Addition Of HSO3 Research Articles

A ratiometric fluorescent sensor based on dual-emitting carbon dots for the rapid detection of sulfite

Sulfur dioxide (SO2) derivatives are typically employed as antioxidants in food and pharmaceutical processing. However, excessive sulfite intake could trigger serious health problems. Hence, it is urgent to establish a rapid and effective system for monitoring SO2. This study adopted a one-step hydrothermal method to synthesize dual-emitting nitrogen-doped carbon quantum dots (CECDs) and developed a ratiometric sensor for sulfite using CECDs-Cr (VI) composites. The emission intensity ratio (I440/I500) of the CECDs-Cr (VI) composites increased considerably with the addition of HSO3−. A method based on the ratiometric sensor was established for SO2 derivatives with advanced efficiency and excellent linearity over a broad concentration range of 0–500 μM (R2 = 0.9946). Four medicine-food homology materials (MFHMs) fumigated with sulfur have been accurately detected using this approach. Furthermore, a portable test tube was prepared to achieve rapid and semi-quantitative detection of SO2 residues and applied to real samples. This work presents an effective approach to develop a rapid on-site detection platform for sulfite residues in food and pharmaceuticals.

A colorimetric and NIR fluorescent probe for ultrafast detecting bisulfite and organic amines and its applications in food, imaging, and monitoring fish freshness

Herein, for the first time, we have successfully constructed a novel near-infrared (NIR) emission fluorescent probe Dpyt for ultrafast detecting (within 5 s) bisulfate and organic amines based on a 1,2-dihydrocyclopenta[b]chromene-barbiturate conjugation system. Upon addition of bisulfate or organic amines, Dpyt displayed a distinct color change from blue to colorless or from purple to blue, respectively, suggesting that the Dpyt can be used to detect two analytes by the naked eye. Based on quantum chemistry calculations, the fluorescence quenching of Dpyt after the addition of HSO3− is caused by the photoinduced electron transfer (PET) process of the adduct Dpyt-HSO3−. The fluorescence enhancement of Dpyt caused by most organic amines is due to the enhanced intramolecular charge transfer (ICT) process of deprotonated Dpyt. Notably, Dpyt can be applied for detecting HSO3− in actual food samples such as red wine and sugar, as well as for imaging of HSO3− and representative propylamine in living cells. And more importantly, indicator labels constructed by filter paper loaded with Dpyt can visually monitor the freshness of salmon in real-time by daylight and fluorescence dual-mode. The comparison with national standard method of China manifests that indicator labels are a valid tool to assess the freshness of seafood.

Understanding stress corrosion cracking behavior of 7085-T7651 aluminum alloy in polluted atmosphere

The electrochemical and Stress Corrosion Cracking (SCC) behaviors of 7085-T7651 aluminum alloy in different environments are studied by electrochemical and mechanical testing. The research shows that the type, concentration of the corrosive medium and electrolyte state affect the electrochemical and SCC controlling processes of aluminum alloys. The Thin Electrolyte Layer (TEL) state and the addition of HSO3– increase the corrosion rate and SCC susceptibility. The presence of HSO3– in a corrosive environment can significantly accelerate the corrosion rate and mechanical property degradation, and this effect increases with the increase of HSO3– concentration. Compared with the solution environment, the TEL environment will further aggravate corrosion and mechanical property degradation. With the increase of HSO3– concentration, the pH of the corrosive environment exhibits little change, while the SCC degradation is significantly promoted. This is attributed to the HSO3– induced buffer effect and film-assisted stress effect, yielding the overshadowing effect against solution pH.

Water-soluble ratiometric fluorescent probes for exogenous and endogenous sulfur dioxide derivatives

Abnormal SO2 derivatives level induces mitochondrial and lysosomal dysfunction, which is associated with a variety of diseases. Therefore, it is imperative to develop fluorescent probes which are suitable for detection of SO2 derivatives in biological systems. Herein, we developed two new ratiometric fluorescent probes, MByn and HByn, which can respond to HSO3− in PBS buffer solution accurately and rapidly on basis of Michael addition reaction. After addition of HSO3−, ratiometric response signal increases by 5 folds, accompanied by a macroscopic change of fluorescence color. What's more, the two novel fluorescent probes MByn and HByn exhibited low detection limit (LOD = 0.96/0.79 μM), good photostability and low cytotoxicity. Cell imaging experiments showed that MByn and HByn were able to localize mitochondria and lysosomes accurately and detect both exogenous and endogenous SO2 derivatives in living cells.

Study on the roles of bisulfite in the stress corrosion cracking of 7050-T7451 aluminum alloy in the thin electrolyte layer environment

Effect of bisulfite (HSO3-) on the stress corrosion cracking (SCC) behavior of 7050-T7451 aluminum alloy in the thin electrolyte layer environment in the presence of Cl- is investigated. Addition of HSO3- inhibits the corrosion initiation but promotes the corrosion propagation and hydrogen uptake. With a quantitative calculation, the HSO3- is demonstrated to significantly facilitate the synergistic effect between stress, corrosion, and hydrogen during the in-situ tensile test, resulting in the change of the SCC controlling step from corrosion-induced hydrogen to mechanical-electrochemical-hydrogen interactions. The buffer effect of HSO3- plays a dominant role in the HSO3--induced acceleration of the SCC degradation.

