Water Organic Solvents Research Articles

Solvatochromic fluorescent ethynyl naphthalimide derivatives for detection of water in organic solvents

Three new derivatives of (4-methoxyphenyl) ethynyl-naphthalimide were synthesized by Sonogashira coupling reaction. These compounds showed robust and strong fluorescent signals, which shift from blue to orange as the solvent polarity increases. Computational calculations revealed that in low-polarity solvents, the molecules preferred a 90° rotation between the naphthalimide and ethynyl benzene fragments. In high-polarity solvents, where the energy barrier for rotation of the alkyne bond was higher, the molecules favored the 0° conformer, leading to longer emission wavelengths. The compound with a 2-methoxyethyl group tethered to the naphthalimide nitrogen demonstrated sensitivity to water presence in the ranges of 0–30 % (v/v) in THF, 0–15 % (v/v) in DMSO, 0–30 % (v/v) in MeCN, 0–15 % (v/v) in acetone, and 0–40 % (v/v) in EtOH. The detection limits for water were determined to be 0.0523 %, 0.1365 %, 0.0337 %, 0.0570 %, and 0.1170 % (v/v) in THF, DMSO, MeCN, acetone, and EtOH, respectively. The effectiveness of this compound in quantifying ethanol content in spirit samples was successfully demonstrated.

Detecting Moisture in Building Materials and Commercial Food adducts by 2-Hydroxy-naphthaldehyde Derived Chromo-Fluorogenic Chemosensor.

A great deal of effort has been put into developing a novel and cost-effective molecular probe for selective and sensitive recognition of trace amounts of water in organic solvents due to their tremendous advantages in industrial, pharmaceutical, and laboratory-scale chemistry. Herein, a cost-effective chemosensor L has been designed and studied for the detection of trace amounts of water. The addition of water to the DMSO solution of L exhibited an enhancement of fluorescence emission at 460nm along with a color change from green to colorless. The spectral and color changes occurred due to the self-aggregation of L. The interaction between water and L was performed by dynamic light scattering (DLS), scanning electron microscope (SEM) and finally complemented by quantum mechanical calculation. The detection limit was found to be 0.0093 wt% in DMSO. The L also exhibits a fast visual response and is effectively applied to detect trace amounts of moisture in various food materials (salt, sugar, wheat and honey) and building materials (cement, fly ash, limestone and sand).

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.

Construction of MOF@COF-derived composites for ratiometric fluorescence detection of water with ultralow background

A ratiometric sensor with ultralow background is highly desired due to its low environmental influence and high sensitivity. Herein, inspired by the solubility difference of carboxylate in aqueous and organic solvents, we prepared a core–shell structure porous zirconia–covalent organic framework (COF) composite through thermal hydrolysis of UiO-66-COF precursors in organic alkali solution. The ligand 2-aminoterephthalic acids (H2BDC-NH2) of UiO-66 were transformed into 2-aminoterephthalate salts (ATA salts) that existed in zirconium-oxo clusters building units. The composites emitted only yellow emission (597 nm) from the COF in organic solvent due to the insolubility of ATA salts that induce aggregation-caused quenching (ACQ) and the protection of the COF shell. Contrarily, when water was added into mixture, the ATA salts were released into solution and its fluorescence recovered at 446 nm, while the fluorescence of COF was quenched due to the blockage of the intramolecular charge transfer (ICT) process by water. Thus, a high-sensitivity ratiometric fluorescence method is obtained with ultralow background signal and fast response (less than 1 min) for sensing water in organic solvent. We believe that the proposed ratiometric fluorescence sensor based on the zirconia–COF composite will provide the guidance for detection with wide applications.

Robust Thiazole-Linked Covalent Organic Frameworks for Water Sensing with High Selectivity and Sensitivity.

