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The saltiness enhancement effect can be produced by adding specific substances to dietary salt (sodium chloride). This effect has been used in salt-reduced food to help people forge healthy eating habits. Therefore, it is necessary to objectively evaluate the saltiness of food based on this effect. In a previous study, sensor electrodes based on lipid/polymer membrane with Na+ ionophore have been proposed to quantify the saltiness enhanced by branched-chain amino acids (BCAAs), citric acid, and tartaric acid. In this study, we developed a new saltiness sensor with the lipid/polymer membrane to quantify the saltiness enhancement effect of quinine by replacing a lipid that caused an unexpected initial drop in the previous study with another new lipid. As a result, the concentrations of lipid and ionophore were optimized to produce an expected response. Logarithmic responses have been found on both NaCl samples and quinine-added NaCl samples. The findings indicate the usage of lipid/polymer membranes on novel taste sensors to evaluate the saltiness enhancement effect accurately.

Nowadays, the utilization of a taste sensor with lipid/polymer membranes is one of the most accurate and objective ways to evaluate the tastes of solutions. However, it has been difficult to evaluate uncharged sweet substances, such as sucrose, because the conventional taste sensor uses the potentiometric measurement, which is mainly based on changes in the surface electric charge density of the membrane. Previous studies have reported that a sweetness sensor called GL1 can evaluate the sweetness of sugars and sugar alcohols, and is commercially available for food, beverage, and pharmaceutical industries. However, the response mechanism of GL1 has not been fully elucidated. In this study, we focus on clarifying the effect of concentrations and types of metal ions in the conditioning solution on the response mechanism of the sweetness sensor GL1. Moreover, according to the different concentrations and types of metal ions in conditioning solutions, the complex formation and the hydrated radius were considered to influence the membrane potential measured in a reference solution and the sensor responses. The purpose of this study is to elucidate the response mechanism and improve the selectivity and sensitivity of the sweetness sensor.

A taste sensor with lipid/polymer membranes can objectively evaluate taste. As previously reported, caffeine can be detected electrically using lipid/polymer membranes modified with hydroxybenzoic acids (HBAs). However, a systematic understanding of how HBAs contribute to caffeine detection is still lacking. In this study, we used various HBAs such as 2,6–dihydroxybenzoic acid (2,6–DHBA) to modify lipid/polymer membranes, and we detected caffeine using a taste sensor with the modified membranes. The effect of the concentrations of the HBAs on caffeine detection was also discussed. The results of the caffeine detection indicated that the response to caffeine and the reference potential measured in a reference solution were affected by the log P and pKa of HBAs. Furthermore, the taste sensor displayed high sensitivity to caffeine when the reference potential was adjusted to an appropriate range by modification with 2,6–DHBA, where the slope of the change in reference potential with increasing 2,6–DHBA concentration was steep. This is helpful in order to improve the sensitivity of taste sensors to other taste substances, such as theophylline and theobromine, in the future.

The use of taste sensors with lipid/polymer membranes is one of the methods to evaluate taste. As previously reported, taste sensors can detect non-charged substances such as caffeine by modifying the lipid/polymer membranes with hydroxybenzoic acids (HBAs). The mechanism of caffeine detection by taste sensors was identified to be an allosteric one. Generally, the allosteric mechanism, defined as “regulation at distant sites”, is used to describe the regulation process for proteins. In this study, to improve the sensitivity of taste sensors to caffeine and its analogs using the allosteric mechanism, we used various modifiers of lipid/polymer membranes, and we detected caffeine using taste sensors with the modified membranes. The detection of the caffeine analogs theophylline and theobromine was also analyzed. The results of caffeine detection clarified that the molecular structure underlying the allosteric mechanism capable of effective caffeine detection involves both the carboxyl and hydroxyl groups, where the hydroxyl group can form intermolecular H bonds with caffeine. Furthermore, the taste sensors with a modifier, which has the molecular structure underlying the allosteric mechanism, showed high sensitivity to caffeine and caffeine analogs. The use of an allosteric mechanism may help improve the sensitivity of taste sensors to other non-charged pharmaceutical substances, such as dexamethasone and prednisolone, in the future.

Taste is of five basic types, namely, sourness, saltiness, sweetness, bitterness and umami. In this review, we focus on a potentiometric taste sensor that we developed and fabricated using lipid polymer membranes. The taste sensor can measure the taste perceived by humans and is called an electronic tongue with global selectivity, which is the property to discriminate taste qualities and quantify them without discriminating each chemical substance. This property is similar to the gustatory system; hence, the taste sensor is a type of biomimetic device. In this paper, we first explain the sensing mechanism of the taste sensor, its application to beer evaluation and the measurement mechanism. Second, results recently obtained are introduced; i.e., the application of the senor to high-potency sweeteners and the improvement of the bitterness sensor are explained. Last, quantification of the bitterness-masking effect of high-potency sweeteners is explained using a regression analysis based on both the outputs of bitterness and sweetness sensors. The taste sensor provides a biomimetic method different from conventional analytical methods.

The lipid phosphoric acid di-n-decyl ester (PADE) has played an important role in the development of taste sensors. As previously reported, however, the concentration of PADE and pH of the solution affected the dissociation of H+, which made the measurement results less accurate and stable. In addition, PADE caused deterioration in the response to bitterness because PADE created the acidic environment in the membrane. To solve these problems, our past study tried to replace the PADE with a completely dissociated substance called tetrakis [3,5-bis (trifluoromethyl) phenyl] borate sodium salt dehydrate (TFPB) as lipid. To find out whether the two substances can be effectively replaced, it is necessary to perform an in-depth study on the properties of the two membranes themselves. In this study, we fabricated two types of membrane electrodes, based on PADE or TFPB, respectively, using 2-nitrophenyl octyl ether (NPOE) as a plasticizer. We measured the selectivity to cations such as Cs+, K+, Na+ and Li+, and also the membrane impedance of the membranes comprising PADE or TFPB of the different concentrations. As a result, we found that any concentration of PADE membranes always had low ion selectivity, while the ion selectivity of TFPB membranes was concentration-dependent, showing increasing ion selectivity with the TFPB concentrations. The ion selectivity order was Cs+>K+>Na+>Li+. The hydration of ions was considered to participate in this phenomenon. In addition, the membrane impedance decreased with increasing PADE and TFPB concentrations, while the magnitudes differed, implying that there is a difference in the dissociation of the two substances. The obtained results will contribute to the development of novel receptive membranes of taste sensors.

