The goal of OXASWITCH project was to synthesize new molecules that could act as molecular switches. The term “molecular switches” was first used 40 years ago by biologists to describe movement of proteins under external stimuli like light. Chemists borrowed this term and nowadays it describes a molecule that is able to reversibly convert between two states – including geometrical isomers or conformers – in presence of various triggers such as light, pH, temperature. Examples of common switches are the pH indicators. Switches triggerd by light stimuli are called photoswitches and a particular notorious case of such molecules and their applications reffers to the photoisomerisation of retinal compound which constitutes the chemical basis of visual perception. Thus, the project approached this topic and in the context of the literature background, the young team designed, synthesized and characterised a large number of molecules, several fluorescent, susceptible to be used as photoswitches by means of on-off fluorescence emission, for example. Besides the specific research objectives, which were fully achieved, as described bellow in the number and quality of the published or under preparation scientific papers, the project contributed to establishment and strengthening of a young and dynamic research team. At the beginning of the project, the youngest members were MSc enrolled students. Meanwhile, they became PhD students, therefore, we have directly contributed to training of young human resources for research. In addition, bellow are described the dissemination activities that the members of the project achieved, indicating high quality scientific events to which the young researchers were exposed thanks to project implementation.
Papers
Two are better than one – Synthesis of novel blue and green emissive hydroxy-oxadiazoles, C.C. Anghel, C. Bădescu, A.G. Mirea A.Păun, N.D. Hădade, A.M. Mădălan, M. Matache*, C.C. Popescu* Dyes Pigm. 2021, 197, 109927.
Exploring arylazo-3,5-bis(trifluoromethyl)pyrazoles switches, B.C. Enache, A. Hanganu, C. Tablet, C.. Anghel, C.C. Popescu, A. Paun, N.D. Hădade, A.M. Mădălan, M. Matache*, 2022, 7, 39122−39135
Shifting emission of oxadiazoles via inter- or intramolecular hydrogen bonding, C.C. Anghel, A.G. Mirea, C.C. Popescu, A.M. Mădălan, A. Hanganu, A. Bende, N.D. Hădade,* M. Matache,* M. Andruh, 2023, 210, 111023
Synthesis of oxadiazole-based decorated azo compounds, A. Dobre, B.C. Bogdan, A. Hanganu, C.C. Popescu, A. Păun, I. Nicolau, M. Matache, 2022, manuscript in preparation
Arylazooxa(tia)diazoles in photoswitching, A. Dobre, B.C. Bogdan, N. Sandu, A. Hanganu, A. Paun, C.C. Popescu, M. Matache, 2022, manuscript in preparation
Attending scientific events
In 2021, team members attended a series of events (mostly online) and disseminated the project results through posters and oral communications:
Mihaela Matache, Switching molecules – an overview of applications and particular behaviour of N-acylhydrazones and azoswitches, Invited Speaker, Young Researchers’ International Conference on Chemistry and Chemical Engineering (YRICCCE III), June 04 – 05, 2021, Cluj-Napoca, Romania
Adela F. Dobre, Codruța C. Bădescu-Singureanu, Franck Suzenet, Marie-Aude Hiebel, Mihaela Matache, Codruța C. Popescu, Anca Păun, New π–extended oxadiazoles through Sonogashira coupling using thiones as electrophiles, Poster, Young Researchers’ International Conference on Chemistry and Chemical Engineering (YRICCCE III), June 04 – 05, 2021, Cluj-Napoca, Romania
Codruța C. Bădescu-Singureanu, Cătălin C. Anghel, Anca G. Mirea, Anca Păun, Niculina D. Hădade, Augustin M. Mădălan, Mihaela Matache, Codruța C. Popescu, Novel Oxadiazoles With Green Fluorescein-Like Fluorescence, Poster, Young Researchers’ International Conference on Chemistry and Chemical Engineering (YRICCCE III), June 04 – 05, 2021, Cluj-Napoca, Romania
Bogdan-C. Enache, Anamaria Hanganu, Augustin Mădălan, Mihaela Matache, Synthesis of Novel Arylazopyrazole Photoswitches, Poster, Young Researchers’ International Conference on Chemistry and Chemical Engineering (YRICCCE III), June 04 – 05, 2021, Cluj-Napoca, Romania
Adela Dobre, Anamaria Hanganu, George Costache, Codruța Popescu, Mihaela Matache, Anca Păun, In quest of Novel Oxadiazole-decorated-Azobenzenes as robust molecular photoswitches, Poster, 21st Tetrahedron Symposium, 21-24 June 2021 online
Bogdan-C. Enache, Anamaria Hanganu, Augustin Mădălan, Codruța C. Popescu, Anca Păun, Mihaela Matache, Synthesis of Novel Arylazopyrazole Photoswitches, Poster, 21st Tetrahedron Symposium, 21-24 June 2021 online
Codruța C. Bădescu-Singureanu, Laura E. Paladache, Ioana Nicolau, Anca Păun, Mihaela Matache, Codruța C. Popescu, Challenges and Approaches in the Synthesis of Novel Azoheteroayl-Based Compounds Containing Oxa(thia)diazole Moieties, Poster, 21st Tetrahedron Symposium, 21-24 June 2021 online
Alexandru Bujor, Iuliana Mihalache, Mihaela Matache, Petre Ionita, A preliminary study on the synthesis, characterization and complexation ability of old and new paramagnetic or fluorescent crown-ethers derivatives, Poster, “A. Corbella” International Summer School on Organic Synthesis, 2021 online
In 2022, team members continued to attended a series of events (both online and onsite) and disseminated the project results through posters and oral presentations:
Mihaela Matache, A journey through the world of small-molecules switches – the case of N-acylhydrazones and heteroaryl azo switches, Invited Lecture, “Costin D. Nenitescu” Institute of Organic Chemistry of the Romania Academy, 9th of May 2022
Nicoleta Sandu, Alexandra M. Purcărea, Anca G. Mirea, Anamaria Hanganu, Niculina D. Hădade, Anca Păun, Codruța C. Popescu, Mihaela Matache. Hydrazone-based macrocycles as hosts for organic small-molecules. Poster (Flash Presentation – Online). International Conference “Students for students” (ICSFS XVIIIth edition). 6-10 April 2022. Cluj-Napoca, Romania.