The rational design of covalent organic frameworks (COFs) with hydrochromic properties is of significant value because of the facile and rapid detection of water in diverse fields. In this report, we present a thiazole-linked COF (TZ-COF-6) sensor with a large surface area, ultrahigh stability, and excellent crystallinity. The sensor was synthesized through a simple three-component reaction involving amine, aldehyde, and sulfur. The thiazole and methoxy groups confer strong basicity to TZ-COF-6 at the nitrogen sites, making them easily protonated reversibly by water. Therefore, TZ-COF-6 displayed color change visible to the naked eye from yellow to red when protonated, along with a red shift in absorption in the ultraviolet-visible diffuse reflectance spectra (UV-vis DRS) when exposed to water. Importantly, the water-sensing process was not affected by polar organic solvents, demonstrating greater selectivity and sensitivity compared to other COF sensors. Therefore, TZ-COF-6 was used to detect trace amounts of water in organic solvents. In strong polar solvents, such as N,N-dimethyl formamide (DMF) and ethanol (EtOH), the limit of detection (LOD) for water was as low as 0.06% and 0.53%, respectively. Even after 8 months of storage and 15 cycles, TZ-COF-6 retained its original crystallinity and detection efficiency, displaying high stability and excellent cycle performance.

Water bridges as the trigger in an amino functionalized Zn-MOF for highly selective and sensitive fluorescent sensing of water

Water is a fundamental element for life. The highly selective and sensitive sensing of water is always attractive for mankind in activities such as physiological processes study and extraterrestrial life exploration. Fluorescent MOFs with precise channels and functional groups might specifically recognize water molecules with hydrogen-bond interaction or coordination effects and work as water sensors. As a proof of concept, herein, an amino functionalized Zn-MOF (named as complex 1) with pores that just right for water molecules to form hydrogen bond bridges is revealed for highly selective and sensitive fluorescent sensing of water. The single-crystal X-ray diffraction analysis indicates that the 3D framework of complex 1 is functionalized with free amino groups in the channels. Hydrogen bonds formed in the channel along b-axis as water bridges to connect two adjacent NH2bdc ligands and result in the restriction of intramolecular motions (RIM) which could responsible for the selective turn-on fluorescence response to water. Complex 1 exhibits high sensitive to trace amount of water in organic solvents and could be used for water detection in a wide range water contents. Take advantages of complex 1, portable sensors (complex 1@PMMA) were prepared and used in the highly sensitive water sensing.

Lead-Free Antimony-Based Perovskite Nanocrystals as a Fluorescent Nanoprobe for the Turn-On Detection of Trace Water in Organic Solvents

Lead-Free Antimony-Based Perovskite Nanocrystals as a Fluorescent Nanoprobe for the Turn-On Detection of Trace Water in Organic Solvents

Visualized detection of water by modified metal organic framework-199 and its portable test paper with reversible color change

Herein, we fabricate a melamine modified metal organic framework-199 composite (MOF-199@melamine), of which the structure is affected by the dynamics of the guest H2O molecule with significant color change. It realizes the visualized quantitative detection of water in a variety of organic solvents within 30 s. Moreover, DMF restored the original structure by replacing H2O molecules, realizing the regeneration of the materials. On this basis, PTFE-MOF-199@melamine test paper is developed to portably detect water content in organic solvents (maximum 0 %-98 % (v/v) water content) and ambient relative humidity (11–85 %). The test paper can be recycled four times with a regeneration rate higher than 90 %. The results are expected to solve the problems of existed electrochemical or fluorescence strategy such as the complicated operation process and signal output/reading system.

Eu3+-Doped aluminum Metal-Organic Frameworks: A versatile platform for ratiometric detection of histidine and Water, and visible fingerprint identification

Ratiometric fluorescent sensors possess inherent self-calibration features that enable the mitigation of interference from factors unrelated to the analysis. This characteristic results in heightened sensitivity and more pronounced visual detection during qualitative and quantitative analytical processes. A ratiometric fluorescence probe Eu/Al-MOF has been successfully prepared via Eu3+ doped aluminum metal − organic frameworks. Upon introducing histidine, the fluorescence intensity of Eu3+ showed a noteworthy increase, whereas the intensity originating from the ligand decreased owing to enhancing energy transfer from the ligand to Eu3+ ions in the probe. Eu/Al-MOF could detect histidine over a wider linear range of 0.1–400 μM and a lower detection limit of 0.04 μM. Besides, in the presence of water in organic solvents, the excited state of Eu3+ in the probe could be coupled with the O-H oscillation of water molecules, and the excited state energy from Eu3+ would be transferred to the water molecules so that only the fluorescence intensity of Eu3+ gradually decreased. Thus, the proportional detection of trace water could be realized. In ethanol and DMF, the detection range for water was 0.1–20 % and 0.5–20 %, respectively. Moreover, it was found that Eu/Al-MOF could efficiently achieve the visualization identification of fingerprints, providing the possibilities for applying the nano-sensor as a promising multifunctional fluorescence probe.