An odor sensing system with chemosensitive resistors was used to identify the gases generated from overheated cables to prevent fire. Three different electric cables for a distribution cabinet were used. The cables had an insulation layer made of polyvinyl chloride (PVC) or cross-linked polyethylene (XLPE). The heat resistance of the cables was tested by differential thermal and thermogravimetric analyses. The thermal decomposition products of the cables were investigated by gas chromatography-mass spectrometry (GC-MS). For the odor sensing system, two types of 16-channel array were used to detect the generated gases. One contains high-polarity GC stationary phase materials and the other contains GC stationary phase materials of high to low polarity. The system could distinguish among three cable samples at 270 °C with an accuracy of about 75% through both arrays trained with machine learning. Furthermore, the system could achieve a recall rate of 90% and a precision rate of 70% when the abnormal temperature was set above the cables’ allowable conductor temperature at 130 °C. The odor sensing system could effectively detect the abnormal heating of the cables before the occurrence of fire. Therefore, it is helpful for fire prediction and detection systems in factories and substations.

Technologies for quantifying bitterness are essential for classifying medicines. As previously reported, taste sensors with lipid polymer membranes can respond to bitter hydrochloride substances in pharmaceuticals. However, the acid hydrolysis reaction between the lipid phosphoric acid di-n-decyl ester (PADE) and the plasticizer tributyl o-acetylcitrate (TDAB) led to a deterioration in sensor responses during storage. Given the cost of transportation and preservation for commercialization, membrane components that maintain physical and chemical stability during long-term storage are needed. Here we present a membrane electrode based on hydrophobic tetrakis [3,5-bis (trifluoromethyl) phenyl] borate (TFPB) and a plasticizer 2-nitrophenyl octyl ether (NPOE) for the quantification of pharmaceutical bitterness, they maintain a stable response before and after accelerated deterioration, as well as high selectivity and sensitivity. It is a first attempt to use a completely dissociative substance to replace non-completely dissociative lipids. Our work offsets the long-term stability issue of a bitterness sensor with a negatively charged hydrophobic membrane. Meanwhile, we provide the opportunity to select surface charge modifiers for a membrane surface using ester plasticizers containing oppositely charged impurities.

A taste sensor with lipid/polymer membranes is attracting attention as a method to evaluate taste objectively. However, due to the characteristic of detecting taste by changes in membrane potential, taste sensors cannot measure non-charged bitter substances. Many foods and medicines contain non-charged bitter substances, and it is necessary to quantify these tastes with sensors. Therefore, we have been developing taste sensors to detect bitter tastes caused by non-charged substances such as caffeine. In previous studies, a sensor for detecting bitterness caused by caffeine and theobromine, theophylline, was developed, using a membrane modified with hydroxybenzoic acid (HBA) as the sensing part. The sensor was designed to form intramolecular hydrogen bonds (H-bonds) between the hydroxy group and carboxy group of HBA and to successively cause the intermolecular H-bonds between HBA and caffeine molecules to be measured. However, whether this sensing principle is correct or not cannot be confirmed from the results of taste sensor measurements. Therefore, in this study, we explored the interaction between HBA and caffeine by 1H-nuclear magnetic resonance spectroscopy (NMR). By the 1H NMR detection, we confirmed that both the substances interact with each other. Furthermore, the nuclear Overhauser effect (NOE) of intermolecular spatial conformation in solution was measured, by which 2,6-dihydroxybenzoic acid (2,6-DHBA) preferably interacted with caffeine via the H-bonding and stacking configuration between aromatic rings. Identifying the binding form of 2,6-DHBA to caffeine was estimated to predict how the two substances interact.

A taste sensor with lipid/polymer membranes is one of the devices that can evaluate taste objectively. However, the conventional taste sensor cannot measure non-charged bitter substances, such as caffeine contained in coffee, because the taste sensor uses the potentiometric measurement based mainly on change in surface electric charge density of the membrane. In this study, we aimed at the detection of typical non-charged bitter substances such as caffeine, theophylline and theobromine included in beverages and pharmaceutical products. The developed sensor is designed to detect the change in the membrane potential by using a kind of allosteric mechanism of breaking an intramolecular hydrogen bond between the carboxy group and hydroxy group of aromatic carboxylic acid (i.e., hydroxy-, dihydroxy-, and trihydroxybenzoic acids) when non-charged bitter substances are bound to the hydroxy group. As a result of surface modification by immersing the sensor electrode in a modification solution in which 2,6-dihydroxybenzoic acid was dissolved, it was confirmed that the sensor response increased with the concentration of caffeine as well as allied substances. The threshold and increase tendency were consistent with those of human senses. The detection mechanism is discussed by taking into account intramolecular and intermolecular hydrogen bonds, which cause allostery. These findings suggest that it is possible to evaluate bitterness caused by non-charged bitter substances objectively by using the taste sensor with allosteric mechanism.

In this study, we were challenging to identify characteristic compounds in breast cancer cell lines. GC analysis of extracts from the culture media of breast cancer cell lines (MCF-7, SK-BR-3, and YMB-1) using a solid-phase Porapak Q extraction revealed that two compounds of moderate volatility, 1-hexadecanol and 5-(Z)-dodecenoic acid, were detected with markedly higher amount than those in the medium of fibroblast cell line (KMST-6). Furthermore, LC-TOF/MS analysis of the extracts clarified that in addition to the above two fatty acids, the amounts of five unsaturated fatty acids [decenoic acid (C10:1), decadienoic acid (C10:2), 5-(Z)-dodecenoic acid (C12:1), 5-(Z)-tetradecenoic acid (C14:1), and tetradecadienoic acid (C14:2)] in MCF-7 medium were higher than those in medium of KMST-6. Interestingly, H2O2-oxidation of 5-(Z)-dodecenoic acid and 5-(Z)-tetradecenoic acid produced volatile aldehydes that were reported as specific volatiles in breath from various cancer patients, such as heptanal, octanal, nonanal, decanal, 2-(E)-nonenal, and 2-(E)-octenal. Thus, we concluded that these identified compounds over-produced in breast cancer cells in this study could serve as potential precursors producing reported cancer-specific volatiles.