Adela F. Dobre, Mihaela Matache, Anamaria Hanganu, Codruța Popescu, Anca Păun, Ioana Nicolau, Exploring Photoswitching Capacity of Novel Azo Compounds Decorated With Oxadiazole Moieties, 17th Belgian Organic Synthesis Symposium,, poster, July, 3-8, 2022, Namur, Belgium
Bogdan-C. Enache, Anamaria Hanganu, Codruța C. Popescu, Anca Păun, Mihaela Matache, Synthesis of Novel 3,5-bis(trifluoromethyl)-4-arylazopyrazole Photoswitches, poster, 17th Belgian Organic Synthesis Symposium,, July, 3-8, 2022, Namur, Belgium
Mihaela Matache, Bogdan-C. Enache, Adela F. Dobre, Anamaria Hanganu, Codruța C. Popescu, Anca Păun, Ioana Nicolau, Exploring novel azo compounds as molecular photoswitches, poster 8th EuChemS Chemistry Congress, 27th August-1st September, 2022, Lisbon, Portugal
Bogdan-C. Enache, Adela F. Dobre, Anamaria Hanganu, Augustin M. Mădălan, Codruța C. Popescu, Anca Păun, Mihaela Matache, Influence of electronic effects onto performance of novel arylazopyrazole photoswitches, poster, 8th EuChemS Chemistry Congress, 27th August-1st September, 2022, Lisbon, Portugal
Nicoleta Sandu, Alexandra M. Purcărea, Anca G. Mirea, Anamaria Hanganu, Niculina D. Hădade, Anca Păun, Codruța C. Popescu, Mihaela Matache, Synthesis and investigation of hosting efficiency of emissive hydrazone-based macrocycles targeting fluorescent-based sensing applications, poster, 8th EuChemS Chemistry Congress, 27th August-1st September, 2022, Lisbon, Portugal
Contributions to PhD thesis
Catalin C. Anghel – joint PhD thesis between University of Bucharest and babes-Bolyai University of Cluj-Napoca, coordinators Acad. Marius Andruh and Prof. Ion Grosu, member of the supervising committee Dr. Mihaela Matache
Alexandru Bujor – PhD student @ University of Bucharest, coordinator Prof. Petre Ionita, member of the supervising committee Dr. Mihaela Matache
Adela Dobre – PhD student @ University of Bucharest, coordinator Prof. Petre Ionita, member of the supervising committee Dr. Mihaela Matache
Bogdan Enache – PhD student @ University of Bucharest, coordinator Prof. Petre Ionita, member of the supervising committee Dr. Mihaela Matache
Contributions to MSc dissertation thesis @ University of Bucharest
Adela Dobre – Synthetic methodological development for preparation of 1,3,4-oxadiazole-based azo and alkynylated derivatives – MSc June 2021 – Chemistry of Medicines and Cosmetic – supervisors – Dr. Anca Paun and Dr. Codruta Popescu
Bogdan Enache – Azoheteroaryl molecular photoswitches – MSc June 2021 – Chemistry of Medicines and Cosmetic – supervisor Dr. Mihaela Matache
Codruța-Christiana Bădescu-Singureanu, Synthesis of novel compounds extending reaction scope for alkynylated oxadiazoles and constructing peptide-small molecules conjugates for oligomerization platforms – MSc June 2021 – Biomolecules – supervisors – Dr. Codruta Popescu and Dr. Ioana Nicolau
Laura Elena Paladache, 2-Amino-5-phenyloxa(thia)diazoles as intermediates in coupling reactions – MSc June 2021 – Biomolecules – supervisors – Dr. Codruta Popescu and Dr. Ioana Nicolau
Adriana Anghel – Using click chemistry in synthesis of novel functional N-acylhydrazones – MSc June 2021 – Biomolecules – supervisors – Dr. Mihaela Matache and Dr. Anca paun
Cristina Ionete – Design and synthesis of azide- and alkyne-decorated peptoids and small molecules for bio-related applications – MSc June 2021 – Biomolecules – supervisors – Dr. Anca Paun and Dr. Mihaela Matache
Nicoleta Sandu – Synthesis and investigation of complexation and emission ability of hydrazone-based macrocycles – MSc June 2022 – Chemistry of Medicines and Cosmetic – supervisor Dr. Mihaela Matache
Contributions to BSc thesis @ University of Bucharest
Andreea Minea – Synthesis of multifunctionalised formyl compounds – BSc June 2021 – Pharmaceutical Chemistry – supervisor – Dr. Mihaela Matache
George Costache – Synthesis of aryaopyrazole intermediate for novel switching compounds – BSc June 2022 – Pharmaceutical Chemistry – supervisor – Dr. Mihaela Matache