissipative fashion the conformational equilibria of the calix[4]arene scaffold. Chapter 6 and 7 deal with the use of nitroacetic acid, a highly reactive and water-soluble ACA, to trigger the dissipative operation of supramolecular systems in water. Firstly, the host guest interaction between  cyclodextrin and an aminoacid was controlled over time, and secondly, in collaboration with Ricci’s group, nitroacetic acid was used to program the operation of DNA based pH responsive nanodevices. Moving back to organic solvents, Chapter 8 shows how ACAs can be used to control over time the distribution of components in dynamic library of imines, a useful tool to design highly dynamic systems based on covalent bonds. Finally, in Chapter 9 the results obtained during my six months stay in Mainz hosted by Walther group, are presented, showing how ACAs can be employed not only to control nanoscopic pH responsive supramolecular systems, but also macroscopic hydrogel based devices.

Produzione scientifica

11573/1675836 - 2023 - Dissipative systems driven by the decarboxylation of activated carboxylic acids
Del Giudice, Daniele; Di Stefano, Stefano - 01a Articolo in rivista
rivista: ACCOUNTS OF CHEMICAL RESEARCH (Washington, DC : American Chemical Society, 1968-) pp. 889-899 - issn: 1520-4898 - wos: WOS:000967548600001 (4) - scopus: 2-s2.0-85150335509 (4)

11573/1678719 - 2023 - Controlling the Conformation of 2-Dimethylaminobiphenyls by Transient Intramolecular Hydrogen Bonding
Del Giudice, Daniele; Valentini, Matteo; Sappino, Carla; Spatola, Emanuele; Murru, Aurora; Ercolani, Gianfranco; Di Stefano, Stefano - 01a Articolo in rivista
rivista: JOURNAL OF ORGANIC CHEMISTRY (Washington, DC : American Chemical Society, 1936-) pp. 4379-4386 - issn: 1520-6904 - wos: WOS:000952225500001 (4) - scopus: 2-s2.0-85150463692 (2)

11573/1670607 - 2023 - Autonomous Soft Robots Empowered by Chemical Reaction Networks
Fusi, Giorgio; Del Giudice, Daniele; Skarsetz, Oliver; Di Stefano, Stefano; Walther, Andreas - 01a Articolo in rivista
rivista: ADVANCED MATERIALS (Wiley-VCH Verlag GmBH:PO Box 101161, D 69451 Weinheim Germany:011 49 6201 606147, EMAIL: service@wiley-vch.de, INTERNET: http://www.wiley-vch.de, Fax: 011 49 6201 606328) pp. 1-8 - issn: 0935-9648 - wos: WOS:000899647200001 (24) - scopus: 2-s2.0-85144175243 (17)

11573/1677337 - 2023 - Cyclization reactions in confined space
Spatola, E.; Frateloreto, F.; Del Giudice, D.; Olivo, G.; Di Stefano, Stefano - 01g Articolo di rassegna (Review)
rivista: CURRENT OPINION IN COLLOID & INTERFACE SCIENCE (Elsevier Science Limited:Oxford Fulfillment Center, PO Box 800, Kidlington Oxford OX5 1DX United Kingdom:011 44 1865 843000, 011 44 1865 843699, EMAIL: asianfo@elsevier.com, tcb@elsevier.co.UK, INTERNET: http://www.elsevier.com, http://www.elsevier.com/locate/shpsa/, Fax: 011 44 1865 843010) pp. - - issn: 1359-0294 - wos: WOS:000962503700001 (0) - scopus: 2-s2.0-85150855057 (0)

11573/1691319 - 2023 - Combining X-ray Absorption and NMR spectroscopies to investigate a chemical reaction in solution
Tavani, Francesco; Del Giudice, Daniele; Di Berto Mancini, Marika; Frateloreto, Federico; Busato, Matteo; Lanzalunga, Osvaldo; Di Stefano, Stefano; D’Angelo, Paola - 01a Articolo in rivista
rivista: RADIATION PHYSICS AND CHEMISTRY (Elsevier Science Limited:Oxford Fulfillment Center, PO Box 800, Kidlington Oxford OX5 1DX United Kingdom:011 44 1865 843000, 011 44 1865 843699, EMAIL: asianfo@elsevier.com, tcb@elsevier.co.UK, INTERNET: http://www.elsevier.com, http://www.elsevier.com/locate/shpsa/, Fax: 011 44 1865 843010) pp. 111199-1-111199-6 - issn: 0969-806X - wos: (0) - scopus: 2-s2.0-85168825418 (0)