We have developed a method to quantify the sweetness of negatively charged high-potency sweeteners coexisting with other taste substances. This kind of sweetness sensor uses lipid polymer membranes as the taste-sensing part. Two types of outputs have been defined in the measurement of the taste sensor: one is the relative value and the other is the CPA (the change in membrane potential caused by adsorption) value. The CPA value shows a good selectivity for high-potency sweeteners. On the other hand, the relative value is several times higher than the CPA value, but the relative value is influenced by salty substances. In order to obtain both high sensitivity and selectivity, we established a model for predicting the concentration of sweeteners with a nonlinear regression analysis method using the relative values of both the sweetness sensor and the saltiness sensor. The analysis results showed good correlations with the estimated concentration of acesulfame potassium coexisting with salty substances, as represented by R2 = 0.99. This model can correspond well to the prediction of acesulfame K in a concentration of 0.2&ndash, 0.7 mM, which is commonly used in food and beverages. The results obtained in this paper suggest that this method is useful for the evaluation of acesulfame K using the taste sensors.

In this study, we developed a surface plasmon resonance (SPR) sensor chip based on 2,4,6-trinitrotoluene (TNT) recognition peptide-modified single-walled carbon nanotubes (SWCNTs). The carboxylic acid-functionalized SWCNTs were immobilized on a 3-aminopropyltriethoxysilane (APTES)-modified SPR Au chip surface. Through &pi, stacking between the aromatic amino acids and SWCNTs, the TNT recognition peptide TNTHCDR3 was immobilized onto the surface of the SWCNTs. The peptide&ndash, SWCNTs-modified sensor surface was confirmed and evaluated by atomic force microscope (AFM) observation. The peptide&ndash, SWCNTs hybrid SPR sensor chip exhibited enhanced sensitivity with a limit of detection (LOD) of 772 ppb and highly selective detection compared with commercialized carboxymethylated dextran matrix sensor chips.

We investigated the bitter compounds in coffee brews using multivariate analysis of the data obtained from analytical instrument and electronic taste sensor experiments. Coffee brews were prepared from coffee beans roasted to four different degrees. Each brew was fractionated into four fractions by liquid-liquid extraction. The relative amounts of 30 compounds in each fraction were analyzed by analytical instruments, and the bitterness response value of each fraction was analyzed by a taste sensor. Candidate bitter compounds in the coffee brews were identified with reference to their variable importance in projection and by coefficient of projection to latent structure regression (PLS-R) analysis. PLS-R analysis suggested that nicotinic acid, l-lactic acid, and nicotinamide contributed to the bitterness of the coffee brews. In fact, the coffee brews with added nicotinic acid, l-lactic acid, and nicotinamide had an increased bitterness response value compared to those without.

The saltiness enhancement effect is the effect whereby saltiness is enhanced by adding specific substances to salt (sodium chloride). Since this effect can be used in the development of salt-reduced foods, a method to objectively evaluate the saltiness with this effect is required. A taste sensor with lipid/polymer membranes has been used to quantify the taste of food and beverages in recent years. The sensor electrodes of this taste sensor have the feature of selectively responding to each of the five basic tastes, which is realized by the lipid/polymer membranes. In this study, we developed a new saltiness sensor based on the lipid/polymer membrane with the aim of quantifying the saltiness enhancement effect. In addition to the conventional components of a lipid, plasticizer, and polymer supporting reagent, the membrane we developed comprises ionophores, which selectively capture sodium ions. As a result, the response of the sensor increased logarithmically with the activity of NaCl in measured samples, similarly to the taste response of humans. In addition, all of the sensor responses increased upon adding saltiness-enhancing substances, such as citric acid, tartaric acid and branched-chain amino acids (BCAAs), to NaCl samples. These findings suggest that it is possible to quantify the saltiness enhancement effect using a taste sensor with lipid/polymer membranes.

This paper reports the improvement of a bitterness sensor based on a lipid polymer membrane consisting of phosphoric acid di-n-decyl ester (PADE) as a lipid and bis(1-butylpentyl) adipate (BBPA) and tributyl o-acetylcitrate (TBAC) as plasticizers. Although the commercialized bitterness sensor (BT0) has high sensitivity and selectivity to the bitterness of medicines, the sensor response gradually decreases to almost zero after two years at room temperature and humidity in a laboratory. To reveal the reason for the deterioration of the response, we investigated sensor membranes by measuring the membrane potential, contact angle, and adsorption amount, as well as by performing gas chromatography-mass spectrometry (GC-MS), liquid chromatography-tandem mass spectrometry (LC-MS/MS). We found that the change in the surface charge density caused by the hydrolysis of TBAC led to the deterioration of the response. The acidic environment generated by PADE promoted TBAC hydrolysis. Finally, we succeeded in fabricating a new membrane for sensing the bitterness of medicines with higher durability and sensitivity by adjusting the proportions of the lipid and plasticizers.

In this study, a rationally-designed 2,4,6-trinitrotoluene (TNT) binding peptide derived from an amino acid sequence of the complementarity-determining region (CDR) of an anti-TNT monoclonal antibody was used for TNT detection based on a maleimide-functionalized surface plasmon resonance (SPR) sensor. By antigen-docking simulation and screening, the TNT binding candidate peptides were obtained as TNTHCDR1 derived from the heavy chain of CDR1, TNTHCDR2 derived from CDR2, and TNTHCDR3 from CDR3 of an anti-TNT antibody. The binding events between candidate peptides and TNT were evaluated using the SPR sensor by direct determination based on the 3-aminopropyltriethoxysilane (APTES) surface. The TNT binding peptide was directly immobilized on the maleimide-functionalized sensor chip surface from N-γ-maleimidobutyryl-oxysuccinimide ester (GMBS). The results demonstrated that peptide TNTHCDR3 was identified and selected as a TNT binding peptide among the other two candidate peptides. Five kinds of TNT analogues were also investigated to testify the selectivity of TNT binding peptide TNTHCDR3. Furthermore, the results indicated that the APTES-GMBS-based SPR sensor chip procedure featured a great potential application for the direct detection of TNT.

