Tetrakis 4-sulfophenyl Porphine Research Articles

A Preliminary Study for Tunable Optical Assessment of Exhaled Breath Ammonia Based on Ultrathin Tetrakis(4-sulfophenyl)porphine Nanoassembled Films

The detection of chemical substances excreted from the human body offers an attractive approach for non-invasive, early diagnostics of certain diseases. In this preliminary study, we proposed a susceptible optical sensor capable of quantitatively detecting ammonia from exhaled breath. The proposed sensor consists of nanoassembled ultrathin films composed of tetrakis(4-sulfophenyl)porphine (TSPP) and poly(diallyldimethylammonium chloride) (PDDA) deposited on quartz substrates using a layer-by-layer method. Measurement principles are based on the ammonia-induced absorbance changes at 489 (Soret band) and 702 nm (Q band), associated with the deprotonation of the J-aggregated TSPPs inside the film. Before exposure to breath, the PDDA/TSPP thin film was calibrated using known concentrations of ammonia gases with a projected detection limit of 102 ± 12 parts per billion (ppb). Calibrated sensor films were then exposed to human breath and urine samples to determine the ammonia concentration. Concentrations of exhaled ammonia are influenced significantly by the consumption of food or the amount of urea. Sensor response and maximum sensitivity, obtained from the absorbance changes induced by ammonia, were achieved by initial sensor exposure to HCl vapor. Previously reported procedures for the Helicobacter pylori (HELIC Ammonia Breath) test based on urea reaction with urease were reproduced using the proposed sensor. The observed behavior corresponded very well with the kinetics of the interactions between urea and urease, i.e., ammonia reached a maximum concentration approximately 5 min after the start of the reaction. A large-scale study involving 41 healthy volunteers in their 20s to 60s was successfully conducted to test the capabilities of the sensor to determine the concentration of exhaled ammonia. The concentration of ammonia for the healthy volunteers ranged between 0.3 and 1.5 ppm, with a mean value of ca. 520 ppb in the morning (before eating) and ca. 420 ppb in the afternoon (immediately after eating). These real-test mean values are meaningful when considered against the projected LOD.

Fabrication of Humidity-Resistant Optical Fiber Sensor for Ammonia Sensing Using Diazo Resin-Photocrosslinked Films with a Porphyrin-Polystyrene Binary Mixture.

Ammonia gas sensors were fabricated via layer-by-layer (LbL) deposition of diazo resin (DAR) and a binary mixture of tetrakis(4-sulfophenyl)porphine (TSPP) and poly(styrene sulfonate) (PSS) onto the core of a multimode U-bent optical fiber. The penetration of light transferred into the evanescent field was enhanced by stripping the polymer cladding and coating the fiber core. The electrostatic interaction between the diazonium ion in DAR and the sulfonate residues in TSPP and PSS was converted into covalent bonds using UV irradiation. The photoreaction between the layers was confirmed by UV-vis and Fourier transform infrared spectroscopy. The sensitivity of the optical fiber sensors to ammonia was linear when exposed to ammonia gases generated from aqueous ammonia solutions at a concentration of approximately 17 parts per million (ppm). This linearity extended up to 50 ppm when the exposure time (30 s) was shortened. The response and recovery times were reduced to 30 s with a 5-cycle DAR/TSPP+PSS (as a mixture of 1 mM TSPP and 0.025 wt% PSS in water) film sensor. The limit of detection (LOD) of the optimized sensor was estimated to be 0.31 ppm for ammonia in solution, corresponding to approximately 0.03 ppm of ammonia gas. It is hypothesized that the presence of the hydrophobic moiety of PSS in the matrix suppressed the effects of humidity on the sensor response. The sensor response was stable and reproducible over seven days. The PSS-containing U-bent fiber sensor also showed superior sensitivity to ammonia when examined alongside amine and non-amine analytes.

