The components of colorimetric sensor arrays are inherently nanoscale. The 36 dyes were selected empirically based on the quality of their color response to a representative selection of different analytes 

The components of colorimetric sensor arrays are inherently nanoscale. The 36 dyes were selected empirically based on the quality of their color response to a representative selection of different analytes 

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The development of an array of chemically-responsive dyes on a porous membrane and in its use as a general sensor for odors and volatile organic compounds(VOCs) is reviewed. These colorimetric sensor arrays (CSA) act as an ``optoelectronic nose{''} by using an array of multiple dyes whose color changes are based on the full range of intermolecular...

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... approximately 5-20 kJ/mol) bond energy. According to some previous research (Suslick, 2004;Suslick et al., 2007;, the molecular interaction based on metal-ligand is approximately 20 000-fold more sensitive than weaker interactions based on physical adsorption and van der Waals forces. Furthermore, to meet the second requirement of fluorescent sensor fabrication, the molecular structure must possess highly conjugated macrocycles, including π electrons, to produce the fluorescence spectrum. ...
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Metalloporphyrin-based fluorescent sensor was developed for the acid value in frying oil. The electronic and structural performances of iron tetraphenylporphyrin (FeTPP) were theoretically investigated using time-dependent density functional theory (TD-DFT) and DFT at the B3LYP/LANL2DZ level. The quantified FeTPP-based fluorescent sensor results revealed its excellent performance in discriminating different analytes. In the present work, the acid value of palm olein was determined after every single frying cycle. A total of 10 frying cycles were conducted each day for 10 consecutive days. The FeTPP-based fluorescent sensor was used to quantify the acid value and the results were compared with the chemical data obtained by conventional titration method. The synchronous fluorescence spectrum for each sample was recorded. Parallel factor analysis (PARAFAC) was used to decompose the three-dimensional spectrum data. Then, the support vector regression (SVR), partial least squares (PLS), and back-propagation artificial neural network (BP-ANN) methods were applied to build the regression models. After the comparison of the constructed models, the SVR models exhibited the highest correlation coefficients among all models, with 0.9748 and 0.9276 for the training and test set, respectively. The findings suggested the potential of FeTPP-based fluorescent sensor in rapid monitoring of the used frying oil quality and perhaps also in other foods with higher oil content.
... Suslick and co-workers have made substantial findings in this field, regarding the development of an optoelectronic nose. Their group used arrays of chemically responsive dyes to sense and distinguish between volatile organic compounds, beer, and explosives, to name a few, for a wide field of applications 4,[7][8][9][10] . Their prior work focused on low-cost, but one time use optical gas sensors on paper 4,10 . ...
... In this optoelectronic nose, utilizing an array of dyes mimics the biological olfactory systems, where the specificity in odor detection originates from pattern recognition of responses of many cross-reactive olfactory receptors 4,8 . Types of dyes that are commonly used in these optoelectronic nose arrays include Bronsted acidic or basic dyes, Lewis acidic or basic dyes, redox responsive dyes, or dyes with large permanent dipoles including solvatochromic or zwitterionic dyes 4 . ...
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A fabrication method for a stable entrapment of optically responsive dyes on a thread substrate is proposed to move towards a detection system that can be integrated into clothing. We use the dyes 5,10,15,20-Tetraphenyl-21H,23H-porphine manganese(III) chloride (MnTPP), methyl red (MR), and bromothymol blue (BTB), for a proof-of-concept. Our optical approach utilizes a smartphone to extract and track changes in the red (R), green (G) and blue (B) channel of the acquired images of the thread to detect the presence of an analyte. We demonstrate sensing of 50–1000 ppm of vapors of ammonia and hydrogen chloride, components commonly found in cleaning supplies, fertilizer, and the production of materials, as well as dissolved gas sensing of ammonia. The devices are shown to be stable over time and with agitation in a centrifuge. This is attributed to the unique dual step fabrication process that entraps the dye in a stable manner. The facile fabrication of colorimetric gas sensing washable threads is ideal for the next generation of smart textile and intelligent clothing.
... Consequently, physisorption-based sensors, the basis of traditional electronic nose technology, are almost always dominated by a single dimension in a statistical sense. 14,59,335 The sensor may indeed be constructed as an arraythat is, they can be constructed from many rows and columns containing different metal oxides or polymer compositesbut the resulting output space is highly covariant, and that results in a low overall dimensionality. In general, in such arrays, there is a single dominant dimension that describes the vast majority (>90%) of both the raw output space and discriminatory ability: most often this dimension is essentially hydrophobicity. ...
