Phosphonate Appended Porphyrins as Versatile Chemosensors for Selective Detection of Trinitrotoluene

abstract

Fluorescent molecular probes based on phosphonate-functionalized porphyrin derivatives have been designed for selective detection of nitroaromatics. It is shown that molecular recognition is based on cooperative hydrogen bonding and pi-pi stacking interactions with electron-deficient molecules (nitro-aromatic compounds, NACs), displaying superior detection toward trinitrotoluene (TNT). The P=O functional groups decrease the lowest unoccupied molecular orbital (LUMO) energy level of the porphyrins and, consequently, facilitate the electron inoculation to TNT through a photoinduced electron transfer (PET) process. The hydroxyl groups of the phosphonates and pyrrole -NH protons are further engaged in donor acceptor interactions with TNT by strong intermolecular hydrogen bonding interactions (as evidenced by single crystal X-ray, NMR, and density functional theory (DFT)) showing turn off fluorescence behavior. The nonplanarity of the porphyrins induced by protonation at the central core of the porphyrin H(4)TPPA(2+) undergoes additional interactions, furnishing an anomalous increase in the selectivity of TNT at nanomolar levels in solution (limit of detection, LOD similar to 5 nM). Porphyrin-doped hybrid PMMA. [poly(methyl methacrylate)] polymer films demonstrate the reversibility of the fluorescence behavior and exhibit high photostability. The formation of discrete molecular aggregates on the surface of hybrid films and efficient diffusion of TNT vapors (10 ppb) displayed high selectivity in the solid state. The hybrid films are further used to demonstrate the detection of NACs in the aqueous medium, ultimately providing a platform for a practical strategy and implementation for the detection of toxic NACs.

keywords

EXPLOSIVE NITROAROMATICS; MOLECULAR RECOGNITION; TNT; ACID; POLYMERS; SENSORS; FACILE; ARRAY

subject category

Chemistry

authors

Venkatramaiah, N; Pereira, CF; Mendes, RF; Paz, FAA; Tome, JPC

Groups

G1 - Porous Materials and Nanosystems

Projects

CICECO - Aveiro Institute of Materials (UID/CTM/50011/2013)

Centre for Research in Ceramics and Composite Materials - CICECO (LA0011: 2013-2014) (PEst-C/CTM/LA0011/2013)

Robust Nanometric Coordination Polymers for Gas Separation and Light Emission (EXPL/CTM-NAN/0013/2013)

acknowledgements

We would like to thank Fundacao para a Ciencia e a Tecnologia (FCT, Portugal), the European Union, QREN, FEDER through the COMPETE program; QOPNA research unit (project PEst-C/QUI/UI0062/2013; FCOMP-01-0124-FEDER-037296) and CICECO-Aveiro Institute of Materials (ref. FCT UID/CTM/50011/2013), financed by national funds through the FCT/MEC and when applicable cofinanced by FEDER under the PT2020 Partnership Agreement, PEst-C/CTM/LA0011/2013; FCOMP-01-0124-FEDER-037271 for their general funding scheme. We further wish to thank FCT for funding the R&D project (EXPL/CTM-NAN/0013/2013; FCOMP-01-0124-FEDER-041282). The authors acknowledge FCT for the postdoctoral and doctoral grants SFRH/BPD/79000/2011 (to N.V.), SFRH/BD/86303/2012 (to C.F.P.), and SFRH/BD/84231/2012 (to R.F.M.). We thank Prof. Satish Patil, SSCU, Indian Institute of Science (IISc), Bangalore, for useful discussions.