Fluorescence Sensing Properties of a Bibranched Cyanostilbene Derivative Containing -NH2 for Trace Water and Picric Acid Determination.

In order to design organic small molecule fluorescent materials with multiple sensing, a bibranched -NH2 modified cyanostilbene derivative (AM) was synthesized. It exhibits solvent and aggregation-induced emission effects, with a solid-state quantum yield of 28%, which is seven times higher than that in THF. The synthesized sample AM demonstrated high sensitivity to trace water via a fluorescence "turn-off" response, achieving a low detection limit of 0.41 µM in THF and 0.80 µM in EtOH. AM also exhibits a "turn-off" response to picric acid, attributed to the photo-induced electron transfer effect it induces. The recognition of picric acid by AM demonstrates specificity and resistance to interference from nitro explosives, with a detection limit of 300 ppb and a linear relationship (R2 = 0.9981) at the range of 0-4 equivalents AM. Such acid recognition can facilitate the design of qualitative test papers and safety inks. Additionally, AM can function as a temperature sensor with a linear relationship (R2 = 0.9976) within the temperature range of 25-110 °C. Leveraging these unique characteristics, a series of methods were proposed for the direct quantitative determination of trace water in nonaqueous solvents, picric acid, and temperature.

A novel fluorescent indicator-based fluorene derivative for rapid and visual trace water sensing.

Fluorene nucleus derivatives show great potential for building outstanding fluorescence probes. In this paper, a novel fluorescent probe was developed by reacting with fluorene core with azacyclobutane, which exhibits typical solvation chromogenic effect in solvent. The fluorescence of the probe quenched in highly polar solvent. Based on this phenomenon, a novel fluorescence system for trace water was constructed. The response of this probe was fast (30 s) and sensitive for the detection of trace water in organic solvents, and the detection limit of water content in DMSO reached 0.13%. In addition, the probe can also be made as a test strip combined with homemade portable device and a smartphone for rapid detection of trace water. The luminescence mechanism of the probe is theoretically calculated based on time-contained density functional theory (TDDFT). To showcase its practicality, it has been applied for the detection of trace water in honey and alcohol by dipstick. This method provides a new idea for designing efficient fluorescent probes based on dipstick and mobile phone rapid detection.

A tert-Butyldiphenylsilyl-Containing Polyimide-Based Chemosensor for Sequential Detection of Fluoride Ions and Trace Water in Organic Solvents.

A tert-butyldiphenylsilyl-containing polyimide (PI-OSi) has been established as a colorimetric and ratiometric chemosensor for rapid detecting fluoride ions (F-). The UV-vis absorbance ratio value (A322/A288) of PI-OSi in a DMF solution displays a wide linear range change to F- concentrations with a detection limit (DL) value of 2.13 µM. Additionally, adding incremental amounts of F- to a DMF solution of PI-OSi shows an immediate color change to yellow and finally to green from colorless. More interestingly, the resulting PI-OSi plus F- system (PI-OSi·F) could detect trace water in DMF. The A292/A322 value of PI-OSi·F almost linearly increases with low water content, which suggests convenient quantitative sensing of trace water content in DMF. The DL value of PI-OSi·F for sensing water in DMF is determined to be 0.00149% (v/v). The solution color of PI-OSi·F returns to colorless when the water content increases, indicating that PI-OSi·F can conveniently estimate water content in DMF by naked-eye detection. The detection mechanisms confirmed by an 1H NMR study and a DFT calculation involve a F--induced desilylation reaction of PI-OSi to form phenolate anion followed by protonation with trace water. Finally, PI-OSi film was fabricated for the colorimetric detection of F- and water in CH3CN.

A Humidity-Induced Large Electronic Conductivity Change of 107 on a Metal-Organic Framework for Highly Sensitive Water Detection.

