Objective 1.
Progress and conclusions: We tried to synthesize 2,7,12,17-Tetrapropylporphycene with Pt, Pd, and Os a metal center. However, synthesis failed due to the polymerization of its precursor compound 2-methyl-4-propyl-3,5 dicarbethoxy pyrrole during synthesis.
As a contingency plan, we collaborators with Prof. Nobuo Kimizuka at Kyushu University, Japan, and Prof. Fabienne Dumoulin at Acibadem Mehmet Ali Aydinlar University Turkey. They provided us with a newly synthesized NIR sensitizer ((Os(m-peptpy)2(TFSI)2) and Zn-phthalocyanine). The (Os(m-peptpy)2(TFSI)2) was used for NIR to blue photon upconversion and Zn-phthalocyanin was used for NIR sensitized molecular photoswitching. The structure of sensitizers is shown in Fig. 1. The commercially available red and green sensitizer PdTPBP was successfully used to fabricate red to blue and green to blue photon upconversion
Objective 2.
Progress and conclusions: We synthesized four ionic annihilators, 1) Sodium-diphenylanthracenesulfonate (DPAS), 2) Disodium di-phenylanthracene bisulfonate (DPBS), 3) Disodium para-ter-phenyl biulfonate (p-ter-PBS) and 4) Sodium-TIPS-anthracene 2-sulfonate (TIPS-AnS) as shown in Figure 2. The DPAS and DPBS were used to prepare green to blue TTA-UC film and TIPS-AnS was used to form NIR/Red to blue TTA-UC films.
Objective 3.
Progress and conclusions: We investigated the formation of protein-surfactant-chromophores co-assembly with different sensitizer-annihilator pair and protein surfactant systems. The surfactants used were triton X-100 (TX), TX-100 reduced (TXr), Polyalkylene glycol and PEG-PPG-PEG, Pluronic® L-31 (Figure 3). First, we investigated the photophysical properties of chromophores in the native surfactants. The TX-100 performed best for G-TX-PtOEP-DPAS film ( green to blue UC). We replaced TX100 due to its toxicity with TX-100-reduced to form NIR / red to blue films. Other surfactants performed well but chromophores showed low fluorescence quantum yields. We tested proteins (gelatin, zein, and beta-Lactoglobullin, Figure 4) as matrices to fabricate surfactant-chromophore systems in the solid-state due to their oxygen barrier. Among them, gelatin forms optically transparent films. Zein and beta-Lactoglobullin form yellow and white translucent film hence were not used further.
The protein-surfactant-chromophores coassembled films were fabricated upon one-step drop-casting of the solution on a glass plate and air drying for 48 h (Figure 5). The NIR to blue and red to blue films are composed of G-TXr- Os(m-peptpy)2(TFSI)2-DPAS and G-TXr- PdTPBP-TIPS-AnS systems (Figure 6). The green to blue film showed a high UC quantum yield of 7.6 % whereas the red to blue film showed a UC quantum yield of 8.2 % in the air. The NIR to blue film has been prepared for proof-of-concept demonstration and its detailed analysis will be published later. Hence we could successfully fabricate new photon upconversion bioplastics films showing wide spectrum photon harvesting (530 nm to 730 nm).
Dissemination:
o Publications in Scientific Journals
1) Bharmoria et al.J Mat. Chem. C, 2021, 2021,9, 11655-11661.
2) Bharmoria et al., Chem. Soc. Rev. 2020, 49, 6529-6554 (Highlighted at the Front Cover).
3) Fredrik et al. Bharmoria, J. Phys. Chem. B., 2021, 125, 6255–6263.
4) The Red/NIR to blue TTA-UC bioplastics film is submitted for publication in the journal "Adv. Funct. Mater."
The developed work was presented at many international Conferences and institutions for wide outreach.
Represented Images for the presentation of the overall theme of the project are provided as Scheme 1-3.