The detection and recognition of metabolically derived aldehydes, which have been identified as important products of oxidative stress and biomarkers of cancers; are considered as an effective approach for early cancer detection as well as health status monitoring. Quartz crystal microbalance (QCM) sensor arrays based on molecularly imprinted sol-gel (MISG) materials were developed in this work for highly sensitive detection and highly selective recognition of typical aldehyde vapors including hexanal (HAL); nonanal (NAL) and bezaldehyde (BAL). The MISGs were prepared by a sol-gel procedure using two matrix precursors: tetraethyl orthosilicate (TEOS) and tetrabutoxytitanium (TBOT). Aminopropyltriethoxysilane (APT); diethylaminopropyltrimethoxysilane (EAP) and trimethoxy-phenylsilane (TMP) were added as functional monomers to adjust the imprinting effect of the matrix. Hexanoic acid (HA); nonanoic acid (NA) and benzoic acid (BA) were used as psuedotemplates in view of their analogous structure to the target molecules as well as the strong hydrogen-bonding interaction with the matrix. Totally 13 types of MISGs with different components were prepared and coated on QCM electrodes by spin coating. Their sensing characters towards the three aldehyde vapors with different concentrations were investigated qualitatively. The results demonstrated that the response of individual sensors to each target strongly depended on the matrix precursors; functional monomers and template molecules. An optimization of the 13 MISG materials was carried out based on statistical analysis such as principle component analysis (PCA); multivariate analysis of covariance (MANCOVA) and hierarchical cluster analysis (HCA). The optimized sensor array consisting of five channels showed a high discrimination ability on the aldehyde vapors; which was confirmed by quantitative comparison with a randomly selected array. It was suggested that both the molecularly imprinting (MIP) effect and the matrix effect contributed to the sensitivity and selectivity of the optimized sensor array. The developed MISGs were expected to be promising materials for the detection and recognition of volatile aldehydes contained in exhaled breath or human body odor.

This review describes an “electronic dog nose” based on a surface plasmon resonance (SPR) sensor and an antigen–antibody interaction for security and safety. We have concentrated on developing appropriate sensor surfaces for the SPR sensor for practical use. The review covers different surface fabrications, which all include variations of a self-assembled monolayer containing oligo(ethylene glycol), dendrimer, and hydrophilic polymer. We have carried out detection of explosives using the sensor surfaces. For the SPR sensor to detect explosives, the vapor or particles of the target substances have to be dissolved in a liquid. Therefore, we also review the development of sampling processes for explosives, and a protocol for the measurement of explosives on the SPR sensor in the field. Additionally, sensing elements, which have the potential to be applied for the electronic dog nose, are described.

Taste evaluation technology has been developed by several methods, such as sensory tests, electronic tongues and a taste sensor based on lipid/polymer membranes. In particular, the taste sensor can individually quantify five basic tastes without multivariate analysis. However, it has proven difficult to develop a sweetness sensor, because sweeteners are classified into three types according to the electric charges in an aqueous solution; that is, no charge, negative charge and positive charge. Using membrane potential measurements, the taste-sensing system needs three types of sensor membrane for each electric charge type of sweetener. Since the commercially available sweetness sensor was only intended for uncharged sweeteners, a sweetness sensor for positively charged high-potency sweeteners such as aspartame was developed in this study. Using a lipid and plasticizers, we fabricated various lipid/polymer membranes for the sweetness sensor to identify the suitable components of the sensor membranes. As a result, one of the developed sensors showed responses of more than 20 mV to 10 mM aspartame and less than 5 mV to any other taste. The responses of the sensor depended on the concentration of aspartame. These results suggested that the developed sweetness sensor had high sensitivity to and high selectivity for aspartame.

Recently, highly functional biosensors have been developed in preparation for possible large-scale terrorist attacks using chemical warfare agents. Practically applicable sensors are required to have various abilities, such as high portability and operability, the capability of performing rapid and continuous measurement, as well as high sensitivity and selectivity. We developed the detection method of capsaicinoids, the main component of some lachrymators, using a surface plasmon resonance (SPR) immunosensor as an on-site detection sensor. Homovanillic acid, which has a vanillyl group similar to capsaicinoids such as capsaicin and dihydrocapsaicin, was bound to Concholepas concholepas hemocyanin (CCH) for use as an immunogen to generate polyclonal antibodies. An indirect competitive assay was carried out to detect capsaicinoids using SPR sensor chips on which different capsaicin analogues were immobilized. For the sensor chip on which 4-hydroxy-3-methoxybenzylamine hydrochloride was immobilized, a detection limit of 150 ppb was achieved. We found that the incubation time was not required and the detection can be completed in five minutes.

In this study, we modified a surface plasmon resonance immunosensor chip with a polymer using surface-initiated atom transfer polymerization (SI-ATRP) for the highly sensitive detection of 2,4,6-trinitrotoluene (TNT). To immobilize a TNT analogue on the polymer, mono-2-(methacryloyloxy)ethylsuccinate (MES), which has a carboxyl group, was used in this study. However, the anti-TNT antibody may adsorb non-specifically on the polymer surface by an electrostatic interaction because MES is negatively charged. Therefore, a mixed monomer with MES and diethylaminoethylmethacrylate (DEAEM), which has a tertiary amino group and is positively charged, was prepared to obtain electroneutrality for suppressing the nonspecific adsorption. The detection of TNT was performed by inhibition assay using the polymer surface. To ensure high sensitivity to TNT, the affinity between the surface and the antibody was optimized by controlling the density of the initiator for ATRP by mixing two types of self-assembled monolayer reagents. As a result, a limit of detection of 5.7 pg/mL (ppt) for TNT was achieved using the optimized surface.

A highly sensitive and fast method for electrochemical detection of 2,3-dimethyldinitrobutane (DMNB) on a graphite working electrode modified with a TiO2 thin film including single-walled carbon nanotubes (SWCNTs) is proposed. Incorporation of the SWCNTs into the inorganic matrix allowed the preparation of a highly stable film with an integrated electrochemical chip. The sensing mechanism is based on the current change generated at the specific voltage due to the redox reaction of the DMNB NO2 functional group. The detection limit and sensitivity were significantly improved due to the interaction between the SWCNTs and the analyte, which considerably enhanced the electron transferability. Under the optimized conditions, the linear range of the DMNB detection was 10 ppb to 10 ppm with a detection limit of 12 ppb, showing a sensitivity of 61 nA ppb -1 .