The electronic conductivity (EC) of metal-organic frameworks (MOFs) is sensitive to strongly oxidizing guest molecules. Water is a relatively mild species, however, the effect of H2 O on the EC of MOFs is rarely reported. We explored the effect of H2 O on the EC in the MOFs (NH2 )2 -MIL-125 and its derivatives with experimental and theoretical investigations. Unexpectedly, a large EC increase of 107 on H2 SO4 @(NH2 )2 -MIL-125 by H2 O was observed. Brønsted acid-base pairs formed with the -NH2 groups, and H2 SO4 played an important role in promoting the charge transfer from H2 O to the MOF. Based on H2 SO4 @(NH2 )2 -MIL-125, a high-performance chemiresistive humidity sensor was developed with the highest sensitivity, broadest detection range, and lowest limit of detection amongst all reported sensing materials to date. This work not only demonstrated that H2 O can remarkably influence the EC of MOFs, but it also revealed that post-modification of the structure of MOFs could enhance the influence of the guest molecule on their EC to design high-performance sensing materials.

Trace Water as Prominent Factor to Induce Peptide Self-Assembly: Dynamic Evolution and Governing Interactions in Ionic Liquids.

The interaction between water and biomolecules including peptides is of critical importance for forming high-level architectures and triggering life's functions. However, the bulk aqueous environment has limitations in detecting the kinetics and mechanisms of peptide self-assembly, especially relating to interactions of trace water. With ionic liquids (ILs) as a nonconventional medium, herein, it is discovered that trace amounts of water play a decisive role in triggering self-assembly of a biologically derived dipeptide. ILs provide a suitable nonaqueous environment, enabling us to mediate water content and follow the dynamic evolution of peptide self-assembly. The trace water is found to be involved in the assembly process of dipeptide, especially leading to the formation of stable noncovalent dipeptide oligomers in the early stage of nucleation, as evident by both experimental studies and theoretical simulations. The thermodynamics of the growth process is mainly governed by a synergistic effect of hydrophobic interaction and hydrogen bonds. Each step of assembly presents a different trend in thermodynamic energy. The dynamic evolution of assembly process can be efficiently mediated by changing trace water content. The decisive role of trace water in triggering and mediating self-assembly of biomolecules provides a new perspective in understanding supramolecular chemistry and molecular self-organization in biology.

Advances on fluorescence chemosensors for selective detection of water.

Water, although an important part of everyday life, is acts as one of the most significant contaminants in various applications such as biomedical monitoring, chemical production, petroleum-based fuel and food processing. In fact, the presence of water in other solvents is a huge concern. For the quantification of trace water content, different methods such as Karl-Fischer, electrochemical, nuclear magnetic resonance, chromatography, and thermogravimetric analysis have been used. Although every technique has its own benefit, each one suffers from several drawbacks that include high detection costs, lengthy procedures and specialized operations. Nowadays, the development of fluorescence-based chemical probes has become an exciting area of research for the quick and accurate estimation of water content in organic solvents. A variety of chemical processes such as hydrolysis reaction, metal ions promoted oxidation reaction, suppression of the -C═N isomerization, protonation and deprotonation reactions, and molecular aggregation have been well researched in the last few years for the fluorescent detection of trace water. These chemical processes eventually lead to different photophysical events such as aggregation-induced emission (AIE), aggregation-induced emission enhancement (AIEE), aggregation-caused quenching (ACQ), fluorescent resonance energy transfer (FRET), charge transfer, photo-induced electron transfer (PET), excited state intramolecular proton transfer (ESIPT) that are responsible for the detection. This review presents a summary of the fluorescence-based chemosensors reported in recent years. The design of water sensors, sensing mechanisms and their potential applications are reviewed and discussed.

A reversible fluorescent sensor for continuous detection of fluoride ion and trace water in chemical reagents.