Article
A comprehensive review on the development and state of the art of colorimetric and fluorometric sensor arrays is presented. Chemical sensing aims to detect subtle changes in the chemical environment by transforming relevant chemical or physical properties of molecular or ionic species (i.e., analytes) into an analytically useful output. Optical arrays based on chemoresponsive colorants (dyes and nanoporous pigments) probe the chemical reactivity of analytes, rather than their physical properties (e.g., mass). The chemical specificity of the olfactory system does not come from specific receptors for specific analytes (e.g., the traditional lock-and-key model of substrate–enzyme interactions), but rather olfaction makes use of pattern recognition of the combined response of several hundred olfactory receptors. In a similar fashion, arrays of chemoresponsive colorants provide high-dimensional data from the color or fluorescence changes of the dyes in these arrays as they are exposed to analytes. This provides chemical sensing with high sensitivity (often down to parts per billion levels), impressive discrimination among very similar analytes, and exquisite fingerprinting of extremely similar mixtures over a wide range of analyte types, in both the gas and liquid phases. Design of both sensor arrays and instrumentation for their analysis are discussed. In addition, the various chemometric and statistical analyses of high-dimensional data (including hierarchical cluster analysis (HCA), principal component analysis (PCA), linear discriminant analysis (LDA), support vector machines (SVMs), and artificial neural networks (ANNs)) are presented and critiqued in reference to their use in chemical sensing. A variety of applications are also discussed, including personal dosimetry of toxic industrial chemical, detection of explosives or accelerants, quality control of foods and beverages, biosensing intracellularly, identification of bacteria and fungi, and detection of cancer and disease biomarkers.
... Currently, NIRS and e-nose based sensors cannot be used for pure VOCs quantification in materials. Porphyrins dyes are known to bind with various volatiles leading to intense colour changes [3,4], as a result of their strong molecular interactions [5,6]; and the coordination mechanism of their central metals with VOCs [7,8]. Porphyrins dyes are sensitive to a wide range of volatiles [9,10] with none known to be specifically sensitive to any VOC [11]. ...
Article
Volatile organic compounds (VOCs) detection and measurement in materials with near infrared spectroscopy (NIRS) have been an unresolved constraint till date. This paper focused on the use of NIRS for rapid detection and quantification of pure VOCs (ethanol, ethyl acetate and acetic acid) in mixed VOCs via employing sensitive intermediary chemo-responsive dyes as capture probes, whose NIRS spectra were scanned, preprocessed and used to build partial least squares (PLS) prediction models. Average predicted rates based on the PLS-built prediction models for the pure VOCs in the mixed VOCs yielded 98.60 ±17.41%. 78.26% of the pure VOCs prediction rates ranged between 85–114% and normally distributed. The high prediction rates achieved imply the technique may be deployed as a panacea to widen the usage scope of NIRS and e-nose based colorimetric sensors for rapid detection and quantification of VOCs content in materials which hitherto had been a constraint for both systems.
... Colorimetric arrays are such a versatile technique because of their ability to serve as effective detection tools for a diverse range of analytes including odorants and gases (Janzen et al., 2006;Suslick et al., 2007;Kemling and Suslick, 2011;Askim et al., 2013;Feng et al., 2010aFeng et al., , 2010bFeng et al., , 2010cJanzen et al., 2006;Kemling and Suslick, 2011;Suslick et al., 2007), metal ions (Ariza-Avidad et al., 2014;Sener et al., 2014), nanoparticles (Mahmoudi et al., 2016), sugars (Musto and Suslick, 2010;Musto et al., 2009), amines (Bang et al., 2008;Bueno et al., 2015;Soga et al., 2013;), anions (Feng et al., 2012;Palacios et al., 2007), organic compounds in water (Zhang and Suslick, 2005), narcotics (Baumes et al., 2010;Burks et al., 2010;Lyon et al., 2011;Smith et al., 2012), food spoilage Salinas et al., 2014b), organic solvents (Rankin et al., 2015), fuels (Li et al., 2015b), and pesticides (Qian and Lin, 2015). Complex mixtures including beer, coffee, and soft drinks have also been characterized Zhang et al., 2006;Suslick et al., 2010). ...