The current study demonstrated that theasinensin A (TSA) had a potential to form the complex with hydrophobic Trp-containing dipeptides, and to reduce their membrane potential by artificial-lipid membrane taste sensor. At a 1:3 molar ratio of the 6 Trp-containing dipeptides together with TSA, we observed a significant chemical shift of the protons of the dipeptides (Δδ) to a high magnetic field, when analyzed using 1H-nuclear-magnetic resonance (NMR) spectroscopy. The Δδ values were correlated with the hydrophobicity (log P) of the dipeptides and significant correlations were obtained (P = 0.022, R2 = 0.77); e.g., Trp-Leu with the highest log P value of 1.623 among the tested dipeptides showed the highest Δδ value of 0.105 ppm for the H7 proton of Trp-Leu, while less chemical shifts were observed in theasinensin B and epigallocatechin-3-O-gallate. Diffusion-ordered NMR spectroscopy revealed that the diffusion coefficient of 3 mM of Trp-Leu (7.6 × 10−11 m2/s) at a pulse field gradient in the range 0.05–0.3 T/m decreased in the presence of 3 mM TSA (6.6 × 10−11 m2/s), suggesting that Trp-Leu forms a complex with TSA. Quantum mechanical calculations and rotating frame nuclear Overhauser effect-NMR spectroscopy provided configuration information on the geometry of the complex that Trp-Leu formed with TSA (1:1 complex) with a ΔG energy of –8.7 kJ/mol. A sensor analysis using artificial-lipid membranes demonstrated that the changes in membrane potential of 1 mM Trp-Leu (21.8 ± 1.3 mV) and Leu-Trp (5.3 ± 0.9 mV) were significantly (P < 0.001) reduced by 1 mM TSA (Trp-Leu, 13.1 ± 2.4 mV; Leu-Trp, 3.5 ± 0.5 mV; TSA alone, 0.2 ± 0.01 mV), indicating the effective suppression of hydrophobicity of dipeptides by TSA-formed complex.

Effective R&D and strict quality control of a broad range of foods, beverages, and pharmaceutical products require objective taste evaluation. Advanced taste sensors using artificial-lipid membranes have been developed based on concepts of global selectivity and high correlation with human sensory score. These sensors respond similarly to similar basic tastes, which they quantify with high correlations to sensory score. Using these unique properties, these sensors can quantify the basic tastes of saltiness, sourness, bitterness, umami, astringency and richness without multivariate analysis or artificial neural networks. This review describes all aspects of these taste sensors based on artificial lipid, ranging from the response principle and optimal design methods to applications in the food, beverage, and pharmaceutical markets.

Quartz crystal microbalance (QCM) gas sensors based on the alternate adsorption of TiO(2) and polyacrilic acid (PAA) were developed for the sensitive detection of amine odors. Individual TiO(2) gel layers could be regularly assembled with a thickness of approximately 0.3 nm by the gas-phase surface sol-gel process (GSSG). The thickness of the poly(acrylic acid) (PAA) layer is dependent on its molecular weight, showing different thicknesses of approximately 0.4 nm for PAA(25) (Mw 250,000) and 0.6-0.8 nm for PAA(400) (Mw 4,000,000). The QCM sensors showed a linear response to ammonia in the concentration range 0.3-15 ppm, depending on the deposition cycle of the alternate TiO(2)/PAA layer. The ammonia binding is based on the acid-base interaction to the free carboxylic acid groups of PAA and the limit of detection (LOD) of the 20-cycle TiO(2)/PAA(400) film was estimated to be 0.1 ppm when exposed to ammonia. The sensor response was very fast and stable in a wide relative humidity (rH) range of 30-70%, showing almost the same frequency changes at a given concentration of ammonia. Sensitivity to n-butylamine and ammonia was higher than to pyridine, which is owing to the difference of molecular weight and basicity of the amine analytes. The alternate TiO(2)/PAA(400) films have a highly effective ability to capture amine odors, and the ambient ammonia concentration of 15 ppm could be condensed up to approximately 20,000 ppm inside the films.

A surface plasmon resonance (SPR) immunosensor for detection of 2,4-dinitrotoluene (2,4-DNT), which is a signature compound of 2,4,6-trinitrotoluene-related explosives, was developed by using a novel oligo (ethylene glycol) (OEG)-based sensor surface. A rabbit polyclonal antibody against 2,4-DNT (anti-DNPh-KLH-400 antibody) was prepared, and the avidity for 2,4-DNT and recognition capability were investigated by indirect competitive ELISA. The sensor surface was fabricated by immobilizing a 2,4-DNT analog onto an OEG-based self-assembled monolayer formed on a gold surface via an OEG linker. The fabricated surface was characterized by Fourier-transform infrared-refractive absorption spectrometry (FTIR-RAS). The immunosensing of 2,4-DNT is based on the indirect competitive principle, in which the immunoreaction between the anti-DNPh-KLH-400 antibody and 2,4-DNT on the sensor surface was inhibited in the presence of free 2,4-DNT in solution. The limit of detection for the immunosensor, calculated as three times the standard deviation of a blank value, was 20 pg mL(-1), and the linear dynamic range was found to be between 1 and 100 ng mL(-1). Additionally, the fabricated OEG-based surface effectively prevented non-specific adsorption of proteins, and the specific response to anti-DNPh-KLH-400 antibody was maintained for more than 30 measurement cycles.

In order to develop the fully integrated portable surface plasmon resonance (SPR) system for detection of explosives, the amplification strategy of SPR signal was investigated. Indirect competitive inhibition method allowed the middle-sized SPR sensor to detect trinitrotoluene (TNT) at ppt level. However, this enhanced SPR signal was not high enough to detect TNT at ppt level by a miniaturized SPR sensor. Therefore, localized surface plasmon resonance (LSPR) effect using Au nanoparticle as further signal amplification approach was used. The amplification method of indirect competitive inhibition and LSPR were combined together for fabrication of the immunosurface using Au nanoparticle. TNT detectable range of this immunosurface was from 10 ppt (10 pg/ml) to 100 ppb (100 ng/ml), which was almost comparable to that without Au nanoparticle. The observed resonance angle change due to binding monoclonal TNT antibody (M-TNT Ab) with the immunosurface modified with Au nanoparticle was amplified to four times higher than that in absence of Au nanoparticle.