Continuously monitorable fluorescence sensors can provide fast, immediate, in-field detection of analytes without tedious process. A simple fluorescent sensor (BN) constructed from naphthol Schiff base was developed for reversible monitoring of F- and trace water. Sensor BN showed specific selectivity toward F- over other anions giving rise to a fluorescence "turn-on" response. After added F-, the BN solution caused a dramatically observable color change from non-fluorescence to blue-green, and the limit of detection reached 78.5 nM. The Job's and 1H NMR analysis confirmed that the recognition mechanism could be concluded to F- caused deprotonation of sensor BN by hydrogen bonding interaction. Moreover, the deprotonated form BN∙F obtained by using F- was acted as excellent sensitivity sensor for trace water detection with instant response through reprotonation. After addition of trace water, the emission color and spectral signal of BN∙F reverted to the original BN sate with the limit of detection of 0.0011 %. The reversible detection characteristic was conducive to the development of an inkless writing and encryption device. And importantly, BN∙F was utilized as a promising fluorescent sensor in the quantitative determination of water content in routinely chemical reagents.

Rapid and ultra-sensitive trace water determination in organic solvents utilizing nitrobenzoxadiazole (NBD)-based fluorescent sensing system.

The presence of minute quantities of water in organic solvents can affect the progress of many reactions and cause unnecessary losses and even safety accidents in the chemical industry, especially in the productions process of organic fine chemicals. Therefore, it is necessary to carry out high-performance strategies for trace water detections in commonly used organic solvents. In this work, a fluorescent sensing system based on competitive binding of protons has been developed, demonstrating remarkable responses by UV-vis absorption and fluorescence two-modes toward a trace amount of water in organic solvents including 1,4-dioxane (Diox), tetrahydrofuran (THF), acetonitrile (MeCN), acetone (ACE), dimethylsulfoxide (DMSO) and mixed organic solvents (THF: MeCN=1: 1). The key component of the sensing system is a newly designed fluorophore NBD-PMA, which can be deprotonated to form a dynamic non-luminescent adduct, namely NBD-PMA-F, by an organic fluoride salt tetrabutylammonium fluoride (TBAF). NBD-PMA-F can be reprotonated via using trace water, exhibiting fluorescence turn on of the system. The as-prepared sensing system shows superior sensitivity, low detection limits (v/v, 0.0007 %), quick response speed (≤1.2 s) and good reversibility. Moreover, naked-eye visual rapid detection has also been successfully realized at ambient temperature, which demonstrated their practical applications value for trace water determinations.

A "turn-on" fluorescent sensor based on three-component covalent organic framework for trace water detection.

Trace amount of H2O is difficult to eliminate in laboratory environments and chemical industries as impurities. In some chemical reactions, trace amount of H2O can alter final reaction products, yield, and selectivity. So, the detection of trace H2O is very important. Herein, a series of TFPT[X]-BMTH- covalent organic frameworks (COFs) (X = 0, 33, 50, 67, 100 %) with intramolecular charge transfer effect (ICT) and aggregate-induced emission (AIE) characteristics were synthesized by amino-aldehyde condensation reaction between 2,5-bis(2-methoxyethoxy)terephthalohydrazide (BMTH)/ 1,3,5-tris(p-formylphenyl)benzene (TFPB) and 4,4',4''-(1,3,5-triazine-2,4,6-triyl)tribenzaldehyde (TFPT). By changing TFPT' content in TFPT[X]-BMTH-COFs, the ICT and AIE of TFPT[X]-BMTH-COFs can be controlled, and accordingly the response to trace H2O can be adjusted. A H2O sensor based on TFPT[67]-BMTH-COF with a wide linear range from 0 wt% to 0.5 wt% was developed and the detection limit was 0.00007 wt%. In addition, a portable fluorescent test paper based on TFPT[67]-BMTH-COF for visual detection of trace H2O in honey samples and salt was constructed. This work has important guiding significance for the development of fluorescent probes for the visual detection of trace water.

Metal-Organic Framework Flowers as a Naked-Eye Colorimetric Indicator of Trace Water.

Convenient and sensitive trace water indication is of great significance in various industrial processes. Here, a flower-like metal-organic framework Cu-FMM is assembled from ultrathin nanosheets that change its coordination structure reversibly with the capture and loss of water molecules, enabling sensitive trace water naked-eye colorimetric indication ability. A recognizable black/yellow color change can be observed when the dried Cu-FMM is exposed to the atmosphere or solvent with trace water as low as RH 3% and a water content of 0.25‰ (v/v) and further enables potential trace water imaging applications. The excellent accessibility of the multi-scale pore structure of Cu-FMM contributes to a fast response time of 3.8 s with good reversibility (>100 cycles), outperforming traditional coordination polymer humidity sensors. The present study provides new inspirations for the design of sensitive and applicable naked-eye water indicator materials that are applicable to in situ and continuous monitoring in industrial processes.