Water detection in organic solvents using a copolymer membrane immobilised with a fluorescent intramolecular charge transfer-type dye: effects of intramolecular hydrogen bonds.

Numerous fluorescent dye-based optical sensors have been developed to detect water in organic solvents. However, only a few such sensors can detect water in polar solvents such as methanol or dimethyl sulfoxide, and their detection range is generally narrow. Therefore, in this study, a copolymer membrane incorporated with a pyridinium betaine dye (denoted PB1), which exhibited intramolecular charge transfer (ICT) characteristics, was developed to realise simple water detection in organic solvents. The pyridinium betaine structure, comprising intramolecular hydrogen bonds between the oxygen in the maleimide moiety and the hydrogen in the pyridinium, was vital for achieving efficient fluorescence emission. The membrane was prepared by copolymerising PB1 with the N,N-dimethyl acrylamide/acrylamide monomer on a glass plate, and the fluorescence in water-mixed organic solvents was investigated (λabs = 490 nm, λfl = 630 nm). The fluorescence intensity of the dye-immobilised membrane decreased with increasing water content of the organic solvents. The detection ranges in tetrahydrofuran, ethanol, methanol, and dimethyl sulfoxide were approximately <40, <40, <40, and <60 vol% water, respectively. In contrast, membranes based on a quaternary pyridinium dye (without intramolecular hydrogen bonds) did not detect water in methanol and dimethyl sulfoxide, although it was more sensitive than PB1 in the narrow region of low water concentration in THF. Theoretical calculations corroborated the importance of the pyridinium betaine structure in detecting water in organic solvents, with the increase in polarity and the formation of intermolecular hydrogen bonds between PB1 and water found to induce molecular rotation and fluorescence quenching.

Luminescence turn-on sensor for the selective detection of trace water and methanol based on a Zn(ii) coordination polymer with 2,5-dihydroxyterephthalate.

A highly selective detection of trace water in organic solvents is urgently required for the chemical industry. In this work, the simple sonochemical method was used for producing a luminescent sensor, [Zn(H2dhtp)(2,2'-bpy)(H2O)]n (Zn-CP) (H2dhtp2- = 2,5-dihydroxyterephthalate and 2,2'-bpy = 2,2'-bipyridine). Zn-CP exhibits reversible thermally-induced and methanol-mediated structural transformation. Importantly, Zn-CP has exceptional water sensing performance in both dry methanol and dry ethanol, with high selectivity, wide linear ranges, and a low limit of detection (LOD) of 0.08% (v/v). Upon the incremental addition of water, the luminescent intensities enhanced and shifted, along with the emission color changing from green to greenish yellow. In addition, Zn-CP can detect methanol selectively through turn-on luminescence intensity with LODs of 0.28, 0.52, and 0.35% (v/v) in dry ethanol, dry n-propanol, and dry n-butanol, respectively. The excited-state proton transfer of linker H2dhtp2-via enol-keto tautomerism and collaboration with structural transformation could be attributed to the sensing mechanism.

Revisiting the excited state proton transfer dynamics in N-oxide-based fluorophores: a keto–enol/enolate interplay to detect trace water in organic solvents

This work highlights the unique proton transfer ability observed in cyanoquinoxaline N-oxide-based fluorophores and its use in water detection.

Construction of a zero-dimensional halide perovskite in micron scale towards a deeper understanding of phase transformation mechanism and fluorescence applications.

Zero-dimensional (0D) halide perovskites have garnered significant interest due to their novel properties in optoelectronic and energy applications. However, the mechanisms underlying their phase transformations and fluorescence properties remain poorly understood. In this study, we have synthesized a micron-scale 0D perovskite observable under confocal laser scanning microscopy (CLSM). This approach enables us to trace the phase transformation process from 0D to three-dimensional (3D) structures, offering a deeper understanding of the underlying mechanisms. Remarkably, we discovered that this in situ transformation is highly sensitive to water, allowing for label-free fluorescent analysis of trace amounts of water in organic solvents through the phase transformation process. Additionally, we have designed a reusable paper strip for humidity analysis leveraging this sensitivity as an application of the micron scale material. Our findings not only elucidate the physicochemical properties of perovskites but also expand the potential of halide perovskite materials in analytical chemistry.