11573/1652783 - 2022 - Chemical Tools for the Temporal Control of Water Solution pH and Applications in Dissipative Systems
Del Giudice, D.; Frateloreto, F.; Sappino, C.; Di Stefano, Stefano - 01a Articolo in rivista
rivista: EUROPEAN JOURNAL OF ORGANIC CHEMISTRY (Weinheim : Wiley-VCH-Verl.) pp. - - issn: 1099-0690 - wos: WOS:000815356300001 (13) - scopus: 2-s2.0-85132577278 (9)

11573/1603364 - 2022 - Two Faces of the Same Coin: Coupling X-Ray Absorption and NMR Spectroscopies to Investigate the Exchange Reaction Between Prototypical Cu Coordination Complexes
Del Giudice, D.; Tavani, F.; Di Berto Mancini, M.; Frateloreto, F.; Busato, M.; Oliveira De Souza, D.; Cenesi, F.; Lanzalunga, O.; Di Stefano, Stefano; D'angelo, P. - 01a Articolo in rivista
rivista: CHEMISTRY-A EUROPEAN JOURNAL (Wiley-VCH Verlag GmBH:PO Box 101161, D 69451 Weinheim Germany:011 49 6201 606147, EMAIL: service@wiley-vch.de, INTERNET: http://www.wiley-vch.de, Fax: 011 49 6201 606328) pp. - - issn: 0947-6539 - wos: WOS:000730219700001 (8) - scopus: 2-s2.0-85121358737 (6)

11573/1633338 - 2022 - Dissipative Dynamic Covalent Chemistry (DDCvC) Based on the Transimination Reaction
Del Giudice, D.; Valentini, M.; Melchiorre, G.; Spatola, E.; Di Stefano, Stefano - 01a Articolo in rivista
rivista: CHEMISTRY-A EUROPEAN JOURNAL (Wiley-VCH Verlag GmBH:PO Box 101161, D 69451 Weinheim Germany:011 49 6201 606147, EMAIL: service@wiley-vch.de, INTERNET: http://www.wiley-vch.de, Fax: 011 49 6201 606328) pp. e202200685- - issn: 0947-6539 - wos: WOS:000772906300001 (13) - scopus: 2-s2.0-85127261650 (10)

11573/1660743 - 2022 - Dissipative Dynamic Libraries (DDLs) and Dissipative Dynamic Combinatorial Chemistry (DDCC)
Del Giudice, D; Spatola, E; Valentini, M; Ercolani, G; Di Stefano, Stefano - 01a Articolo in rivista
rivista: CHEMSYSTEMSCHEM (Weinheim: Wiley-VCH Verlag) pp. - - issn: 2570-4206 - wos: WOS:000859925700001 (5) - scopus: (0)

11573/1670870 - 2022 - Following a Silent Metal Ion: A Combined X-ray Absorption and Nuclear Magnetic Resonance Spectroscopic Study of the Zn2+ Cation Dissipative Translocation between Two Different Ligands
Frateloreto, Federico; Tavani, Francesco; Di Berto Mancini, Marika; Del Giudice, Daniele; Capocasa, Giorgio; Kieffer, Isabelle; Lanzalunga, Osvaldo; Di Stefano, Stefano; D'angelo, Paola - 01a Articolo in rivista
rivista: THE JOURNAL OF PHYSICAL CHEMISTRY LETTERS (Washington, DC: American Chemical Society) pp. 5522-5529 - issn: 1948-7185 - wos: WOS:000819338000001 (7) - scopus: 2-s2.0-85133100528 (9)

11573/1620197 - 2022 - Temporal Control of the Host-Guest Properties of a Calix[6]arene Receptor by the Use of a Chemical Fuel
Rispoli, Francesco; Spatola, Emanuele; Del Giudice, Daniele; Cacciapaglia, Roberta; Casnati, Alessandro; Baldini, Laura; Di Stefano, Stefano - 01a Articolo in rivista
rivista: JOURNAL OF ORGANIC CHEMISTRY ([Washington, D.C: American Chemical Society) pp. 3623-3629 - issn: 0022-3263 - wos: WOS:000773458100133 (13) - scopus: 2-s2.0-85125817070 (16)

11573/1600025 - 2022 - Dissipative control of the fluorescence of a 1,3-dipyrenyl calix[4]arene in the cone conformation
Spatola, Emanuele; Rispoli, Francesco; Del Giudice, Daniele; Cacciapaglia, Roberta; Casnati, Alessandro; Marchiò, Luciano; Baldini, Laura; Di Stefano, Stefano - 01a Articolo in rivista
rivista: ORGANIC & BIOMOLECULAR CHEMISTRY (Royal Society of Chemistry:Thomas Graham House, Science Park, Cambridge CB4 0WF United Kingdom:011 44 1223 432360, EMAIL: sales@rsc.org, INTERNET: http://www.rsc.org, http://www.chensoc.org, Fax: 011 44 1223 423429) pp. 132-138 - issn: 1477-0520 - wos: WOS:000721939500001 (12) - scopus: 2-s2.0-85121667473 (10)

