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.

The Relationship between Parent-Offspring Communication and the School Adaptation of Leftover Children in Overseas Countries: The Mediating Role of Companionship and the Moderating Role of a Sense of Safety.

BACKGROUND: In the diasporic eastern coastal region of China, leftover children are a unique group of children; their social adaptation challenges are more prominent due to transnational separation from parents. This study explores the relationship between parent-offspring communication and school adaptation among leftover children. METHODS: We administered questionnaires to 957 children from six schools in June and December of 2022. All students in the sample were randomly selected from within the classrooms. In total, 561 (47.95% female, mean age = 12.84, SD = 0.95) of them were leftover children. Self-report questionnaires on communication with their parents, school adaptation, companionship, and feelings of safety were used in this investigation We subsequently used SPSS software and the PROCESS plugin to analyze the relationships between variables. RESULTS: A significant and positive relationship was found between parent-offspring communication and school adaptation in leftover children. Companionship mediated this effect. Additionally, the impact of parent-offspring communication on companionship was moderated by a sense of safety. CONCLUSIONS: The study concluded that parent-offspring communication, school adaptation, companionship, and a sense of safety were all positively correlated. In addition, companionship partially mediated the relationship between parent-offspring communication and school adaptation. Moreover, a sense of safety played a moderating role. These conclusions can provide empirical support for improving the school adaptation of leftover children.

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.

Printed colorimetric chemosensor array on a 96-microwell paper substrate for metal ions in river water.

Here, we propose a printed 96-well microtiter paper-based chemosensor array device (PCSAD) to simultaneously detect metal ions for river water assessment. Colorimetric chemosensors for metal ions have been designed based on molecular self-assembly using off-the-shelf catechol dyes and a phenylboronic acid (PBA) derivative. The colorimetric self-assembled chemosensors consisting of catechol dyes and a PBA derivative on a 96-well microtiter paper substrate demonstrated various color changes according to the disassembly of the ensembles by the addition of nine types of metal ions. An in-house-made algorithm was used to automate imaging analysis and extract color intensities at seven types of color channels from a captured digital image, allowing for rapid data processing. The obtained information-rich inset data showed fingerprint-like colorimetric responses and was applied to the qualitative and quantitative pattern recognition of metal ions using chemometric techniques. The feasibility of the 96-well microtiter PCSAD for environmental assessment has been revealed by the demonstration of a spike-and-recovery test against metal ions in a river water sample.

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.

Dynamic Threshold Effect of Directed Technical Change Suppress on Urban Carbon Footprint in China.

Promoting technical change is an important driving force for promoting the sustainable development of urban economy and ecology; however, the technical change is not always neutral and technical change may has a certain direction. This paper uses the DEA-Malmquist index to measure the directed technical change of 280 cities in China from 2009 to 2019, and uses the DMSP/OLS night light data to characterize the urban economic development level. It uses the dynamic threshold regression model to analyze the impact of directed technical change on urban carbon footprint under different economic development levels. The results show that: (1) during the study period, the carbon footprint of Chinese cities has a positive spatial correlation, and the direction of technical change is towards capital-saving overall. (2) The impact of capital-saving technical change on urban carbon footprint presents a negative double-threshold characteristic in China, and the inhibition of capital-saving technical change on the urban carbon footprint becomes stronger with the increasing economic development level. (3) The inhibitory effect of capital-saving technical change on carbon footprint has regional heterogeneity, and the inhibitory effect of capital-saving technical change on carbon footprint is stronger in eastern China than other regions. (4) Industrial structure, energy structure and innovation efficiency are mediating variables of the inhibitory effect of capital-saving technical change on carbon footprint except for population density.

Freshness monitoring of raw fish by detecting biogenic amines using a gold nanoparticle-based colorimetric sensor array.

We herein report the quantitative detection of biogenic amines using a gold nanoparticle-based colorimetric chemosensor array for food analysis. The gold nanoparticles are functionalized with carboxylate derivatives, which capture target amines through hydrogen bonds and electrostatic interactions. The simultaneous discrimination of 10 amine derivatives was achieved by a linear discriminant analysis with a 100% correct classification based on the multi-colorimetric response pattern of structural differences. Furthermore, a real sample analysis for raw fish (i.e., tuna) demonstrated highly accurate determination of histamine concentrations by a support vector machine, the result of which was matched with high-performance liquid chromatography. Most importantly, the chemosensor array succeeded in detecting the time-dependent concentration change of histamine in the raw fish, meaning that the decomposition of the fish could be monitored by the colorimetric changes. Hence, the proposed chemosensor array combined with pattern recognition techniques can be a user-friendly analytical method for food freshness monitoring.

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.

Exploring Two Decades of Research in Community Resilience: A Content Analysis Across the International Literature.