An intrinsically zwitter-ionic COF: a carboxylic acid and pseudo-tetrahedral sp3 nitrogen functionalized covalent organic framework with potential for humidity sensing

A carboxylic acid functionalized sp3 N-rich imine bonded COF shows a humidity-dependent visible color change. This COF is easily exfoliated to nanosheets, which are explored as a potential humidity sensor that detects trace water in organic solvents.

Synthesis of polyoxothiometalates through site-selective post-editing sulfurization of polyoxometalates.

Polyoxometalates (POMs) function as platforms for synthesizing structurally well-defined inorganic molecules with diverse structures, metals, compositions, and arrangements. Although post-editing of the oxygen sites of POMs has great potential for development of unprecedented structures, electronic states, properties, and applications, facile methods for site-selective substitution of the oxygen sites with other atoms remain limited. Herein, we report a direct site-selective oxygen-sulfur substitution method that enables transforming POMs [XW12O40]4- (X = Si, Ge) to Keggin-type polyoxothiometalates (POTMs) [XW12O28S12]4- using sulfurizing reagents in an organic solvent. The resulting POTMs retain the original Keggin-type structure, with all 12 surface W[double bond, length as m-dash]O groups selectively converted to W[double bond, length as m-dash]S without sulfurization of other oxygen sites. These POTMs show high stability against water and O2 in organic solvents and a drastic change in the electronic states and redox properties. The findings of this study represent a facile method for converting POMs to POTMs, leading to the development of their unique properties and applications in diverse fields, including (photo)catalysis, sensing, optics, electronics, energy conversion, and batteries.

Porphyrin based covalent organic polymer for the fluorescence sensing of water in organic solvents

One porphyrin covalent organic polymer (PorMeO-COP) via Schiff base condensation using 5,10,15-tris(4-aminophenyl)porphyrin and 2,5-dimethoxyterephthaladehyde as the monomers have been designed and synthesized for fluorescence sensing of water content in organic solvents. The resulting PorMeO-COP display significant fluorescence enhancing upon the addition of different amount of water in eight common hydrophilic solvents. The sensing ranges are achieved over 0.2–6%, 1–20 %, 0.2–15 %, 1–16 %、1–40 %、2–10 %、4–14 % and 0.2–25 % (v/v) for water in methanol, ethanol, acetonitrile, acetone, tetrahydrofuran, N,N-dimethylformamide, dimethyl sulfoxide and 1,4-dioxane, respectively, and the limit of detection (LOD) are 0.032 %, 0.076 %, 0.054 %, 0.007 %, 0.014 %, 0.037 % and 0.024 % (v/v), respectively. These findings reveal PorMeO-COP can serve as fluorescence sensor to detect water content in organic solvents.

The design of multifunctional fluorescent probe for detecting Zn2+/ ClO−/H2O and application in high-security level information encryption

In this article, a Schiff base-structured compound (TNB) was synthesized using 3-hydroxy-2-naphthaldehyde hydrazone and 2-hydroxy-5-tert-butylbenzaldehyde as starting materials. The structure of TNB was characterized using NMR spectroscopy, high-resolution MS, and IR spectroscopy. Studies showed that TNB can selectively recognize Zn2+/ClO− in solvent system of H2O/DMSO. Fluorescence and UV–vis spectrophotometry were used to investigate the spectral properties of TNB. TNB displayed a significant fluorescence enhancement effect when bound to Zn2+, while binding to ClO− resulted in fluorescence quenching. Job’s plot and NMR titration were used to study the binding mechanism of TNB with Zn2+/ClO−. Linear standard curves were fitted for different Zn2+/ClO− concentrations corresponding to fluorescence intensity, and detection limits (LOD) were determined as 5.0300 × 10−9 mol/L (Zn2+) and 3.1700 × 10−9 mol/L (ClO−). Furthermore, TNB was used to determine trace water in organic solvents. The fluorescence intensity changes with water content were measured in three organic solvents (THF, DMSO, and acetone). Detection limits (LOD) were calculated as 1.4 × 10−4 % (THF), 8.3 × 10−4 % (DMSO), and 1.2 × 10−3 % (acetone). Using the characteristic reactions of TNB with Zn2+, a two-dimensional code information encryption technology was developed and can be used for high-security information encryption and transmission.