INVITED] Porphyrin-nanoassembled fiber-optic gas sensor fabrication: Optimization of parameters for sensitive ammonia gas detection

Highly sensitive fiber-optic ammonia gas sensors were fabricated via layer-by-layer deposition of poly(diallyldimethylammonium chloride) (PDDA) and tetrakis(4-sulfophenyl)porphine (TSPP) onto the surface of the core of a hard-clad multimode fiber that was stripped of its polymer cladding. The effects of film thickness, length of sensing area, and depth of evanescent wave penetration were investigated to clearly understand the sensor performance. The sensitivity of the fiber-optic sensor to ammonia was linear in the concentration range of 0.5–50 ppm and the response and recovery times were less than 3 min, with a limit of detection of 0.5 ppm, when a ten-cycle PDDA/TSPP film was assembled on the surface of the core along a 1 cm-long stripped section of the fiber. The sensor’s response towards ammonia was also checked under different relative humidity conditions and a simple statistical data treatment approach, principal component analysis, demonstrated the feasibility of ammonia sensing in environmental relative humidity ranging from dry 7% to highly saturated 80%. Penetration depths of the evanescent wave for the optimal sensor configuration were estimated to be 30 and 33 nm at wavelengths of 420 and 706 nm, which are in a good agreement with the thickness of the 10-cycle deposited film (ca. 30 nm).

Selective Methanol Gas Detection Using a U‐Bent Optical Fiber Modified with a Silica Nanoparticle Multilayer

SUMMARYThe development of an evanescent wave optical fiber sensor modified with an organic–inorganic hybrid nanoporous thin film for the detection of organic solvent vapors was demonstrated. The optical fiber with a core diameter of 200 μm was bent into U‐shape to enhance the penetration depth of light transferred into the evanescent field, and modified with a multilayered thin film of poly (allylamine hydrochloride) and silica nanoparticles (PAH/SiO2)n, via layer‐by‐layer (LbL) film deposition. The mesoporous film structure led to higher molecular diffusion and the highest selectivity to methanol among the six alcohols and water, which were used as target analytes, by the aid of tetrakis (4‐sulfophenyl) porphine (TSPP) infused inside the film.

A long period grating optical fiber sensor with nano-assembled porphyrin layers for detecting ammonia gas

In this study, the ability of a long period grating (LPG) optical fiber sensor coated with a multilayer film of poly(diallyldimethyammonium chloride) (PDDA) and tetrakis(4-sulfophenyl)porphine (TSPP) to detect ammonia gas was demonstrated. The nano-assembled thin film was prepared using a layer-by-layer deposition technique. This combination of an LPG and TSPP could allow highly sensitive optical sensors that specifically bind ammonia to be fabricated. An LPG with a period of 100μm and a PDDA/TSPP coating produced by depositing fifteen layers afforded a limit of detection of 0.67ppm for ammonia gas. TSPP molecules in the film acted as ammonia receptors because the TSPP morphologically changed from J- or H-aggregates to free base monomers when it was deprotonated by being exposed to ammonia. Interestingly, HCl vapor could be used to increase the relative amount of J-aggregation in the TSPP and to restore the sensor response. The reversibility of the morphological change in the TSPP allowed reversible changes to occur in the properties of the coating, including the refractive index, film thickness and density, and electrostatic interactions; these influenced the transmission spectrum of the LPG.

Optical Gas Sensor Fabrication Based on Porphyrin-Anchored Electrostatic Self-Assembly onto Tapered Optical Fibers

Tapered optical fibers with nano-assembled coatings of thicknesses of order tens of nanometres were used for the detection of ammonia gas. The film coating was composed of alternate layers of tetrakis-(4-sulfophenyl) porphine (TSPP) and poly(allylamine hydrochloride) (PAH), which were deposited using the electrostatic self-assembly process (ESA). Exposure of a PAH/TSPP nano-assembled non-adiabatic tapered optical fiber with a waist diameter of 10 µm to ammonia induced significant optical changes in the transmission spectrum of the optical fiber. The fiber optic sensor showed a linear sensitivity to the concentration of ammonia in the range of 10–100 ppm, with response and recovery times less than 100 and 240 sec, respectively. The 3σ limit of detection (LOD) was estimated to be ca. 2 ppm.