INTRODUCTION: Community resilience (CR) has gradually become a hot topic in uncertain times, especially in the last five years. The current study presents a systematic review based on content analysis to present a knowledge graph of CR research over the last 20 years. METHODS: We use an approach of Leximancer to conduct the content analysis to explore the intellectual foundations, research context, topics, and methods of CR literature based on 583 published studies. RESULTS: The results show that framework research of CR is a hot topic throughout the last 20 years. In the first stage (from 2001 to 2015), CR connected with the themes of "framework, disaster, change, and model". Comparatively, in the second stage (from 2016 to 2020), the themes of "social capital, capacity, and framework" are more salient connecting with CR. Additionally, the study detected that the key issues varied across countries. Specifically, research in the US focused on the social support dynamic, while in Australia, recovery from the disaster was the predominant theme. Furthermore, in the UK, studies mostly explore resilience issues in the background related to flooding. DISCUSSION: Our findings provide a comprehensive picture of CR research covering the last 20 years and put forward thoughts and recommendations for future resilience studies considering 1) obstacles within daily life, 2) resilience set within organizational perspectives, and 3) cultural context.

Legitimate but "not for me": The role of validation in migrant entrepreneur understanding of COVID-19 business support policies in Shanghai.

COVID-19 pandemic destroyed lives and the global economy, and in the wake left businesses struggling to re-open in urban China. The Chinese party-state implemented fiscal reforms targeted towards small businesses, however little research has evaluated business' understanding of policies and implementation, particular to the focus on rural migrant entrepreneurs. Therefore, we conducted an ethnographic case study including in-depth interviews to determine to what extent rural migrant micro-entrepreneurs understand and adopt COVID-19 business support policies at two retail markets in Shanghai amid a pandemic. Applying an inductive grounded theory approach, the data demonstrated participants believe policies are legitimate but not for me because I am getihu by myself. We maintain their understanding is a legacy of hukou and is confirmed through the theory of validation including recognition through agreement with significant others including other entrepreneurs and family; corroboration with life experiences in Shanghai; and resonance of their migration story as self-sufficient entrepreneurs surviving with their own capabilities. They have a degree of certainty their understanding is fact because it has been repeatedly validated through life experiences of a migrant lacking hukou in Shanghai. The study encourages consideration for the migrant entrepreneur context and has important practical implications for policymakers.

Toward Food Freshness Monitoring: Coordination Binding-Based Colorimetric Sensor Array for Sulfur-Containing Amino Acids.

Herein, a self-assembled colorimetric chemosensor array composed of off-the-shelf catechol dyes and a metal ion (i.e., Zn2+) has been used for the sulfur-containing amino acids (SCAAs; i.e., glutathione, glutathione disulfide, L-cysteine, DL-homocysteine, and L-cystine). The coordination binding-based chemosensor array (CBSA) fabricated by a competitive assay among SCAAs, Zn2+ ions, and catechol dyes [i.e., pyrocatechol violet (PV), bromopyrogallol red (BPR), pyrogallol red (PR), and alizarin red S (ARS)] yielded fingerprint-like colorimetric changes. We succeeded in the qualification of SCAAs based on pattern recognition [i.e., a linear discrimination analysis (LDA)] with 100% correct classification accuracy. The semiquantification of reduced/oxidized forms of SCAAs was also performed based on LDA. Furthermore, we carried out a spike test of glutathione in food samples using the proposed chemosensor array with regression analysis. It is worth mentioning that we achieved a 91-110% recovery rate in real sample tests, which confirmed the accuracy of the constructed model. Thus, this study represents a step forward in assessing food freshness based on supramolecular analytical methods.

A Printed Paper-Based Anion Sensor Array for Multi-Analyte Classification: On-Site Quantification of Glyphosate.

We report a paper-based chemosensor array device (PCSAD) for the quantitative detection of oxyanions including the herbicide glyphosate (GlyP) in aqueous media. The mechanism of the oxyanion detection relies on a coordination-binding-based sensor array. In this study, the competitive coordination binding among Zn2+ , four catechol dyes, and seven oxyanions caused noticeable colour changes. The colour changes were employed for qualitative and quantitative analyses using an in-house automated image-processing algorithm with pattern recognition for digital images. A linear discrimination analysis discerned similarly structured oxyanions with 100 % accuracy. The regression analysis allowed the accurate quantification of GlyP in the herbicide products with a limit of detection of 16 mg/L, which is lower than the health advisory value for children (20 mg/L) stipulated by the environmental protection agency (EPA). PCSAD is a powerful sensor device for the on-site quantification of aqueous anions for environmental assessment.

96-Well Microtiter Plate Made of Paper: A Printed Chemosensor Array for Quantitative Detection of Saccharides.