A biological olfaction system is one of the highest performance chemical sensing systems for low-molecular-weight compounds. An ability of recognizing a various molecular properties based on their structures is essential for a biological odor recognition process. For the development of a sensor mimicking the olfactory system, we have formed benzene-patterned self-assembled monolayer (SAM) on the sensor surface using SAMs with nanostructure that serves as adsorption sites for benzene ring, which is representative substructure of aromatics. The structure of the benzene-patterned SAM surface was analyzed by contact-angle measurement, ellipsometry, cyclic voltammetry (CV) and atomic force microscopy (AFM). Moreover, the electrodes evaluated as sensor surfaces with cyclic surface-polarization impedance (cSPI) sensor that measures changes in impedance of the electrode surface by adsorption of substances. The results of cSPI indicated the benzene-patterned SAM surface could distinguish benzene by recognizing of the hydrophobicity and the molecular size.

Recent concern on international terrorism and weapons of mass destruction demands the development of novel analytical methods for identification and quantification of explosive molecules. In this article, we describe the development of high-performance immunosensors for detection of 2,4,6-trinitrotoluene (TNT), a prime component of the landmines and bombs used by terrorist and military forces. The immunosensors were constructed by physical adsorption and self-assembly methods, and their binding interactions with a monoclonal anti-TNT antibody were evaluated for TNT detection using the surface plasmon resonance technique. A home-made 2,4,6-trinitrophenyl-keyhole limpet hemocyanine conjugate was used for physical adsorption. A poly(ethylene glycol) hydrazine hydrochloride thiolate was used in the construction of self-assembled monolayer surface and was immobilized with trinitrophenyl-β-alanine by the amide coupling method. The immunosensors were highly selective, regenerable, rapid, and exhibited remarkable...

It is possible to evaluate the taste of foods or medicines using a taste sensor. The taste sensor converts information on taste into an electrical signal using several lipid/polymer membranes. A lipid/polymer membrane for bitterness sensing can evaluate aftertaste after immersion in monosodium glutamate (MSG), which is called "preconditioning". However, we have not yet analyzed the change in the surface structure of the membrane as a result of preconditioning. Thus, we analyzed the change in the surface by performing contact angle and surface zeta potential measurements, Fourier transform infrared spectroscopy (FTIR), X-ray photon spectroscopy (XPS) and gas cluster ion beam time-of-flight secondary ion mass spectrometry (GCIB-TOF-SIMS). After preconditioning, the concentrations of MSG and tetradodecylammonium bromide (TDAB), contained in the lipid membrane were found to be higher in the surface region than in the bulk region. The effect of preconditioning was revealed by the above analysis methods.

In this study, we report the sensitive detection of aromatic nitro compounds using a surface plasmon resonance (SPR) immunosensor based on the indirect competitive method. The vapors from the substances were sampled with a preconcentrator developed here. The solutions of the sampled vapors were measured using SPR immunosensor. Three kinds of explosives such as 2,4-dinitrobenzene, 2,4-dinitrotoluene, and 2,4,6-trinitrotoluene were detected at 1 ppb. Sampling time at 1 l/min was 3 min. Total detection time was brought down to 5 min, which is relatively short for second scanning in landmine detection. Efforts are being made to integrate the SPR immunosensor and preconcentrator for rapid sensitive detection of nitro aromatic compounds under simulated field conditions.

A taste sensor using lipid-polymer membranes has been developed to evaluate the taste of foods, beverages and medicines. The response of the taste sensor, measured as a change in the membrane potential caused by adsorption (CPA), corresponds to the aftertaste felt by humans. The relationships between the CPA value and the amount of adsorbed taste substances, quinine and iso-α acid (bitterness), and tannic acid (astringency), have been studied so far. However, that of epigallocatechin gallate (EGCg) has not been clarified, although EGCg is abundantly present in green tea as one of its astringent substances. This study aimed at clarifying the response of the taste sensor to EGCg and its relationship with the amount of EGCg adsorbed onto lipid-polymer membranes. The lipid concentration dependence of the CPA value was similar to that of the amount of adsorbed EGCg, indicating a high correlation between the CPA value and the amount of adsorbed EGCg. The CPA value increased with increasing amount of adsorbed EGCg, however, the CPA value showed a tendency of leveling off when the amount of adsorbed EGCg further increased.

A surface plasmon resonance (SPR) immunosensor based on a competitive immunoreaction for the determination of trinitrophenol (TNP) is described. A goat anti-mouse IgG (1st antibody), which recognizes an Fc moiety of an antibody, was immobilized on a gold film of an SPR sensor chip by physical adsorption. A TNP solution containing a fixed concentration of a mouse anti-TNP monoclonal antibody (2nd antibody) and a TNP-keyhole limpet hemocyanin (KLH) conjugate was incubated in one-pot and introduced into the sensor chip. The TNP-KLH conjugate competes with TNP for binding with the 2nd antibody. The resulting complex of the 2nd antibody with the TNP-KLH conjugate was bound to the 1st antibody, which is immobilized on the sensor chip. The SPR sensor signal based on resonance angle shift is dependent on the concentration of TNP in the incubation solution in the range from 25 ppt to 25 ppb, and the coefficient of variation of the SPR signals for the 25 ppb TNP solution was determined to be 13% (n = 4). The experimental results for the adsorption constant of the 1st antibody on the sensor chip and the binding constant of the 1st antibody complex with the 2nd antibody are discussed, together with theoretical considerations.

A surface plasmon resonance (SPR) immunosensor for the determination of 2,4,6-trinitrotoluene (TNT) has been developed based on the principle of indirect competitive immunoreaction. 2,4,6-trinitrophenol-bovine serum albumin (TNP-BSA) conjugate was immobilized onto a SPR gold chip by means of simple physical adsorption. Binding of anti-TNP antibody with TNP-BSA conjugate was detected based on an increase in resonance angle due to antigen-antibody interaction. Preincubation of anti-TNP antibody with TNT suppresses its interaction with immobilized TNP-BSA conjugate, which leads to a decrease in resonance angle shift. Following the dependence of the resonance angle shift, concentration of TNT was detected. Pepsin solution was used for the regeneration of the sensing surface. The response time for TNT measurement is about 22 min. The immunosensor showed excellent sensitivity to TNT in a wide concentration range from 60 ppt to 1000 ppb with good selectivity, stability, and reproducibility. The proposed system is promising for future application for the on-site detection of landmines.