A highly water-soluble hydrogen-bond-induced emission carbon dots for ratiometric fluorescent detection of water content in organic solvents

Water in organic solvents is a prevalent impurity that significantly influences chemical reactions and industrial processes. Carbon dots (CDs) gained attention as promising tools for chemosensing due to their advantageous characteristics, including easy synthesis, cost-effectiveness, and excellent adjustability and stability. However, limited solubility in water and turn off fluorescence response mode hinder the practical utilization of CDs for water sensing. To tackle such dilemma, a highly water-soluble CDs with distinctive hydrogen-bond-induced emission (HBIE) was rationally designed through introducing sulfone group into the widely employed p-phenylenediamine precursor. The inclusion of sulfone group imparts the CDs with notable water solubility, as well as distinctive ratiometric fluorescent response towards water content, exhibiting high sensitivity and selectivity. Upon exposure to water, the emission color of CDs undergoes a real-time transition from blue to yellow-green, which can be readily discerned by naked eyes. The CDs have been successfully applied in detecting water in commercially available alcohol. This study presents a straightforward yet efficacious approach for rationally design of CDs with unique HBIE characteristics and ratiometric fluorescent response, offering great potential for practical chemosensing applications.

Visual detection of water content in liquor with near-infrared fluorescence sensor assisted by smartphone

Water content was an essential indicator in organic solvents, and it was necessary to develop a facile, cheap and readily available tool for the real-time, specifical and sensitive detection of water content. In this work, two novel D-π-A type near-infrared fluorescence sensors (DCM-1 and DCM-2) were designed and synthesized for the detection of trace water in organic solvents. DCM-1 and DCM-2 with solvent-dependent effects and large Stokes shift (>120 nm) showed good linear “intensity-to-content” relationships in four commonly-used organic solvents, and accomplished the ultra-fast and high-accuracy detection of the trace water in organic solvents. More importantly, a portable, fast, and accurate smartphone-assisted visual assay was designed for visual quantitative detection of the water content in organic solvents with a detection limit as low as 1.028 % v/v (e.g. in ethanol) and a wide detection range (0–60 % v/v). The smartphone-based visual assay was further applied to estimate the water content in disinfection alcohol and commercial liquor, which furnished a new strategy and broad prospects to achieve the accurate onsite detection of water content.

Multi-analyte fluorescence sensing based on a post-synthetically functionalized two-dimensional Zn-MOF nanosheets featuring excited-state proton transfer process

Covalent post-synthetic modification of metal–organic frameworks (MOFs) represents an underexplored but promising avenue for allowing the addition of specific fluorescent recognition elements to produce the novel MOF-based sensory materials with multiple-analyte detection capability. Here, an excited-state proton transfer (ESPT) active sensor 2D-Zn-NS-P was designed and constructed by covalent post-synthetic incorporation of the excited-state tautomeric 2-hydroxypyridine moiety into the ultrasonically exfoliated amino-tagged 2D Zn-MOF nanosheets (2D-Zn-NS). The water-mediated ESPT process facilitates the highly accessible active sites incorporated on the surface of 2D-Zn-NS-P to specifically respond to the presence of water in common organic solvents via fluorescence turn-on behavior, and accurate quantification of trace amount of water in acetonitrile, acetone and ethanol was established using the as-synthesized nanosheet sensor with the detection sensitivity (<0.01% v/v) superior to the conventional Karl Fischer titration. Upon exposure to Fe3+ or Cr2O72−, the intense blue emission of the aqueous colloidal dispersion of 2D-Zn-NS-P was selectively quenched even in the coexistence of common inorganic interferents. The prohibition of the water-mediated ESPT process and local emission, induced by the coordination of ESPT fluorophore with Fe3+ or by Cr2O72− competitively absorbs the excitation energy, was proposed to responsible for the fluorescence turn-off sensing of the respective analytes. The present study offers the attractive prospect to develop the ESPT-based fluorescent MOF nanosheets by covalent post-synthetic modification strategy as multi-functional sensors for detection of target analytes.