Influence of Residual Water Traces on the Electrochemical Performance of Hydrophobic Ionic Liquids for Magnesium-Containing Electrolytes.

A trace amount of water is typically unavoidable as an impurity in ionic liquids, which is a huge challenge for their application in Mg-ion batteries. Here, we employed molecular sieves of different pore diameters (3, 4, and 5 Å), to effectively remove the trace amounts of water from 1-methyl-1-propylpiperidinium bis(trifluoromethylsulfonyl)imide (MPPip-TFSI) and 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide (BMP-TFSI). Notably, after sieving (water content <1 mg ⋅ L-1 ), new anodic peaks arise that are attributed to the formation of different anion-cation structures induced by minimizing the influence of hydrogen bonds. Furthermore, electrochemical impedance spectroscopy (EIS) reveals that the electrolyte resistance decreases by ∼10 % for MPPip-TFSI and by ∼28 % for BMP-TFSI after sieving. The electrochemical Mg deposition/dissolution is investigated in MPPip-TFSI/tetraglyme (1 : 1)+100 mM Mg(TFSI)2 +10 mM Mg(BH4 )2 using Ag/AgCl and Mg reference electrodes. The presence of a trace amount of water leads to a considerable shift of 0.9 V vs. Mg2+/ Mg in the overpotential of Mg deposition. In contrast, drying of MPPip-TFSI enhances the reversibility of Mg deposition/dissolution and suppresses the passivation of the Mg electrode.

Triboelectric Mechanism of Oil-Solid Interface Adopted for Self-Powered Insulating Oil Condition Monitoring.

The liquid-solid contact electrification mechanism has been explored in the aqueous solution system, but there are few systematic studies on oil-solid triboelectrification. Herein, an oil droplet triboelectric nanogenerator (Oil-droplet TENG) is designed as the probe to investigate the charge transfer properties at oil-solid interface. The charge transfer kinetics process is disclosed by the electrical signals produced, showing that the electron species initially predominated the oil-solid triboelectrification. The molecular structure and electronic properties of oil also affect triboelectric performance. Further, the charge transfer principle in multi-component liquid mixture during the electric double layer (EDL) development process is proposed to explain the component competition effect. As a proof of concept, a tubular-TENG is designed as a self-powered sensor for transformer oil trace water detection. The device demonstrates high water sensitivity with a detection limit of 10 µL L-1 and a response range of 10-100 µL L-1 . This work not only reveals the oil-solid triboelectric and charge transfer competition mechanism in EDL, but also open up a new channel for real-time online monitoring of trace water in transformer oil, which holds promise for information perception and intelligent operation of transformers in the power industry.

Detection of Trace Water Based on Electro-oxidation of Molybdenum Disulfide Nanomaterials to Form Molybdenum Oxysulfide.

Molybdenum disulfide nanomaterials nowadays are very popular in electrocatalysis field due to their outstanding catalytic performance toward many electrochemical reactions. However, the electrochemical oxidation reaction of molybdenum disulfide nanomaterials in the range of positive potential has not been studied thoroughly. Herein, we have investigated electro-oxidation of molybdenum disulfide nanomaterials and put forward a new reaction mechanism: molybdenum disulfide nanomaterials are electro-oxidized with water to form molybdenum oxysulfide (MoOS2) and hydrogen ions, leading to the release of hydrogen on the counter electrode. Various characterization methods such as contact angle measurement, scanning electron microscope (SEM), transmission electron microscope (TEM) with energy dispersive X-ray spectroscopy (EDS), X-ray photoelectron spectroscopy (XPS), X-ray absorption near edge structure (XANES) spectroscopy, time-of-flight secondary ion mass spectrometry (ToF-SIMS), and gas chromatography (GC) were applied to attest the doping of oxygen and the generation of hydrogen. Based on this reaction, we constructed a novel ultrasensitive electrochemical sensor for detecting trace water with the minimum detectable content of 0.0010% (v/v) in various organic solvents and ionic liquids, which is comparable to the Karl Fischer titration, but with much simpler reagent.