... Colorimetric arrays are such a versatile technique because of their ability to serve as effective detection tools for a diverse range of analytes including odorants and gases (Janzen et al., 2006;Suslick et al., 2007;Kemling and Suslick, 2011;Askim et al., 2013;Feng et al., 2010aFeng et al., , 2010bFeng et al., , 2010cJanzen et al., 2006;Kemling and Suslick, 2011;Suslick et al., 2007), metal ions (Ariza-Avidad et al., 2014;Sener et al., 2014), nanoparticles (Mahmoudi et al., 2016), sugars (Musto and Suslick, 2010;Musto et al., 2009), amines (Bang et al., 2008;Bueno et al., 2015;Soga et al., 2013;), anions (Feng et al., 2012;Palacios et al., 2007), organic compounds in water (Zhang and Suslick, 2005), narcotics (Baumes et al., 2010;Burks et al., 2010;Lyon et al., 2011;Smith et al., 2012), food spoilage Salinas et al., 2014b), organic solvents (Rankin et al., 2015), fuels (Li et al., 2015b), and pesticides (Qian and Lin, 2015). Complex mixtures including beer, coffee, and soft drinks have also been characterized Zhang et al., 2006;Suslick et al., 2010). ...
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There is a significant demand for devices that can rapidly detect chemical-biological-explosive (CBE) threats on-site and allow for immediate responders to mitigate spread, risk, and loss. The key to an effective reconnaissance mission is a unified detection technology that analyzes potential threats in real time. In addition to reviewing the current state of the art in the field, this review illustrates the practicality of colorimetric arrays composed of sensors that change colors in the presence of analytes. The review also describes an outlook towards future technologies, and describes how they could possibly be used in areas such as war zones to detect and identify hazardous substances.
... Interactions such as p-p molecular complexation, bond formation, acid-base interaction, physical adsorption and van der Waals interactions can take place when they are exposed to different analytes. 5 These interactions change the optical properties of a colorimetric sensor array which then presents different colors or spectra. 6 Combined with certain chemometric methods, qualitative or quantitative analysis could be realized utilizing the response signal of all dyes in the array. ...
Article
A new method based on a multi-spectral technique was proposed to characterize the signal of colorimetric sensor arrays for gas detection. Firstly, the characteristic wavelengths, which are most relevant to the detected substance, were extracted from the hyperspectral information of the colorimetric sensor arrays. Then, narrowband filters with the corresponding central wavelengths were selected to isolate the effective signal of the sensor arrays. In this study, ammonia (NH3) was taken as an example to test the performance of the proposed multi-spectral method. Prediction of NH3 concentration based on the hyperspectral method and normal tri-color (R/G/B) method was also performed for comparison. Compared with the tri-color method, the correlation coefficient for the testing set (Rt) based on the multi-spectral method increased from 0.902 to 0.976, root mean squared error of prediction (RMSEP) decreased from 1.213 to 0.548, and residual predictive deviation for the testing set (RPDt) increased from 2.903 to 6.151, which means that the results were notably improved both in accuracy and stability. Furthermore, the multi-spectral method possesses the advantages of low cost, easy operation and greatly reduced data size. The proposed multi-spectral method could be used to characterize the signal of colorimetric sensor arrays for gas detection.
... Chemo responsive pigments are those pigments that change color in either reected or absorbed light, upon changes in their chemical environment. 3,10 The basic principle of this method is the utilization of the color change induced by reaction between volatile compounds and an array of chemical dyes upon ligand binding for chemical vapor detection and differentiation. Chemical dyes are oen selected according to their sensitivity to the specic Volatile Organic Compounds (VOCs). ...
Article
Total Volatile Basic-Nitrogen (TVB-N) content is one of core measures in evaluating chicken freshness. This study reported the feasibility to quantify Total Volatile Basic-Nitrogen (TVB-N) content in chicken meat by a low cost colorimetric sensor array with the help of chemometric analysis. We fabricated a colorimetric sensor array by printing 12 chemically responsive dyes (i.e. 9 porphyrins/metalloporphyrins and 3 pH indicators) on a C2 reverse silica-gel flat plate for the fast and non-destructive quantitative determination of TVB-N content in chicken. A colour change profile for each sample was obtained by differentiating the image of the sensor array before and after exposure to volatile organic compounds (VOCs). Linear algorithm; partial least squares regression (PLSR) and nonlinear algorithms; back propagation artificial neural network (BPANN), Adaptive Boosting BPANN (BP-AdaBoost) and support vector machine regression (SVMR) methods based on particle swarm optimization (PSO) were used to build the TVB-N prediction model. Experimental results showed that the predictive precision of the PSO-SVMR model was superior to linear and classic non-linear models. The optimum PSO-SVMR model was obtained with 4 support vectors and Rp of 0.8981, RMSEP of 5.5255. The overall results are encouraging for the application of low cost colorimetric sensors combined with an appropriate chemometric method in the poultry industry for quality assessment because it is practical, non-invasive, rapid and simple.
