Herein, we describe the synthesis of the first boron nitride-doped polyphenylenic material obtained through a [4 + 2] cycloaddition reaction between a triethynyl borazine unit and a biscyclopentadienone derivative, which undergoes organogel formation in chlorinated solvents (the critical jellification concentration is 4% w/w in CHCl3). The polymer has been characterized extensively by Fourier-transform infrared spectroscopy, solid-state 13C NMR, solid-state 11B NMR, and by comparison with the isolated monomeric unit. Furthermore, the polymer gels formed in chlorinated solvents have been thoroughly characterized and studied, showing rheological properties comparable to those of polyacrylamide gels with a low crosslinker percentage. Given the thermal and chemical stability, the material was studied as a potential support for solid-state electrolytes. showing properties comparable to those of polyethylene glycol-based electrolytes, thus presenting great potential for the application of this new class of material in lithium-ion batteries.
The group is led by Professor Davide Bonifazi at the Institute of Organic Chemistry in the University of Vienna.
We do research in synthetic organic chemistry to develop supramolecular architectures that, through the exploitation of their peculiar physical and structural properties, can contribute to the demonstration of key functions or basic concepts at the intersection of physical organic chemistry, materials science and biology.
Boron Nitride-Doped Polyphenylenic Organogels
Expanding the Library of 2-Phenylbenzotellurazoles: Red-Shifting Effect of Ethoxy Functionalities on the UV/Vis Absorption Properties
This work describes the high-yield synthesis of a novel series of benzotellurazoles bearing a phenyl ring in 2-position, which is differently functionalized with ethoxy chains. Changing the number and the position of these functional groups determines differences in the self-assembly in the solid state, as well as in the photophysical properties of the targeted molecules. As anticipated by theoretical calculations of the HOMO-LUMO gap of each molecule, the presence of ethoxy chains in o– and p-positions determines up to 20 nm red-shifts in the absorption peaks, when compared to unsubstituted benzotellurazole. Similarly, more significant changes are observed in the chemical shifts of 125Te NMR spectra for those derivatives bearing o– and p-ethoxy functionalization.
IGDQ motogenic peptide gradient induces directional cell migration through integrin (αv)β3 activation in MDA-MB-231 metastatic breast cancer cells
In the context of breast cancer metastasis study, we have shown in an in vitro model of cell migration that IGDQ-exposing (IsoLeu-Gly-Asp-Glutamine type I Fibronectin motif) monolayers (SAMs) on gold sustain the adhesion of breast cancer MDA-MB-231 cells by triggering Focal Adhesion Kinase and integrin activation. Such tunable scaffolds are used to mimic the tumor extracellular environment, inducing and controlling cell migration. The observed migratory behavior induced by the IGDQ-bearing peptide gradient along the surface allows to separate cell subpopulations with a “stationary” or “migratory” phenotype. In this work, we knocked down the integrins α5(β1) and (αv)β since they are already known to be implicated in cell migration. To this aim, a whole proteomic analysis was performed in beta 3 integrin (ITGB3) or alpha 5 integrin (ITGA5) knock-down MDA-MB-231 cells, in order to highlight the pathways implied in the integrin-dependent cell migration.
Our results showed that i) ITGB3 depletion influenced ITGA5 mRNA expression, ii) ITGB3 and ITGA5 were both necessary for IGDQ-mediated directional single cell migration and iii) integrin (αv)β3 was activated by IGDQ fibronectin type I motif. Finally, the proteomic analysis suggested that co-regulation of recycling transport of ITGB3 by ITGA5 is potentially necessary for directional IGDQ-mediated cell migration.