Simple, rapid, and accurate detection methods for saccharides are potentially applicable to various fields such as clinical and food chemistry. However, the practical applications of on-site analytical methods are still limited. To this end, herein, we propose a 96-well microtiter plate made of paper as a paper-based chemosensor array device (PCSAD) for the simultaneous classification of 12 saccharides and the quantification of fructose and glucose among 12 saccharides. The mechanism of the saccharide detection relied on an indicator displacement assay (IDA) on the PCSAD using four types of catechol dyes, 3-nitrophenylboronic acid, and the saccharides. The design of the PCSAD and the experimental conditions for the IDA were optimized using a central composite design. The chemosensors exhibited clear color changes upon the addition of saccharides on the paper because of the competitive boronate esterification. The color changes were employed for the subsequent qualitative, semiquantitative, and quantitative analyses using an automated algorithm combined with pattern recognition for digital images. A qualitative linear discrimination analysis offered discrimination of 12 saccharides with a 100% classification rate. The semiquantitative analysis of fructose in the presence of glucose was carried out from the viewpoint of food analysis utilizing a support vector machine, resulting in clear discrimination of the various concentrations of fructose. Most importantly, the quantitative detection of fructose in two types of commercial soft drinks was also successfully carried out without sample pretreatments. Thus, the proposed PCSAD can be a powerful method for on-site food analyses that can meet the increasing demand from consumers for sensors of saccharides.

Easy-to-Prepare Mini-Chemosensor Array for Simultaneous Detection of Cysteine and Glutathione Derivatives.

We herein propose an easy-to-prepare mini-chemosensor array constructed by two-types of off-the-shelf coumarin dyes for simultaneous classification and quantification of sulfur-containing amino acids (SCAAs) (i.e., l-cysteine, l-cystine, l-homocysteine, glutathione, and glutathione disulfide). The detection mechanism of SCAAs relied on a coordination-based sensor array (CBSA) utilizing the competitive binding among the coumarin dye, a Zn2+ ion and SCAAs. The reversible feature of the coordination bond of the coumarin-Zn2+ resulted in UV/vis spectral shifts and fluorescence enhancement in response to the analytes, offering the multianalyte detection in high accuracy. Furthermore, a mixture of glutathione and l-cysteine was successfully quantified in a sample containing human blood serum. This study would be an important example of the optical chemosensor array toward the rapid and accurate detection of biomarkers.

Suppression of Malachite Green-Induced Toxicity to Human Liver Cells Utilizing Host-Guest Chemistry of Cucurbit[7]uril.

We investigated a host-guest complex between cucurbit[7]uril and malachite green, and its effect on the toxicity to human liver cells. The host-guest complexation was evaluated by a UV/vis titration and electrospray-ionization mass spectrometry. Interestingly, the host-guest complex resulted in remarkable suppression of the toxicity of malachite green in its practical concentration range (ca. ∼6 µM). This study is one step forward to the active control of the biological effects of potent toxicants utilizing host-guest chemistry.

Supramolecular Sensor for Astringent Procyanidin C1: Fluorescent Artificial Tongue for Wine Components.

An artificial tongue that detects astringent components for a comprehensive evaluation of taste has not been established to date. Herein, we first propose fluorescent polythiophene (PT) derivatives (S1-S3) modified with 3-pyridinium boronic acid as supramolecular chemosensors for wine components including astringent procyanidin C1. After numerous attempts for the synthetic conditions, more than 95 mol % of the PT unit was modified with the pyridinium boronic acid moiety. To evaluate the PT derivatives as chemosensors of the artificial tongue, qualitative and quantitative analyses were performed with four types of wine components (i.e., sweet, sour, bitter, and astringent tastes) in combination with pattern recognition models. Notably, procyanidin C1 in the actual wine sample was successfully detected in a quantitative manner. In other words, we have established an authentic artificial tongue using PT based supramolecular chemosensors.

Fluorescence Anion Chemosensor Array Based on Pyrenylboronic Acid.

A novel fluorescence chemosensor array composed of pyrenylboronic acid-based probes for multi- anion detection has been developed. The pyrenylboronic acid derivatives showed fluorescence quenching or enhancement due to photoinduced electron transfer originating from anion binding. The recognition ability was assessed by fluorescence titrations and electrospray ionization mass spectrometry. Because the array is constructed with cross-reactive probes, the combination of differential binding affinities for anions (i.e., fluoride, acetate, oxalate, malonate, citrate, dihydrogen phosphate, and pyrophosphate) and pattern recognitions, such as linear discriminant analysis, offered a successful simultaneous anion detection with a classification rate of 100%. Furthermore, the chemosensor array allowed for quantitative prediction of oxalate, malonate, and citrate in mixtures using a support vector machine. Importantly, the array system employs low-cost and commercially available reagents as probes. Thus, this study could lead to the development of user-friendly and high-throughput methods to detect a variety of analytes in complicated systems.