... Moreover, the olfactory receptor inspired decision making process that relies on pattern generation from weakly interacting receptors against various target molecules provides novel opportunities to design more effective E-nose sensors using off-the-shelf polymers, chemical dyes, metals and semiconductors. [137][138][139][140] All of these advances by mimicking biological sensing systems have provided with excellent design principles to improve the selectivity and sensitivity of the sensors. ...
Article
Detection of desired target chemicals in sensitive and selective manner is critically important to protect human health, environment and national security. Nature has been a great source of inspiration for the design of sensitive and selective sensors. In this mini-review, we overview the recent developments in bio-inspired sensor development. There are four major components of sensor design: Design of receptors for specific targets; coating material to integrate receptors to transducing machinery; sensitive transducing of signals; and decision making based on the sensing results. We discuss the biomimetic methods to discover specific receptors followed by a discussion about bio-inspired nanocoating material design. We then review the recent developments in phage-based biospired transducing systems followed by a discussion of biomimetic pattern recognition-based decision making systems. Our review will be helpful to understand recent approaches to reverse-engineer natural systems to design specific and
... Chemo-responsive pigments are those pigments that change color in either reected or absorbed light, upon changes in their chemical environment. 3,10 The basic principle of this method is the utilization of the color change induced by the reaction between volatile compounds and an array of chemical dyes upon ligand binding for chemical vapor detection and differentiation. Chemical dyes are oen selected according to their sensitivity to specic volatile organic compounds (VOCs). ...
Article
Total volatile basic nitrogen (TVB-N) content is an important indicator for evaluating meat’s freshness. This study attempted to quantify TVB-N content non-destructively in chicken using a colorimetric sensors array with the help of multivariate calibration. First, we fabricated a colorimetric sensor array by printing 12 chemically responsive dyes on a C2 reverse silica-gel flat plate. A color change profile was obtained by differentiating the image of sensor array before and after exposure to volatile organic compounds (VOCs) released from chicken sample. In addition, we proposed a novel algorithm for modeling, which is back propagation artificial neural network (BP-ANN) and adaptive boosting (AdaBoost) algorithm, namely AdaBoost-BPANN, and we compared it with the commonly used algorithms. Experimental results showed the optimum model was achieved by AdaBoost–BPANN algorithm with RMSEP = 7.7124 mg/100 g and R = 0.8915 in the prediction set. This work sufficiently demonstrated that the colorimetric sensors array has a high potential in non-destructive sensing chicken’s freshness, and AdaBoost-BPANN algorithm has a strong performance in solution to a complex data calibration.
... Metalloporphyrins have shown to be excellent candidates for the detection of amines, among other volatile organic compounds (VOCs), given their ability to interact with metal-ligating vapors [18][19][20][21]. In particular, metal-derivatives of tetraphenylporphyrin (TPP) have been used for amine sensing with satisfactory results [22,23]. ...
Article
In this work, we have used a tripodal porphyrin, 1,3-di[5-(3-hydroxyphenyl)-10,15,20-(triphenyl)porphyrin]-2-(5-(3-hydroxyphenyl)-10,15,20-(triphenyl) porphyrin)-2-methylpropane Zn(II) (ZnTriad), to detect amines through UV–vis spectroscopy. We have also compared ZnTriad to its single unit, Zn(II) 5,10,15,20-tetraphenylporphyrin (ZnTPP) to assess the influence of the branched structure on the molecular aggregation and sensing capabilities. The comparison between tripodal ZnTriad and monomeric ZnTPP has shown that this multiporphyrin system can reduce the aggregation of porphyrins in films prepared by spin coating. ZnTPP deposition on glass resulted in completely unusable films after less than 1 h from their preparation due to extreme aggregation, while ZnTriad showed excellent stability. The gas-sensing properties of ZnTriad films have been analyzed through their exposure to butylamine as testing gas, featuring intense and reversible spectral changes in the form of shift of their Soret band to longer wavelengths and increase of its maximum absorbance. The sensor also shows fast response and repeatability after consecutive exposure-recovery cycles. In order to test if the geometry of ZnTriad facilitates the selective detection of amines regarding their size and shape, we have chosen a total of five primary amines, being three of them linear or one-dimensional with increasing length (propylamine, butylamine and hexylamine), one planar or two-dimensional (aniline) and one three-dimensional (tert-butylamine). The exposure of ZnTriad films to these analytes has resulted in selective responses toward the amine vapors. The linear amines have produced the fastest and more intense spectral changes on ZnTriad films, followed by tert-butylamine and aniline. Overall, films made with ZnTriad have shown great stability, preventing porphyrin aggregation, and ability to discriminate amines regarding their size and/or shape. Therefore, this porphyrin would be an excellent candidate for its inclusion in multisensor arrays.