Tweaking the Optoelectronic Properties of S-Doped Polycyclic Aromatic Hydrocarbons by Chemical Oxidation
Peri-thiaxanthenothiaxanthene, an S-doped analog of peri-xanthenoxanthene, is used as a polycyclic aromatic hydrocarbon (PAH) scaffold to tune the molecular semiconductor properties by editing the oxidation state of the S-atoms. Chemical oxidation of peri-thiaxanthenothiaxanthene with H2O2 led to the relevant sulfoxide and sulfone congeners, whereas electrooxidation gave access to sulfonium-type derivatives forming crystalline mixed valence (MV) complexes. These complexes depicted peculiar molecular and solid-state arrangements with face-to-face p-p stacking organization. Photophysical studies showed a widening of the optical bandgap upon progressive oxidation of the S-atoms, with the bis-sulfone derivative displaying the largest value (E00 = 2.99 eV). While peri-thiaxanthenothiaxanthene showed reversible oxidation properties, the sulfoxide and sulfone derivatives mainly showed reductive events, corroborating their n-type properties. Electric measurements of single crystals of the MV complexes exhibited a semiconducting behavior with a remarkably high conductivity at room temperature (10-1-10-2 S cm-1 and 10-2-10-3 S cm-1 for the O and S derivatives, respectively), one of the highest reported so far. Finally, the electroluminescence properties of the complexes were tested in light-emitting electrochemical cells (LECs), obtaining the first mid-emitting PAH-based LECs.
International Day of Women and Girls in Science
In occasion of the “International Day of Women and Girls in Science”, Bonifazi group @ Institute of Organic Chemistry, UniWien, is organizing IUPAC Global Women’s Breakfast 2022 taking place online on February 16th.
The aim is to celebrate the accomplishments of women in science and to inspire younger generations to pursue careers in science.
The theme for this year is “Empowering Diversity in Science”. The program will include talks from scientists in academia and industry on their personal experiences as women in science. To create mutual connections, there will be a theme quiz and a panel discussion.
You are very welcome to join us on February 16, 08:45 CET with this link.
Click here for the full program: Program-GWB-2022
Organization of STiBNite/VIT Summer School: Self-assembled organic materials
Sponsored by two of our on going EU projects, VIT and STiBNite, the summer school took place at the UniVie Skylounge conference room on 4-5 July 2022.
We were delighted to host stimulating lectures both by external speakers and consortia representatives on the topic of self-assembled organic materials.
Big thanks to our wonderful speakers Renaud Nicolay, Francesco Picchioni, Chiara Gualandi, Timothy Swager, Richard Kelly, Laura Maggini, Takuji Hatakeyama, Emilio Perez, Milan Kivala, Susana Otero, Alexander Kros!
For more information about the STiBNite and VIT projects.
These projects have received funding from the European Union’s Horizon 2020 research and innovation programme under the Marie-Sklodowska-Curie grant agreements No 956923 and 101008237.
FFG Spin-off Fellowship awarded
The “IrrevoChrom” project is one out of total eleven recently granted FFG spin-off fellowships that will be led by FFG fellow Laura Maggini and host Davide Bonifazi at the Institute of Organic Chemistry, University of Vienna.
The FFG-funded IrrevoChrom Spin-off Fellowship will build on the patent developed in the Bonifazi group (EP application No EP22164076.6) within the framework of the Charisma Marie-Sklodowska Curie project they are coordinating, entailing the formulation of an irreversible EC matrix composed of both the chromogenic material, an anti-oxidant and electrolyte, to develop and scale-up a commercially viable and completely irreversible electrochromic ink compatible with industrial manufacturing processes.
Upon activation, this ink will provide a stark and permanent color transition (colorless to black), impossible to reverse. Thanks to the new formulations developed in this Fellowship, we will match our technology with industrial ECDs productions processes, jump starting its commercial exploitation, and develop in collaboration with Silicon Austria Labs activatable tamperproof demos.
Best flash talk award for Ruben Ferreira
At the European-Winter School on Physical Organic Chemistry (E-WISPOC 23, www.ewispoc.com) that took place in Bressasone between February 5-10, Rúben Ferreira was awarded with the best flash talk award for his poster with the title “Dynamic Covalent Photowriting“
Congratulations to your prize!
New DoSChem awardees of “New Ideas” program
DoSChem awards with 24811.20 Euro the joint expertise of Martina Crosta (Institute of Organic Chemistry, Davide Bonifazi group) and David Hernández-Castillo (Institute for Theoretical Chemistry, Leticia González group) with the proposal “Conjugation-Induced TADF Emitters: A Theoretically-Driven Experimental Design”.
Good luck Martina and David with their project!