Optical fibre long period grating with a nanoporous coating formed from silica nanoparticles for ammonia sensing in water

A fibre optic long period grating (LPG) with an nano-assembled mesoporous coating of alternate layers of poly(diallyldimethylammonium chloride) (PDDA) and SiO2 nanospheres was used for the development of a highly sensitive fibre-optic chemical sensor. Sensor fabrication involves a 2-stage process: firstly, the deposition of the base mesoporous thin film (PDDA/SiO2) over an LPG written in the optical fibre using a layer-by layer technique, followed by the infusion of a functional material into the porous film. The refractive index of the base mesoporous coating, determined at a wavelength of 633nm using ellipsometry, was found to be 1.2. The infusion of the functional material into the coating resulted in a significant change in the RI of the coating, producing a dramatic change in the transmission spectrum of the LPG. The sensing mechanism exploited is based upon chemically induced desorption of the functional material from the mesoporous coating. The sensing of ammonia in aqueous solution was chosen as an example to demonstrate the sensing principle of the LPG sensor. The operation of the sensor was characterized using two functional materials, tetrakis-(4-sulfophenyl)porphine (TSPP) and polyacrylic acid (PAA). The device showed high sensitivity to ammonia with a response time less than 100s and a limit of detection of 140ppb when the TSPP infused (PDDA/SiO2) film was employed as a sensitive element.

Simultaneous Monitoring of Humidity and Chemical Changes Using Quartz Crystal Microbalance Sensors Modified with Nano-thin Films

Quartz crystal microbalance (QCM) electrodes modified with nano-thin films were used to develop a system for measuring significant environment changes (smoke, humidity, hazardous material release). A layer-by-layer approach was used for the deposition of sensitive coatings with a nanometer thickness on the electrode surface. The QCM electrode was modified with self-assembled alternate layers of tetrakis-(4-sulfophenyl) porphine (TSPP) (or its manganese derivative, MnTSPP) and poly(diallyldimethylammonium chloride) (PDDA). The QCM sensors, which had been reported previously for humidity sensing purposes, revealing a high possibility to recognize significant environmental changes. Identifying of the origin of environmental change is possible via differential signal analysis of the obtained data. The sensors showed different responses to humidity changes, hazardous gas (ammonia) or cigarette smoke exposure. Even qualitative analysis is not yet available; it has been shown that ventilation triggers or alarms for monitoring smoke or hazardous material release can be built using the obtained result.

Fiber optic long period grating sensors with a nanoassembled mesoporous film of SiO_2 nanoparticles

A novel approach to chemical application of long period grating (LPG) optical fibers was demonstrated, which were modified with a film nanoassembled by the alternate deposition of SiO(2) nanoparticles (SiO(2) NPs) and poly(diallyldimethyl ammonium chloride) (PDDA). Nanopores of the sensor film could be used for sensitive adsorption of chemical species in water, which induced the changes in the refractive index (RI) of the light propagating in the cladding mode of the optical fiber, with a concomitant effect on the transmission spectrum in the LPG region. The prepared fiber sensor was highly sensitive to the change in the RI of the surrounding medium and the response time was very fast within 10 s. In addition, chemical infusion into the film was tested using a porphyrin compound, tetrakis-(4-sulfophenyl)porphine (TSPP), which could be saturated within a few min. The lowest detectable concentration of the TSPP analyte was 10 microM. The TSPP infusion led to the development of well-pronounced dual resonance bands, indicating a large increase in the optical thickness of the film. The RI of the film was dramatically increased from 1.200 to ca. 1.540.

Nano-assembled thin film gas sensors. I. Ammonia detection by a porphyrin-based multilayer film

A thin film of porphyrin deposited by the layer-by-layer method is employed as the active element for an optical sensor. The usefulness of this film technology and the resulting nanoscale matrix for the detection of volatile organic compounds (VOCs), aromatics and amine-containing substances has been studied. The sensing principle is based on monitoring the optical changes of the Q band at 700 nm, as induced by the analyte in the electrostatic interaction between tetrakis(4-sulfophenyl)porphine (TSPP) and poly(diallyldimethylam- monium chloride) (PDDA) layers. Three thin film samples with different thicknesses were prepared to assess the effect of film thickness on the sensitivity. For ammonia, the sensor shows a linear sensitivity in the concentration range 0-100 ppm and the sensor response was within 30 seconds. Sensor response could be regenerated by rinsing in distilled water.