Nanoarchitectonics of highly dispersed polythiophene on paper for accurate quantitative detection of metal ions.

π-Conjugated polymers such as polythiophene provide intramolecular wire effects upon analyte capture, which contribute to sensitive detection in chemical sensing. However, inherent aggregation-induced quenching causes difficulty in fluorescent chemical sensing in the solid state. Herein, we propose a solid-state fluorescent chemosensor array device made of a paper substrate (PCSAD) for the qualitative and quantitative detection of metal ions. A polythiophene derivative modified by dipicolylamine moieties (1poly), which shows optical changes upon the addition of target metal ions (i.e., Cu2+, Cd2+, Ni2+, Co2+, Pb2+, Zn2+, and Hg2+), was highly dispersed on the paper substrate using office apparatus. In this regard, morphological observation of the PCSAD after printing of 1poly suggested the contribution of the fiber structures of the paper substrate to the homogeneous dispersion of 1poly ink to suppress aggregation-induced quenching. The optical changes in the PCSAD upon the addition of metal ions was rapidly recorded using a smartphone, which was further applied to imaging analysis and pattern recognition techniques for high-throughput sensing. Indeed, the printed PCSAD embedded with 1poly achieved the accurate detection of metal ions at ppm levels contained in river water. The limit of detection of the PCSAD-based sensing system using a smartphone (48 ppb for Cu2+ ions) is comparable to that of a solution-based sensing system using a stationary spectrophotometer (16 ppb for Cu2+ ions). Therefore, the methodology based on a combination of a paper-based sensor array and a π-conjugated polymer will be a promising approach for solid-state fluorescent chemosensors.

An organic transistor for detecting the oxidation of an organic sulfur compound at a solid-liquid interface and its chemical sensing applications.

The development of chemical sensors has advanced due to an increase in demand; however, the potential of chemical sensors as devices to monitor organic reactions has not been revealed yet. Thus, we aim to propose a chemical sensor platform for facile monitoring of chemical reactions, especially at a solid-liquid interface. In this study, an extended-gate-type organic field-effect transistor (OFET) has been employed as a platform to detect chemical reactions at an interface between the extended-gate electrode and an aqueous solution. The OFET device functionalized with 4,4'-thiobisbenzenthiol has shown time- and concentration-dependent shifts in transistor characteristics upon adding H2O2. In a selectivity test using seven oxidant agents, the transistor responses depended on the oxidation of the organic sulfur compound (i.e., 4,4'-thiobisbenzenthiol) stemming from the ability of the oxidant agents. Therefore, the observed changes in the transistor characteristics have suggested the generation of sulfur-oxidized products at the interface. In this regard, the observed responses were caused by disulfide formation accompanied by changes in the charges under neutral pH conditions. Meanwhile, weak transistor responses derived from the generation of oxygen adducts have also been observed, which were caused by changes in the dipole moments. Indeed, the yields of the oxygen adducts have been revealed by X-ray photoelectron spectroscopy. The monitoring of gradual changes originating from the decrease in the disulfide formation and the increase in the oxygen adducts implied a novel aspect of the OFET device as a platform to simultaneously detect reversible and irreversible reactions at interfaces without using large-sized analytical instruments. Sulfur oxidation by H2O2 on the OFET device has been further applied to the indirect monitoring of an enzymatic reaction in solution. The OFET-based chemical sensor has shown continuous changes with an increase in a substance (i.e., lactate) in the presence of an enzyme (i.e., lactate oxidase), which indicates that the OFET response depends on the H2O2 generated through the enzymatic reaction in the solution. In this study, we have clarified the versatility of organic devices as platforms to monitor different chemical reactions using a single detection method.

Leaf-Inspired Host-Guest Complexation-Dictating Supramolecular Gas Sensors.

We report unique conductive leaf-inspired (in particular, stomata-inspired) supramolecular gas sensors in which acetylated cyclodextrin derivatives rule the electric output. The gas sensors consist of polymers bearing acetylated cyclodextrin, adamantane, and carbon black. Host-guest complexes between acetylated cyclodextrin and adamantane corresponding to the closed stomata realize a flexible polymeric matrix. Effective recombination of the cross-links contributes to the robustness. As gas sensors, the supramolecular materials detect ammonia as well as various other gases at 1 ppm in 10 min. The free acetylated cyclodextrin corresponding to open stomata recognized the guest gases to alter the electric resistivity. Interestingly, the conductive device failed to detect ammonia gases at all without acetylated cyclodextrin. The molecular recognition was studied by molecular dynamics simulations. The gas molecules existed stably in the cavity of free acetylated cyclodextrin. These findings show the potential for developing wearable gas sensors.

