Development of composite optical waveguide based on azobenzene-modified titanium metal-organic framework film for study of gas adsorption kinetics.

This study investigates the fabrication and gas adsorption kinetics of an azobenzene (AZB)-modified titanium metal-organic framework (AZB@Ti-MOF) film composite optical waveguide (COWG) that recognizes ethylenediamine (EDA) gas. After modification with AZB, the surface of the Ti-MOF film became rough and evolved from a hemispherical structure to a petal-like structure; a large pore size and small specific surface area accompanied the evolution of the surface morphology. The AZB@Ti-MOF film COWG exhibited a positive response to EDA gas co-existing with the same concentration (1000 ppm) of benzenes, amines, and acidic gases. It is postulated that charge transfer occurs when the AZB@Ti-MOF film COWG adsorbs EDA gas, leading to significant strengthening of the intramolecular hydrogen bonds as EDA works as an electron donor. Incomplete or prolonged EDA desorption from the film surface at room temperature resulted in a decrease in the surface sensitivity of the COWG AZB@Ti-MOF film. The kinetics of EDA adsorption were examined using pseudo-first-order and pseudo-second-order (PSO) kinetic models. The EDA adsorption kinetics fit well with the PSO model. As measured at room temperature, the adsorption capacity (qe) per unit surface of the AZB@Ti-MOF films was 46.50 × 10-2 µg·cm-2.

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 [...].

In situ growth and optical gas adsorption performance of Zn(ii) metal-organic framework membranes at room temperature.

A series of Zn(ii) metal-organic framework membranes, [Zn2(bdc)2(dpNDI)]n (where bdc = terephthalic acid and dpNDI = N,N'-di(4-pyridyl)-1,4,5,8-naphthalenediimide), were grown on a tin-diffused glass substrate using an in situ growth method at room temperature (20 °C). [Zn2(bdc)2(dpNDI)]n thin films were optically transparent and characterized by absorbance, thickness, refractive index and fluorescence techniques. After 20 h of growth, they displayed a complete honeycomb framework with a larger pore size (380 nm), uniform surface and lower refractive index. Also, it is demonstrated that [Zn2(bdc)2(dpNDI)]n thin films exhibited a greater adsorption response to meta-xylene gas with the coexistence of interferents like toluene, styrene and benzene gases, as measured by the planar optical waveguide (POWG) gas detection system under ultraviolet light (395 nm) irradiation. Moreover, when the [Zn2(bdc)2(dpNDI)]n thin film adsorbs meta-xylene gas, the intramolecular hydrogen bonds in the thin film framework were strengthened because of the accumulation of meta-xylene. At room temperature, the meta-xylene gas adsorption kinetics followed a pseudo-second-order (PSO) model, and the adsorption capacity on the unit surface was 6.46 µg cm-2. The highly selective meta-xylene adsorption performance of the [Zn2(bdc)2(dpNDI)]n thin film makes it an ideal sensing material for the recognition of harmful gases that are poisonous to the human body and the environment.

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.

A novel TiO2-modified THPP-BCP composite optical waveguide sensor for the determination of ethylenediamine at ppb level.

Composite thin films OWG sensors show higher sensitivity than single film-based OWG sensors, making them particularly useful in the detection of trace gases. In this work, we developed a new tetra hydroxyphenyl porphyrin (THPP)-bromocresol purple (BCP)/TiO2 gel composite film-based OWG (THPP-BCP/TiO2-OWG) sensor for identifying ethylenediamine (EDA) gas. The fabricated sensor was characterized using ultraviolet and infrared spectroscopy and atomic force microscopy. The test result shows that the response of the THPP-BCP/TiO2-OWG composite film sensor to analytes was 3-4 times higher than that of the single film THPP-OWG sensor. The THPP-BCP/TiO2-OWG sensor exhibited excellent selectivity and remarkable response to EDA gas at a concentration of < 1 ppb at room temperature, with fast response (1 s) and recovery (3 s) times. The high refractive index TiO2 film contributes to OWG's sensitivity, while the THPP and BCP's sensitivity to bases further increased the sensor's response to EDA gas. The combination of THPP-BCP thin film and TiO2 gel film provides a powerful platform for OWG sensors that are highly sensitive, specific, and stable in the detection of trace gases.

Exploring optical and electrical gas detection based on zinc-tetra-phenyl-porphyrin sensitizer.

