Substituent Effect on Porphyrin Film-Gas Interaction by Optical Waveguide: Spectrum Analysis and Molecular Dynamic Simulation

Substituent effect on optical gas sensing performance in porphyrin-based optical waveguide detection system was studied by molecular dynamics simulation (MDS), absorption/emission spectrum analysis, and optical waveguide (OWG) detection. The affinities of porphyrin with seven types of substituents (–H, –OH, –tBu, –COOH, –NH2, –OCH3, –SO3−) on para position of meso-phenyl porphyrin toward gas molecules in adsorption process were studied in different size of boxes with the same pressure and concentration. Analyte gases (CO2, H2S, HCl, NO2) were exposed to porphyrin film in absorption spectrophotometer, and in OWG with evanescent field excited by a guiding laser light with 670 nm wavelength. The extent of interaction between host molecule and the guest analytes was analyzed by the number of gas molecules in vicinity of 0.3 nm around substituents of porphyrin molecules. Optical waveguide results reveal that sulfonate porphyrin is mostly responsive to hydrochloride, hydrosulfide gas and nitrogen dioxide gases with strong response intensity. Molecular dynamics and spectral analysis provide objective information about the molecular state and sensing properties. Molecular rearrangements induced by gas exposure was studied by spectral analysis and surface morphology before and after gas exposure taking hydrosulfide gas as an example. Film-gas interaction mechanism was discussed in terms of each gas and substituent group characters

Correction: Gulimire Tuerdi, Nuerguli Kari, Yin Yan, Patima Nizamidin and Abliz Yimit *. A Functionalized Tetrakis(4-Nitrophenyl)Porphyrin Film Optical Waveguide Sensor for Detection of H2S and Ethanediamine Gases. Sensors 2017, 17, 2717

The authors wish to make the following corrections to this paper [...

A Functionalized Tetrakis(4-Nitrophenyl)Porphyrin Film Optical Waveguide Sensor for Detection of H2S and Ethanediamine Gases

The detection of hydrogen sulfide (H2S) and ethanediamine, toxic gases that are emitted from industrial processes, is important for health and safety. An optical sensor, based on the absorption spectrum of tetrakis(4-nitrophenyl)porphyrin (TNPP) immobilized in a Nafion membrane (Nf) and deposited onto an optical waveguide glass slide, has been developed for the detection of these gases. Responses to analytes were compared for sensors modified with TNPP and Nf-TNPP composites. Among them, Nf-TNPP exhibited significant responses to H2S and ethanediamine. The analytical performance characteristics of the Nf-TNPP-modified sensor were investigated and the response mechanism is discussed in detail. The sensor exhibited excellent reproducibilities, reversibilities, and selectivities, with detection limits for H2S and ethanediamine of 1 and 10 ppb, respectively, and it is a promising candidate for use in industrial sensing applications

Sensing Behavior of Metal-Free Porphyrin and Zinc Phthalocyanine Thin Film towards Xylene-Styrene and HCl Vapors in Planar Optical Waveguide

The sensing behavior of a thin film composed of metal-free 5, 10, 15, 20-tetrakis (p-hydroxy phenyl) porphyrin and zinc phthalocyanine complex towards m-xylene, styrene, and HCl vapors in a homemade planar optical waveguide (POWG), was studied at room temperature. The thin film was deposited on the surface of potassium ion-exchanged glass substrate, using vacuum spin-coating method, and a semiconductor laser light (532 nm) as the guiding light. Opto-chemical changes of the film exposing with hydrochloric gas, m-xylene, and styrene vapor, were analyzed firstly with UV-Vis spectroscopy. The fabricated POWG shows good correlation between gas exposure response and absorbance change within the gas concentration range 10–1500 ppm. The limit of detection calculated from the logarithmic calibration curve was proved to be 11.47, 21.08, and 14.07 ppm, for HCl gas, m-xylene, and styrene vapors, respectively. It is interesting to find that the film can be recovered to the initial state with trimethylamine vapors after m-xylene, styrene exposures as well as HCl exposure. The gas-film interaction mechanism was discussed considering protonation and π-π stacking with planar aromatic analyte molecules