We have examined the sensing characteristics of a surface plasmon resonance (SPR) immunoassay for the detection of 2,4,6-trinitrotoluene (TNT) using an immunoreaction between 2,4,6-trinitrophenol-ovalbumin (TNP-OVA) conjugate and anti-2,4,6-trinitrophenol antibody (anti-TNP antibody). TNP-OVA conjugate was attached to a SPR-gold sensing surface by means of physical immobilization, which undergoes binding interaction with anti-TNP antibody. Both the immobilization and binding processes were studied from a change in the SPR-resonance angle. The quantification of TNT is based on the principle of indirect competitive immunoassay, in which the immunoreaction between the TNP-OVA conjugate and anti-TNP antibody was inhibited in the presence of free TNT in solution. The decrease in the resonance angle shift is proportional to an increase in concentration of TNT used for incubation. The immunoassay exhibited excellent sensitivity for the detection of TNT in the concentration range from 0.09 to 1000 ng/ml with good stability and reproducibility. The immunosensor developed could detect TNT as low as 0.09 ng/ml, within a response time of approximately 22 min. The sensor surface was regenerated by a brief flow of pepsin solution, which disrupts the antigen-antibody complex without destroying the conjugate biofilm. Cross-reactivity of the SPR sensor to some structurally related nitroaromatic derivative and the detection of TNT in the presence of these nitroaromatic compounds were investigated. The cross-reactivity of the SPR sensor to 2,4-dinitrotoluene (2,4-DNT), 1,3-dinitrobenzene (1,3-DNB), 2-amino-4,6-dinitrotoluene (2A-4,6-DNT) and 4-amino-2,6-dinitrotoluene (4A-2,6-DNT) were very low (or =1.1%). The analytical characteristics of the proposed immunosensor are highly promising for the development of new field-portable sensors for on-site detection of landmines.

A novel odor sensing system which imitates the process of reception of odorants in biological olfactory system had been developed, utilizing surface polarity controlling method as a transducer of the sensor. In biological system, odorants are received by a large number of receptors, which recognize not whole structures but partial structures of molecules. The present sensor responded partial structures of odorants and adsorption interaction of the partial structures were controlled by the surface polarity of the electrode. Sensor output signals were analyzed on the stand point of partial structures of odorants. As a result, the responses to alcohols, aromatic compounds and aromatic alcohols as odorants could be discriminated by similar molecular structures, with principal component analysis (PCA). In addition, regression models of the response to partial structures of odorants were developed by multiple regression analysis, and odor qualities of aromatic alcohols could be evaluated quantitatively by partial structures of odor molecules.

Mimicking the biological olfaction, large odor-sensor arrays can be used to acquire a broad range of chemical information, with a potentially high degree of redundancy, to allow for enhanced control over the sensitivity and selectivity of artificial olfaction systems. The arrays should consist of the largest possible number of individual sensing elements while being miniaturized. Chemosensitive resistors are one of the sensing platforms that have a potential to satisfy these two conditions. In this work we test viability of fabricating a 16-element chemosensitive resistor array for detection and recognition of volatile organic compounds (VOCs). The sensors were fabricated using blends of carbon black and gas chromatography (GC) stationary-phase materials preselected based on their sorption properties. Blends of the selected GC materials with carbon black particles were subsequently coated over chemosensitive resistor devices and the resulting sensors/arrays evaluated in exposure experiments against vapors of pyrrole, benzenal, nonanal, and 2-phenethylamine at 150, 300, 450, and 900 ppb. Responses of the fabricated 16-element array were stable and differed for each individual odorant sample, proving the blends of GC materials with carbon black particles can be effectively used for fabrication of large odor-sensing arrays based on chemosensitive resistors. The obtained results suggest that the proposed sensing devices could be effective in discriminating odor/vapor samples at the sub-ppm level.

The bitterness of bitter substances can be measured by the change in the membrane electric potential caused by adsorption (CPA) using a taste sensor (electronic tongue). In this study, we examined the relationship between the CPA value due to an acidic bitter substance and the amount of the bitter substance adsorbed onto lipid/polymer membranes, which contain different lipid contents, used in the taste sensor. We used iso-α-acid which is an acidic bitter substance found in several foods and beverages. The amount of adsorbed iso-α-acid, which was determined by spectroscopy, showed a maximum at the lipid concentration 0.1 wt % of the membrane, and the same phenomenon was observed for the CPA value. At the higher lipid concentration, however, the amount adsorbed decreased and then remained constant, while the CPA value decreased monotonically to zero. This constant adsorption amount was observed when the membrane potential in the reference solution did not change with increasing lipid concentration. The decrease in CPA value in spite of the constant adsorption amount is caused by a decrease in the sensitivity of the membrane as the surface charge density increases. The reason why the peaks appeared in both the CPA value and adsorption amount is based on the contradictory adsorption properties of iso-α-acid. The increasing charged lipid concentration of the membrane causes an increasing electrostatic attractive interaction between iso-α-acid and the membrane, but simultaneously causes a decreasing hydrophobic interaction that results in decreasing adsorption of iso-α-acid, which also has hydrophobic properties, onto the membrane. Estimates of the amount of adsorption suggest that iso-α-acid molecules are adsorbed onto both the surface and interior of the membrane.

This paper describes an application of taste sensor for detection of cyanide. The taste sensor consists of multichannel sensors with lipid membranes which are modeled on living organisms. One of characteristics of this sensor is a global selectivity. In this study, we have developed a new effective method which is able to control the charge of membranes for high sensitivity and selectivity of lipid membrane sensors. Using this method, sensors for free cyanide and complex cyanide were developed. We could detect total cyanide under the guideline limit. It was possible to detect free cyanide below the concentration 0.5ppm in river water. Measurement time is within five minutes. In conclusion, the taste sensor has a very powerful performance and advantage for real time monitoring of water quality.