Spontaneous preparation of a fluorescent ratiometric chemosensor for metal ions using off-the-shelf materials.

A self-assembled chemosensor prepared using off-the-shelf materials has shown various fluorescence responses including ratiometric and simple ON-OFF switching profiles by adding different toxic metal ions. The unique fingerprint-like responses have been applied to pattern recognition of metal ions in river water for environmental analysis.

Zn(II)-Dipicolylamine-Attached Amphiphilic Polythiophene for Quantitative Pattern Recognition of Oxyanions in Mixtures.

Herein, we propose a novel amphiphilic polythiophene-based chemosensor functionalized with a Zn(II)-dipicolylamine side chain (1poly ⋅ Zn) for the pattern recognition of oxyanions. Optical changes in amphiphilic 1poly ⋅ Zn can be induced by the formation of a random coil from a backbone-planarized structure upon the addition of target oxyanions, which results in blueshifts in the UV-vis absorption spectra and turn-on-type fluorescence responses. Dynamic behavior in a polythiophene wire and/or among wires could be a driving force for obtaining visible color changes, while the molecular wire effect is dominant in obtaining fluorescence sensor responses. Notably, the magnitude of optical changes in 1poly ⋅ Zn has depended on differences in properties of oxyanions, such as their binding affinity, hydrophilicity, and molecular geometry. Thus, various colorimetric and fluorescence response patterns of 1poly ⋅ Zn to oxyanions were obtained, albeit using a single chemosensor. A constructed information-rich dataset was applied to pattern recognition for the simultaneous group categorization of phosphate and carboxylate groups and the prediction of similar structural oxyanions at a different order of concentrations in their mixture solutions.

An organic transistor for the selective detection of tropane alkaloids utilizing a molecularly imprinted polymer.

This study proposes a chemical sensing approach for the selective detection of tropane alkaloid drugs based on an extended-gate-type organic field-effect transistor (OFET) functionalized with a molecularly imprinted polymer (MIP). From the viewpoint of pharmaceutical chemistry, the development of versatile chemical sensors to determine the enantiomeric purity of over-the-counter (OTC) tropane drugs is important because of their side effects and different pharmacological activities depending on their chirality. To this end, we newly designed an OFET sensor with an MIP (MIP-OFET) as the recognition element for tropane drugs based on a high complementarity among a template (i.e., (S)-hyoscyamine) and functional monomers such as N-isopropylacrylamide and 2,2-dimethyl-4-pentenoic acid. Indeed, the MIP optimized by density functional theory (DFT) has succeeded in the sensitive and selective detection of (S)-hyoscyamine (as low as 1 µM) by the combination of the OFET with highly selective recognition sites in the MIP. The MIP-OFET was further applied to determine the enantiomeric excess (ee) of commercially available (S)-hyoscyamine, and the linearity changes in the threshold voltages of the OFET corresponded to the % ee values of (S)-hyoscyamine. Overall, the validation with tropane alkaloids revealed the potential of the MIP combined with OFET as a chemical sensor chip for OTC drugs in real-world scenarios.

Printed 384-Well Microtiter Plate on Paper for Fluorescent Chemosensor Arrays in Food Analysis.

We propose a printed 384-well microtiter paper-based fluorescent chemosensor array device (384-well microtiter PCAD) to simultaneously categorize and discriminate saccharides and sulfur-containing amino acids for food analysis. The 384-well microtiter PCAD requiring 1 µL/4 mm2 of each well can allow high-throughput sensing. The device embedded with self-assembled fluorescence chemosensors displayed a fingerprint-like response pattern for targets, the image of which was rapidly captured by a portable digital camera. Indeed, the paper-based chemosensor array system combined with imaging analysis and pattern recognition techniques not only successfully categorized saccharides and sulfur-containing amino acids but also classified mono- and disaccharide groups. Furthermore, the quantitative detectability of the printed device was revealed by a spike and recovery test for fructose and glutathione in a diluted freshly made tomato juice. We believe that the 384-well microtiter PCAD using the imaging analysis system will be a powerful sensor for multi-analytes at several categorized groups in real samples.