We developed optical waveguide (OWG), ultraviolet-visible spectrophotometry (UV-vis), and electrically operated gas sensors utilizing zinc-tetra-phenyl-porphyrin (ZnTPP) as sensitizer. Strikingly, ZnTPP thin-film/K+-exchanged glass OWG sensing element exhibits a superior signal-to-noise ratio of 109.6 upon 1 ppm NO2 gas injection, which is 29.5 and 3.8 times larger than that of UV-vis (absorbance at wavelength of 438 nm) and ZnTPP electrical sensing elements prepared on an alumina ceramic tube, respectively. Further results on Fourier infrared spectra and UV-vis spectra, confirm a strong chemical adsorption of NO2 gas on ZnTPP. Therefore, our studies highlight the selection of suitable detection technique for analyte sensing with ZnTPP.

Metallic Effects on p-Hydroxyphenyl Porphyrin Thin-Film-Based Planar Optical Waveguide Gas Sensor: Experimental and Computational Studies.

Metal effects on the gas sensing behavior of metal complexes of 5,10,15,20-tetrakis(4-hydroxyphenyl)porphyrin (THPP) thin film was investigated in terms of detecting NO2 gas by the planar optical waveguide. For this purpose, several THPP and metal complexes were synthesized with different central metal ions: Co(II), Ni(II), Cu(II), and Zn(II). Planar optical gas sensors were fabricated with the metalloporphyrins deposited on K+ ion-exchanged soda-lime glass substrate with the spin coating method serving as host matrices for gas interaction. All of the THPP complex's films were fully characterized by UV-Vis, IR and XPS spectroscopy, and the laser light source wavelength was selected at 520 and 670 nm. The results of the planar optical waveguide sensor show that the Zn-THPP complex exhibits the strongest response with the lowest detectable gas concentration of NO2 gas for both 520 nm and 670 nm. The Ni-THPP and Co-THPP complexes display good efficiency in the detection of NO2, while, on the other hand, Cu-THPP shows a very low interaction with NO2 gas, with only 50 ppm and 200 ppm detectable gas concentration for 520 nm and 670 nm, respectively. In addition, molecular dynamic simulations and quantum mechanical calculations were performed, proving to be coherent with the experimental results.

Fabrication and characterization of photo-responsive metal-organic framework membrane for gas sensing using planar optical waveguide sensor.

A facile, novel fabrication approach using UV light irradiation was proposed to fabricate a photo-responsive metal-organic framework (PR-MOF-1, [Zn2-(bdc)2-(dpNDI)]n, where bdc = benzene-1,4-dicarboxylic acid; dpNDI = N,N'-di(4-pyridyl)-1,4,5,8-naphthalenetetracarboxy diimide) membrane. The morphology of the PR-MOF-1 framework evolved from a honeycomb porous structure to a densified ladder-layered structure after 60 min of UV-light illumination. The as-grown film was optically transparent and exhibited a greater sensing response to ethylenediamine (EDA) gas in the presence of interfering substances such as ammonia and dimethylamine as well as benzene, toluene, xylene, and styrene gases, as measured using an asymmetric planar optical waveguide gas sensor. When the EDA gas molecule was adsorbed on the surface of the membrane, charge transfer between them preferably occurred, leading to a change in the membrane surface conformation. As an ideal sensing material for EDA gas detection, the PR-MOF-1 membrane showed a relatively high surface sensitivity (11,000 times cm-1) after 60 min of growth, and it could quickly (in less than 2 s) detect 1 ppb of EDA gas with a significant response (S/N = 3.45). During the static gas adsorption process, the EDA gas adsorption kinetics fit well with pseudo-second-order (PSO) model, and the adsorption capacity (qe) on a unit surface showed a high value of 33.91 µg cm-2 at 283 K. The high selectivity and sensitivity of the PR-MOF-1 membrane for EDA gas indicate the effectiveness of the light irradiation method for alteration of the metal- organic framework membrane structure and control of the gas sensing properties.

Application of bromocresol purple nanofilm and laser light to detect mutton freshness.