The taste sensor showed a similar pattern for chemical substances producing the same taste qualities, while quite different patterns were obtained for substances with different taste qualities. In fact, similar outputs were obtained for, e.g., NaCl, KCl and KBr eliciting saltiness, whereas their patterns differed clearly from those for other basic taste qualities. The taste of amino acids was also classied into several groups in accordance with the human taste sense. The taste sensor has a new concept of global selectivity. What is important in recognition of taste is not discrimination of minute difference in molecules but to transform molecular information contained in interactions with biological membranes into several kinds of groups, i.e., taste intensities and qualities. This function is of a high level, where intelligent sensing is required. In this sense, the taste sensor is essentially an intelligent sensor to reproduce the taste sense, which is a complex, comprehensive sense of humans. Several kinds of commercial drinks such as coffee, beer and mineral water were discriminated easily using the taste sensor. The taste sensor has a sensitivity, reproducibility and durability higher than those of humans. Human taste expressions such as ‘bitterness’ and ‘sourness’ were quantied, and also the physico-chemical indices for food production such as alcohol concentration and titratable acidity were shown to be measured by the taste sensor. Improvements in the membranes and measurement methods have also been made for the purpose of measurements, e.g., by adopting the Langmuir�Blodgett method [38], a monolayer of thiol-containing lipids [39] or impedance measurements [40]. The taste sensor will be applicable for quality control in the food industry and will help the automation of production. The sense of taste is vague and largely depends on subjective factors of human feelings. If we compare the standard index measured by means of the taste sensor with sensory evaluation, we will be able to assess taste objectively. Moreover, the mechanism of information processing of taste in the brain as well as the reception at taste cells will also be claried by developing a taste sensor which has output similar to that of the biological gustatory system. In fact, a recent study [19] has shown that astringency is a taste expressed by bitterness and sourness, whereas astringency has so far been considered not as a taste sense but a tactile sense. The result using the taste sensor indicates that the reception mechanism of taste substances in biological systems should be reconsidered. Objective scales of physical quantities such as length and time were proposed over two thousand years ago. We are now familiar with quantitative, objective scales, although there exists subjective feeling as well. As for taste, however, we have had no scale so far. The taste sensor provides a quantitative, objective measure of taste. ‘Deliciousness’ will be measured simultaneously using other sensors. Excellent odor or gas sensing systems based on various principles have also been developed [41—47]. We are now standing on the threshold of a new age of food culture.

Taste can be quantified using a multichannel taste sensor with lipid/polymer membranes. Its sensitivity and stability are superior to those of humans. A present study is concerned with the first step of miniaturization and integration of the taste sensor with lipid/polymer membranes using FET. As a result, it was found that gate-source voltage of the taste sensing FET showed the same behaviours as the conventional taste sensor utilizing the membrane-potential change due to five kinds of taste substances. Discrimination of foodstuffs was very easy. A thin lipid membrane formed using LB technique was also tried. These results will open doors to fabrication of a miniaturized, integrated taste sensing system.

We have developed a new portable taste sensor with a lipid/polymer membrane and conducted experiments to evaluate the sensor’s performance. The fabricated sensor consists of a taste sensor chip (40 mm × 26 mm × 2.2 mm) with working and reference electrodes and a portable sensor device (80 mm × 25 mm × 20 mm). The working electrode consists of a taste-sensing site comprising a poly(hydroxyethyl)methacrylate (pHEMA) hydrogel layer with KCl as the electrolyte layer and a lipid/polymer membrane as the taste sensing element. The reference electrode comprises a polyvinyl chloride (PVC) membrane layer with a small hole and a pHEMA layer with KCl. The whole device is the size of a USB memory stick, making it suitable for portable use. The sensor’s response to tannic acid as the standard astringency substance showed good accuracy and reproducibility, and was comparable with the performance of a commercially available taste sensing system. Thus, it is possible for this sensor to be used for in-field evaluations and it can make a significant contribution to the food industry, as well as in various fields of research.

Lipid membranes are useful materials to transform information about taste substances into electric signals. A lipid monolayer membrane for a taste sensor has been prepared by adsorbing lipid materials to the hydrophobic surface of a polymer membrane. The lipid-modified membranes respond to such electrolytic taste substances as HCl (sourness) or NaCl (saltiness) with large response magnitudes and such non-electrolytic substances as caffeine (bitterness) or sugar (sweetness) with high sensitivities. Thus the present membrane has a high ability to detect taste.

A taste sensor that uses lipid/polymer membranes can evaluate aftertastes felt by humans using Change in membrane Potential caused by Adsorption (CPA) measurements. The sensor membrane for evaluating bitterness, which is caused by acidic bitter substances such as iso-alpha acid contained in beer, needs an immersion process in monosodium glutamate (MSG) solution, called "MSG preconditioning". However, what happens to the lipid/polymer membrane during MSG preconditioning is not clear. Therefore, we carried out three experiments to investigate the changes in the lipid/polymer membrane caused by the MSG preconditioning, i.e., measurements of the taste sensor, measurements of the amount of the bitterness substance adsorbed onto the membrane and measurements of the contact angle of the membrane surface. The CPA values increased as the preconditioning process progressed, and became stable after 3 d of preconditioning. The response potentials to the reference solution showed the same tendency of the CPA value change during the preconditioning period. The contact angle of the lipid/polymer membrane surface decreased after 7 d of MSG preconditioning; in short, the surface of the lipid/polymer membrane became hydrophilic during MSG preconditioning. The amount of adsorbed iso-alpha acid was increased until 5 d preconditioning, and then it decreased. In this study, we revealed that the CPA values increased with the progress of MSG preconditioning in spite of the decrease of the amount of iso-alpha acid adsorbed onto the lipid/polymer membrane, and it was indicated that the CPA values increase because the sensor sensitivity was improved by the MSG preconditioning.

The purpose of this study is the development of a multichannel taste sensor chip for use in a portable taste sensor. The chip comprises a set of Ti/Ag patterned electrodes with lipid/polymer membranes and a reference electrode. The electrodes are formed on a polycarbonate substrate, which is attached to a polycarbonate sheet by double-sided adhesive tape (polyimide). The polycarbonate sheet has a number of holes in it that give access to the electrodes thus forming multichannel taste sensing sites. A sensor chip was fabricated and evaluated for its performance in tasting samples with basic tastes. The reference electrode did not interact with the basic taste samples, thus providing a stable potential. The outputs from the sensor chip for the various taste samples were at the same levels as those from a conventional taste sensor, indicating that this new taste sensor could provide the key element in the development of a portable taste sensor.