A microfluidic organic transistor for reversible and real-time monitoring of H2O2 at ppb/ppt levels in ultrapure water.

A microfluidic organic transistor functionalized with phenylboronic acid firstly succeeded in reversible and real-time monitoring of H2O2 at ppb/ppt levels in ultrapure water, which would be used not only as portable chemical sensors but also as monitoring tools to clarify unknown reaction mechanisms of phenylboronic acid with H2O2.

Oxytocin detection at ppt level in human saliva by an extended-gate-type organic field-effect transistor.

Herein, we report an extended-gate-type organic field-effect transistor (OFET) sensor for oxytocin. The fabricated OFET-based immunosensor has successfully detected oxytocin at a ppt level in human saliva with high recovery rates (96-102%). We believe our sensor would pave the way for the realization of portable sensors for healthcare monitoring.

Multi-Oxyanion Detection by an Organic Field-Effect Transistor with Pattern Recognition Techniques and Its Application to Quantitative Phosphate Sensing in Human Blood Serum.

We herein report an organic field-effect transistor (OFET) based chemical sensor for multi-oxyanion detection with pattern recognition techniques. The oxyanions ubiquitously play versatile roles in biological systems, and accessing the chemical information they provide would potentially facilitate fundamental research in diagnosis and pharmacology. In this regard, phosphates in human blood serum would be a promising indicator for early case detection of significant diseases. Thus, the development of an easy-to-use chemical sensor for qualitative and quantitative detection of oxyanions is required in real-world scenarios. To this end, an extended-gate-type OFET has been functionalized with a metal complex consisting of 2,2'-dipicolylamine and a copper(II) ion (CuII-dpa), allowing a compact chemical sensor for oxyanion detection. The OFET combined with a uniform CuII-dpa-based self-assembled monolayer (SAM) on the extended-gate gold electrode shows a cross-reactive response, which suggests a discriminatory power for pattern recognition. Indeed, the qualitative detection of 13 oxyanions (i.e., hydrogen monophosphate, pyrophosphate, adenosine monophosphate, adenosine diphosphate, adenosine triphosphate, terephthalate, phthalate, isophthalate, malonate, oxalate, lactate, benzoate, and acetate) has been demonstrated by only using a single OFET-based sensor with linear discriminant analysis, which has shown 100% correct classification. The OFET has been further applied to the quantification of hydrogen monophosphate in human blood serum using a support vector machine (SVM). The multiple predictions of hydrogen monophosphate at 49 and 89 µM have been successfully realized with low errors, which indicates that the OFET-based sensor with pattern recognition techniques would be a practical sensing platform for medical assays. We believe that a combination of the OFET functionalized with the SAM-based recognition scaffold and powerful pattern recognition methods can achieve multi-analyte detection from just a single sensor.

Real-Time Detection of Glyphosate by a Water-Gated Organic Field-Effect Transistor with a Microfluidic Chamber.

This paper reports the development of a real-time monitoring system utilizing the combination of a water-gated organic field-effect transistor (WG-OFET) and a microfluidic chamber for the detection of the herbicide glyphosate (GlyP). For the realization of the real-time sensing with the WG-OFET, the surface of a polymer semiconductor was utilized as a sensing unit. The aqueous solution including the target analyte, which is employed as a gate dielectric of the WG-OFET, flows into a designed microfluidic chamber on the semiconductor layer and the gate electrode. As the sensing mechanism, the WG-OFET-based sensor utilizes the competitive complexation among carboxylate-functionalized polythiophene, a copper(II) (Cu2+) ion, and GlyP. The reversible accumulation and desorption of the positively charged Cu2+ ion on the semiconductor surface induced a change in the electrical double-layer capacitance (EDLC). The optimization of the microfluidic chamber enables a uniform water flow and contributes to real-time quantitative sensing of GlyP at a micromolar level. Thus, this study would lead to practical real-time sensing in water for various fields including environmental assessment.