Optical waveguide gas sensor with bromocresol purple (BCP) nano-film (70-80 nm) composited with silicone deposited on surface of K+-ion exchanged glass slide was fabricated and applied to detect amine gases released during mutton spoilage to test mutton freshness with the help of laser light (632 m). Gas sensing measurements (output light intensity vs. time) proved its high selectivity and good sensitivity (0.01 ppm) toward amines among volatile organic compounds. The optimal fabricating condition (2600 rpm, 0.10% BCP, 5.17% silicone) was selected experimentally, displaying 1 s and 12 s response-recovery time toward gases released from mutton samples stored at 5 °C and 25 °C respectively. The sensing mechanism was explained by combination and competition of diffusion-reaction, considering deprotonating reaction of bromocresol purple molecules and molecular size of analyte gases in diffusion process. UV-vis spectroscopy was used to select the specific wavelength of laser light source in optical waveguide performance and to detect the total volatile basic nitrogen contents in mutton sample to confirm the practicability of as-prepared optical waveguide sensor in detecting mutton freshness. The fabricated sensor is able to detect 7.2 mg/100 g gases released from mutton decomposition, providing a simple, fast, and cheap method to detect meat freshness.

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.

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.

Membrane-Protected Molecularly Imprinted Polymer for the Microextraction of Indole-3-butyric Acid in Mung Bean Sprouts.

Based on the hollow fiber protected molecularly imprinted polymer, a micro-solid-phase extraction (µ-SPE) method was developed and applied for the analysis of indole-3-butyric acid in mung bean sprouts by high-performance liquid chromatography. The extraction conditions of the µ-SPE method were optimized using L9(34) orthogonal, and optimum conditions were found as follows: pH of sample solution was 2.0, chloroform was the organic solvent for embedding the µ-SPE bars, and acetonitrile was the desorption solvent. In addition, the extraction time was 80 min, desorption time was 5 min, stirring speed was 800 rpm, and concentration of NaCl was 10%. Under the optimum conditions, a standard curve was established for IBA, with a correlation coefficient of 0.9999. After extraction with phosphate buffer solution (pH = 9.0), successful pretreatment of mung bean sprouts was achieved by the µ-SPE method. The limit of detection was 0.075 mg/kg, and the recoveries were found to be in the range of 88.9-106.4%. This method is simple, environmentally friendly, and can be used for the determination of indole auxin contents in green bean sprouts quickly and accurately.

Nafion film/K(+)-exchanged glass optical waveguide sensor for BTX detection.

An optical waveguide (OWG) sensor for the detection of BTX gases is reported. The highly sensitive element of this sensor was made by coating the copper Nafion film over a single-mode potassium ion exchanged glass OWG. We used the OWG sensor to detect toluene gas as a typical example BTX gas. The sensor exhibits a linear response to toluene in the range of 0.25-4250 ppm with response and recovery times less than 25 s. The sensor has a short response time, high sensitivity, and good reversibility.

Detection of Trimethylamine Based on a Manganese Tetraphenylporphyrin Optical Waveguide Sensing Element.

The sensitive detection of trimethylamine has been accomplished by using a homogeneous optical waveguide sensor system. Also the sensor can be easily fabricated by using tetraphenylporphyrin manganese (MnTPP) as sensitive materials to detect different volatile organic compounds (VOC). NMR (1H-NMR), field-emission scanning electron microscopy (FESEM), and X-ray photoelectron spectroscopy (XPS), infrared (IR), and ultraviolet-visible (UV-vis) instrumental means were used to characterize its structure. Gas-sensing measurements indicated that the sensing element has shown good selectivity, high sensitivity and a low detection limit level of 0.1 ppm to trimethylamine (TMA) with the presence of interference gases at room temperature. For a range of trimethylamine concentrations from 0.1 to 1000 ppm, the sensor has shown a short response time. Also the response time and recovery time are 1.5 and 50 s, respectively. Simulation experiments (dichloromethane, chloroform and carbon tetrachloride were selected as interference gases) showed little interference with its gas sensing. That may provide an ideal candidate for detecting the freshness of fish and seafood.

Optical-Electricity Gas-Sensing Property Detection of SDBS-WO3 Film at Room Temperature.

In this work, sodium dodecyl benzene sulfonate (SDBS) was used as a dispersing agent; a WO3 nanoparticle suspension was used as a sensing material. The SDBS-WO3 thin film/Sn-doped glass optical waveguide sensor element was prepared by spin coating. The sensing material was characterized by Fourier-transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), and field-emission scanning electron microscopy (FESEM). The gas-sensing characteristics of the fabricated sensors were studied at room temperature for various gases. The experimental results indicate that the sensor exhibited a high selective response toward SO2 and H2S and a low detection limit of 10 ppb to SO2 and H2S. The response/recovery times for SO2 and H2S were 2/23 and 2/18 s. However, during an electrochemical gas-sensing performance test of the SDBS-WO3 film at room temperature, the results indicated that the trend of the variation in resistance was consistent with the variation in the output light.