Mechanisms behind multicolor tunable Near-Infrared triple emission in graphene quantum dots and ratio fluorescent probe for water detection.

Developing environmental-friendly and low-cost strategies of synthesizing red-emission graphene quantum dots (R-GQDs) is a considerable challenge. Herein, we present the green and facile preparation of R-GQDs by using o-phenylenediamine (o-PD) and catechol as precursors via oxidation/polymerization and Schiff base reaction at low temperature (80 °C) for 3 hrs. Results show that the prepared R-GQDs exhibit triple fluorescence emissions, which is enabled by the introduce of different nitrogen (pyrrolic N, pyridinic N, and amino N) species on the surface of R-GQDs. Moreover, the R-GQDs are implemented to detect the moisture in different organic solvent. A highly sensitive ratiometric sensing of water in organic solvents is achieved, and the relationship between the change of fluorescence signal caused by moisture and the corresponding internal emission site is also determined. In the end, the multicolor light emissions of R-GQDs are realized by simply adjusting the polarity of surrounding solvents. And based on the solvatochromism of R-GQDs, the multicolor solid fluorescent powder and ink are prepared for illumination application. All in all, the above research work presents a novel R-GQDs for wide application in detecting and illumination.

High-contrast colourimetric probes for fluoride and trace water based on tautomerization of naphthalimide and application in fingerprint imaging.

Three probes for fluoride ion and trace water based on naphthalimide were designed and synthesized. A new sensing mechanism based on naphthalimide tautomerization induced by fluoride ion and water was explored in the aprotic organic solvent. In the fluoride ion sensing process, the probes exhibited a remarkable absorption peak centred at 560 nm in the visible range of 400-700 nm. When trace water presented, the newly formed absorption peak centred at 560 nm gradually disappeared. The sensitive colour variation of the probe also was used in fingerprint imaging. Accordingly, the significant changes in chemical shift of dept135 and 1HNMR spectrum confirmed the structural transformation of the probes with high contrast. Furthermore, this work also presented an optimization strategy for the sensitivity of the probe based on regulatory tautomerization.

N-hydroxypropyl substituted 4-hydroxynaphthalimide: Differentiation of solvents and discriminative determination of water in organic solvents.

A naphthalimide-based fluorophore (HONIOH) was designed by introducing a hydroxy unit into the 4th position of the aromatic core and a hydroxypropyl unit into the N-imide site. Photophysical properties of HONIOH were highly dependent on solvents, which was ascribed to the excited state proton transfer (ESPT) coupled with intramolecular charge transfer (ICT) mechanism. Further studies demonstrated that HONIOH can be used to recognize N, N-dimethylformamide (DMF) qualitatively and differentiate methanol from ethanol. Three control compounds were synthesized, their photophysical properties were investigated in various solvents, and experimental results revealed that hydroxyl and hydroxypropyl units contribute to the solvents differentiation ability of HONIOH. In addition, HONIOH was successfully applied as a colorimetric, fluorescent probe for the discriminative detection of trace water in organic solvents, such as fluorescence turn-on response accompanied by fluorescent color changes from light yellow to purple in DMF, and fluorescence turn-off response and blue to yellow fluorescent color changes in acetonitrile, tetrahydrofuran, and acetone. We believe that N-substituted 4-hydroxynaphthalimide derivatives may find widespread applications in chemical and biochemical sensing and imaging.

Visual monitoring of trace water in organic solvents based on ecofriendly b/r-CDs ratiometric fluorescence test paper.

