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. 2014 Dec 17;19(12):21239-52.
doi: 10.3390/molecules191221239.

A sensitive A3B porphyrin nanomaterial for CO2 detection

Eugenia Fagadar-Cosma  1 , Dana Vlascici  2 , Gheorghe Fagadar-Cosma  3 , Anca Palade  4 , Anca Lascu  5 , Ionela Creanga  6 , Mihaela Birdeanu  7 , Rodica Cristescu  8 , Ileana Cernica  9
Affiliations

A sensitive A3B porphyrin nanomaterial for CO2 detection

Eugenia Fagadar-Cosma et al. Molecules. .

Abstract

The present report deals with the tailoring, preparation and characterization of novel nanomaterials sensitive to CO2 for use in detection of this gas during space habitation missions. A new nanostructured material based on mixed substituted asymmetrical A3B porphyrin: 5-(4-pyridyl)-10,15,20-tris(3,4-dimethoxyphenyl)-porphyrin (PyTDMeOPP) was synthesized and characterized by 1H-NMR, FT-IR, UV-vis, fluorescence, MS, HPLC and AFM. Introducing one pyridyl substituent in the 5-meso-position of porphyrin macrocycle confers some degree of hydrophilicity, which may cause self-assembly properties and a better response to increased acidity. The influence of pH and nature of the solvent upon H and J aggregates of the porphyrin are discussed. Porphyrin aggregation at the air-THF interface gave a triangular type morphology, randomly distributed but uniformly oriented. When deposition was made by multiple drop-casting operations, a network of triangles of uniform size was created and a porous structure was obtained, being reorganized finally in rings. When the deposition was made from CHCl3, ring structures ranging in internal diameter from 300 nm to 1 µm, but with the same width of the corona circular of approx. 200 nm were obtained. This porphyrin-based material, capable of generating ring aggregates in both THF and CHCl3, has been proven to be sensitive to CO2 detection. The dependence between the intensity of porphyrin UV-vis absorption and the concentration of CO2 has a good correlation of 98.4%.

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Conflict of interest statement

The authors declare no conflict of interest.

Figures

Figure 1
Figure 1
Structure of 5-(4-pyridyl)-10,15,20-tris(3,4-dimethoxyphenyl)porphyrin.
Figure 2
Figure 2
The UV-vis spectrum of 5-(4-pyridyl)-10,15,20-tris(3,4-dimethoxyphenyl)porphyrin.
Figure 3
Figure 3
The superposed UV-vis spectra of 5-(4-pyridyl)-10,15,20-tris(3,4-dimethoxyphenyl)porphyrin, in methanol, pH = 5.5 (blue line), and in methanol-water systems with different amounts of HCl 0.1 N, curves 1 to 4. In detail curve 1.
Figure 4
Figure 4
Excitation and emission spectra of 5-(4-pyridyl)-10,15,20-tris(3,4-dimethoxyphenyl)porphyrin, in THF, at λem = 603 nm (for excitation) and λex = 420 nm (for emission).
Figure 5
Figure 5
2D AFM image of 5-(4-pyridyl)-10,15,20-tris(3,4-dimethoxyphenyl)porphyrin (2.2 × 2.2 µm) from THF by drop-casting: (a) single and (b) multiple deposition.
Figure 6
Figure 6
2D AFM image (2.2 × 2.2 µm) of porphyrin (PyTDMeOPP) ring architectures—single deposition from CHCl3.
Figure 7
Figure 7
Dependence between increasing concentration of CO2 in water and the intensity of absorption of (PyTDMeOPP).
Figure 8
Figure 8
2D AFM images of ring aggregates of porphyrin in THF/water, before CO2 introduction.
Figure 9
Figure 9
2D AFM images of ring aggregates of porphyrin (PyTDMeOPP) in THF/water, after 15 min of CO2 introduction.
See this image and copyright information in PMC

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