Optochemical properties of gas-phase protonated tetraphenylporphyrin investigated using an optical waveguide NH3 sensor.

5,10,15,20-Tetraphenylporphyrin (TPP) was synthesized, and a glass optical waveguide (OWG, which restricts and maintains the light energy in a specific, narrow space and propagates along the space axially) was coated with a gas-phase protonated TPP thin film to develop a sensor for NH3 gas detection. The results show that the TPP thin film agglomerated into H-based J-type aggregates after H2S gas exposure. The molecules in the protonated TPP film OWG sensor acted as NH3 receptors because the gas-phase protonated TPP film morphologically changed from J-type aggregates into free-base monomers when it was deprotonated by NH3 exposure. In this case, H2S gas could be used to increase the relative amount of J-type aggregates in the TPP film and restore the sensor response. The reversible surface morphology of the TPP film was analyzed by 1H NMR spectroscopy, atomic force microscopy, and UV-vis spectroscopy.

Room-temperature H2S Gas Sensor Based on Au-doped ZnFe2O4 Yolk-shell Microspheres.

Room-temperature type H2S sensing devices that use Au-doped ZnFe2O4 yolk-shell microspheres as the active material have been fabricated using a solvothermal method as well as subsequent annealing and a chemical etching process. The samples are characterized using X-ray diffraction (XRD), energy-dispersive X-ray spectroscopy (EDS), field-emission scanning electron microscopy (FESEM), and X-ray photoelectron spectroscopy (XPS). The results demonstrate that the doping of Au does not change the spinel structure of the products, which were yolk-shell microspheres, while the particle size varied with the Au doping concentration. Also, the as-fabricated sensor device exhibited excellent selectivity toward H2S gas at the room temperature; the gas-sensing property of 2 wt% Au-doped ZnFe2O4 microspheres was the best. The Au-doped ZnFe2O4 yolk-shell microspheres can be promising as a sensing material for H2S gas detecting at room temperature.

Optical waveguide sensor of volatile organic compounds based on PTA thin film.

In this study, a sensitive optical waveguide (OWG) sensor for the detection and identification of volatile organic compounds (VOCs) was reported. The sensing membrane is constructed by immobilization of peroxopolytungsten acid (PTA) thin film over a single-mode potassium ion (K(+)) exchanged glass OWG by spin-coating method. A laser beam was coupled into and out of the glass optical waveguide using prism couplers, and dry air functioned as a carrier gas. The sensor was tested for various volatile organic compounds (VOCs), and it showed higher response to the chlorobenzene gas compared to other VOCs. Therefore, we used the OWG sensor to detect chlorobenzene gas as a typical example of VOCs. The sensor exhibits a linear response to chlorobenzene gas in the range of 0.4-1000 ppm with rapid response and good reversibility. The constructed sensor is easy to fabricate and it has some unique qualities which can be characterized as inexpensive, sensitive, and reusable.

Optical waveguide BTX gas sensor based on polyacrylate resin thin film.

An optical sensor sensitive to BTX has been developed by spin coating a thin film of polyacrylate resin onto a tin- diffused glass optical waveguide. A pair of prism coupler was employed for optical coupling matched with diiodomethane (CH2l2). The guided wave transmits in waveguide layer and passes through the film as an evanescent wave. Polyacrylate film has a strong capacity of absorbing oil gases. The film is stable in N2 but benzene exposure at room temperature can result in rapid and reversible changes of transmittance (7) and refractive index (n1) of this film. It has been demonstrated that the sensor containing a 10 mm boardand about a hundred nanometers thick resin film can detect lower than 8 ppm BTX.

Thin film composite optical waveguides for sensor applications: a review.

We review the design and fabrication of thin-film composite optical waveguides (OWG) with high refractive index for sensor applications. A highly sensitive optical sensor device has been developed on the basis of thin-film, composite OWG. The thin-film OWG was deposited onto the surface of a potassium-ion-exchanged (K(+)) glass OWG by sputtering or spin coating (5-9mm wide, and with tapers at both ends). By allowing an adiabatic transition of the guided light from the secondary OWG to the thin-film OWG, the electric field of the evanescent wave at the thin film was enhanced. The attenuation of the guided light in the thin film layer was small, and the guided light intensity changed sensitively with the refractive index of the cladding layer. Our experimental results demonstrate that thin-film, composite OWG gas sensors or immunosensors are much more sensitive than sensors based on other technologies.