11573/1552115 - 2021 - Time-programmable pH: decarboxylation of nitroacetic acid allows the time-controlled rising of pH to a definite value
Del Giudice, Daniele; Spatola, Emanuele; Valentini, Matteo; Bombelli, Cecilia; Ercolani, Gianfranco; Di Stefano, Stefano - 01a Articolo in rivista
rivista: CHEMICAL SCIENCE (Cambridge : Royal Society of Chemistry, 2010-) pp. 7460-7466 - issn: 2041-6520 - wos: WOS:000645225100001 (18) - scopus: 2-s2.0-85107328628 (15)

11573/1570912 - 2021 - Dissipative operation of pH-responsive DNA-based nanodevices
Mariottini, D.; Del Giudice, D.; Ercolani, G.; Di Stefano, Stefano; Ricci, F. - 01a Articolo in rivista
rivista: CHEMICAL SCIENCE (Cambridge : Royal Society of Chemistry, 2010-) pp. 11735-11739 - issn: 2041-6520 - wos: WOS:000681775500001 (29) - scopus: 2-s2.0-85115184990 (27)

11573/1563178 - 2021 - New horizons for catalysis disclosed by supramolecular chemistry
Olivo, Giorgio; Capocasa, Giorgio; Del Giudice, Daniele; Lanzalunga, Osvaldo; Di Stefano, Stefano - 01g Articolo di rassegna (Review)
rivista: CHEMICAL SOCIETY REVIEWS (Royal Society of Chemistry:Thomas Graham House, Science Park, Cambridge CB4 0WF United Kingdom:011 44 1223 432360, EMAIL: sales@rsc.org, INTERNET: http://www.rsc.org, http://www.chensoc.org, Fax: 011 44 1223 423429) pp. 7681-7724 - issn: 0306-0012 - wos: WOS:000651871700001 (98) - scopus: 2-s2.0-85109216445 (99)

11573/1409346 - 2020 - Controlling the liberation rate of the in situ release of a chemical fuel for the operationally autonomous motions of molecular machines
Biagini, Chiara; Capocasa, Giorgio; Del Giudice, Daniele; Cataldi, Valerio; Mandolini, Luigi; Di Stefano, Stefano - 01a Articolo in rivista
rivista: ORGANIC & BIOMOLECULAR CHEMISTRY (Royal Society of Chemistry:Thomas Graham House, Science Park, Cambridge CB4 0WF United Kingdom:011 44 1223 432360, EMAIL: sales@rsc.org, INTERNET: http://www.rsc.org, http://www.chensoc.org, Fax: 011 44 1223 423429) pp. 3867-3873 - issn: 1477-0520 - wos: WOS:000537137600011 (11) - scopus: 2-s2.0-85085586056 (11)

11573/1461822 - 2020 - Time Programmable Locking/Unlocking of the Calix[4]arene Scaffold by Means of Chemical Fuels
Del Giudice, D.; Spatola, E.; Cacciapaglia, R.; Casnati, A.; Baldini, L.; Ercolani, G.; Di Stefano, Stefano - 01a Articolo in rivista
rivista: CHEMISTRY-A EUROPEAN JOURNAL (Wiley-VCH Verlag GmBH:PO Box 101161, D 69451 Weinheim Germany:011 49 6201 606147, EMAIL: service@wiley-vch.de, INTERNET: http://www.wiley-vch.de, Fax: 011 49 6201 606328) pp. 14954-14962 - issn: 0947-6539 - wos: WOS:000577529300001 (20) - scopus: 2-s2.0-85092603605 (17)

11573/1335555 - 2019 - The hydrolysis of the anhydride of 2-cyano-2-phenylpropanoic acid triggers the repeated back and forth motions of an acid–base operated molecular switch
Biagini, C.; Capocasa, G.; Cataldi, V.; Del Giudice, D.; Mandolini, L.; Di Stefano, Stefano - 01a Articolo in rivista
rivista: CHEMISTRY-A EUROPEAN JOURNAL (Wiley-VCH Verlag GmBH:PO Box 101161, D 69451 Weinheim Germany:011 49 6201 606147, EMAIL: service@wiley-vch.de, INTERNET: http://www.wiley-vch.de, Fax: 011 49 6201 606328) pp. 15205-15211 - issn: 0947-6539 - wos: WOS:000493849200001 (19) - scopus: 2-s2.0-85074786690 (21)

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