Developing a green, non-toxic and easy to synthesize of fluorescence probe for fast and visual detecting trace water in various organic solvents was an important task. Here, a novel dual-emission fluorescence probe (b/r-CDs) was designed based on the red CDs (r-CDs) and blue CDs (b-CDs) to detect the trace water and enhance the visualization for naked-eye observation in different organic solvents. Among, the red fluorescence carbon dots (CDs) was found to have the capability to monitor trace amounts of water, which synthesized with green tea by facile ultrasonic method. Further, Such a dual-emission probe could fast monitor trace water in various organic solvents with high stability and fast response. Importantly, a synergistic mechanism of the dynamic process (b-CDs) and static quenching (r-CDs) was proved for the study of water detection. Moreover, the test paper was made for detecting trace water in different organic solvents, achieving convenient and effective detection.

Dual Function Based on Switchable Colorimetric Luminescence for Water and Temperature Sensing in Two-Dimensional Metal-Organic Framework Nanosheets.

A simple, rapid, highly selective, and real-time determination of water is urgently required for preventing danger from water contamination in materials. Herein, the excited-state proton transfer (ESPT) concept-based luminescent sensor [Cd2(2,5-tpt)(4,5-idc)(H2O)4] (1) (2,5-tpt = 2,5-dihydroxyterephthalic acid and 4,5-idc = 4,5-imidazoledicarboxylic acid) has been designed for discriminative detection via enol-keto tautomerism. To improve the sensitivity, two-dimensional (2D) nanosheets of 1 have been synthesized by top-down liquid ultrasonic exfoliation technology for sensing water in dimethylformamide, which lead to fast detection (<30 s), high selectivity, broad-range detection (0-50% v/v), and a low detection limit value (0.25% v/v). This sensor can serve dual sensing mechanisms along with a luminescent color change via shifted emission (green→yellow) in low water content and a turn-off method in high water content. For ease of use, the test-strip paper-based 2D nanosheets of 1 have been prepared and applied for water detection with long-term stability, pH stability, and good reusability. On-site water detection in real time can be evaluated using a smartphone color-scanning application for quantitative scanometric assays coupled with test-strip paper-based 2D nanosheets of 1. Also, 1 can be utilized for a colorimetric luminescent thermometer in the ranges of physiological and high temperature with good linearity and recyclability.

Towards the interaction between calcium carbide and water during gas-chromatographic determination of trace moisture in ultra-high purity ammonia.

The current study focuses on the processes involved during the flow conversion of water into acetylene in a calcium carbide reaction cell for the trace moisture analysis of ammonia by reaction gas chromatography. The factors negatively affecting the reproducibility and the accuracy of the measurements are suggested and discussed. The intramolecular reaction of the HOCaCCH intermediate was found to be a side reaction producing background acetylene during the contact of wet ammonia gas with calcium carbide. The presence of the HOCaCCH intermediate among the reaction products is confirmed by an FTIR spectral study of calcium carbide powder exposed to wet gas. The side reaction kinetics is evaluated experimentally and its influence on the results of the gas chromatographic measurements is discussed in relation to the determination of the optimal operating parameters for ammonia analysis. The reaction gas chromatography method for the trace moisture measurements in an ammonia matrix was experimentally compared to an FTIR long-path length gas cell technique to evaluate the accuracy limitations and the resource intensity.

Colorimetric and fluorometric dual sensing of trace water in methanol based on a Schiff Base-Al3+ ensemble probe.

A new julolidine based Schiff base receptor (L) was synthesized and characterized. L forms a 1:1 complex with Al3+ in methanol, resulting in an immediate color change from chartreuse to orange and a remarkable enhancement in its emission intensity along with a bathochromic shift from 540 nm to 570 nm. Addition of trace amounts of water significantly quenches the fluorescence emission, where a decomplexation of Al3+ from the L-Al3+ complex takes place. The significant quenching effect indicated that the L-Al3+ ensemble system can be used to detect trace water in commercial methanol. From the fluorescence titration, the detection limit for sensing water in methanol was estimated to be 0.0047%. We have also made an easy-to-prepare test strip of L-Al3+ to detect water in methanol through naked-eye observation, which is possible to realize in situ monitoring.