A coumarin/cyanoacetamide-derived lysosome-targeting probe for detecting bisulfite and viscosity changes in living cells and zebrafish

A coumarin/cyanoacetamide-based probe was produced by a simple condensation reaction. The probe exhibits high selectivity towards bisulfite (HSO3−) and viscosity changes based on either fluorescence or UV–Vis spectra in almost pure aqueous media. The addition of HSO3− induced a significant blue shift in the emission maximum of the free probe (from 575 nm to 485 nm) with a short response time (5 min), a broad function pH range (3.0–11.0), and a low detection limit (74 nM), via the recognition mechanism of bisulfite-involved Michael addition reaction. In parallel, the fluorescence intensity at 575 nm of the probe increased significantly along the increasing viscosity of the test media owing to the prohibited rotation of CC bridged rotors in probe 1. Notably, the probe could monitor the level of lysosomal HSO3− and viscosity changes in HeLa cells and zebrafish.

Reversible Near-Infrared Fluorescent Probe for Rapid Sensing Sulfur Dioxide and Formaldehyde: Recognition and Photoactivation Mechanism and Applications in Bioimaging and Encryption Ink.

A novel near-infrared (NIR) fluorescent Probe 1 was successfully developed for the reversible detection of sulfur dioxide derivatives and formaldehyde. The purple solution of Probe 1 faded to colorless in 1.8 s with the addition of HSO3-. Meanwhile, its fluorescence signal disappeared instantaneously with a 39 nM detection limit. The probe exhibited excellent selectivity toward HSO3- over other potential interfering agents. Then, its absorption and fluorescence bands were able to effectively recover in response to formaldehyde. Remarkably, this reverse process was able to accelerate 84 times under UV light in 122 s and achieved a recovery rate of 98% by UV light, the photoactivation mechanism was fully determined by HRMS and theoretical calculation. Furthermore, we demonstrated that Probe 1 was successfully applied for the detection of sulfur dioxide derivatives and formaldehyde in living cells and data encryption.

Designing of a high-performance fluorescent small molecule enables dual-mode and ultra-sensitive fluorescence visualizing of HSO3− and HClO in dried fruit, beverage, and water samples

Herein, a novel hemicyanine derivative (E)-3-(1,1-dimethyl-2-(4-(methylthio)styryl)-1H-benzo[e]indol-3-ium-3-yl)propane-1-sulfonate (BIS) has been reasonably designed. Compound BIS is long-wavelength emissive and water-soluble with a large Stokes shift. Intriguingly, probe BIS provides a dual-mode fluorescence response pattern for the sensing of bisulfite (HSO3−) and hypochlorous acid (HClO) with great limit of detections (3.6 and 57.4 nM). First, the 1,4-Michael addition of HSO3− on the conjugated double bond triggers a ratiometric response (I465/I575). Second, the rapid oxidation of HClO on the thioether moiety provides a turn-on response (I575). Evaluation of HSO3− and HClO levels in dried fruit, beverage, and water samples has been carried out with satisfactory results. Moreover, motivated by an impressive chromatic variation (red to blue), smartphone-assisted signal readout system and thin-film sensing platform are facilely constructed for real-time and on-site measurement of HSO3− levels. Furthermore, probe BIS is used for the in vivo imaging of HSO3− in edible fish models.

The promoting effect of bisulfite on pollutant abatement by Fe(II)/peroxydisulfate: Dual roles of bisulfite as the accelerator of FeII-(FeIII/FeIV) recycling and radical precursor

The advanced oxidation processes (AOPs) with Fe(II) as homogenous activator suffer from the accumulation of insoluble Fe(III) oxides which results in the decrease of available catalyst and increase of iron sludge. Herein, with Fe(II)/peroxydisulfate (Fe(II)/PDS) process as an example, HSO3– was proposed to enhance the regeneration of Fe(II). The results showed that 250 µM of HSO3– increased the removal of benzoic acid (BA) from 18.8% to 41.3% while further increasing HSO3– dosage promoted its scavenging effects and decreased BA removal. Accordingly, multiple-dosing mode of HSO3– was used which enhanced BA removal to 63.8%. Addition of HSO3– recovered Fe(II) from Fe(III)/Fe(IV) and shifted the distribution of reactive species from Fe(IV) to SO4−. Besides as the reductant, the reaction of HSO3– with Fe(III) and Fe(IV) severed as the AOPs and produced SO4−. A mathematic model was constructed for the Fe(II)/PDS/HSO3– process, and it revealed that ∼ 78% of dosed HSO3– was transformed to SO4−, but ∼ 81% of the generated SO4− was consumed by HSO3–. The reaction of Fe(IV) with HSO3– and the activation of in situ formed peroxymonosulfate by Fe(II) are chiefly responsible for SO4− formation with the contributions of ∼ 47% and ∼ 27%, respectively, in the Fe(II)/PDS/HSO3– process. Considering the complexity of the multiple-dosing mode of HSO3– in the real practice, the sparingly soluble CaS2O5 which released HSO3– gradually was synthesized and used. The single dosing of CaS2O5 stood out in terms of promoting pollutant abatement by the Fe(II)/PDS process compared to that adding equivalent of HSO3–. These results will benefit the optimization of the Fe(II)-based AOPs.

A quinoline-based probe for the ratiometric fluorescent detection of sulfite in lysosomes of living cells

A lysosome-targeting ratiometric fluorescent probe was synthesized for detecting sulfite based on sulfite-triggered nucleophilic addition reaction. Due to the specific reaction, the fluorescence intensity ratio (I530/I390) of the probe in an almost aqueous solution (0.5% DMSO) changed significantly after the addition of HSO3−, corresponding to the change in the fluorescence color of the solution from green to blue. The recognition was conducted using high-resolution mass spectrometry, proton nuclear magnetic resonance, and density functional theory calculations. The fluorescent probe could be utilized to quantitatively monitor HSO3− in lysosomes of living C6 glioma cells and real-water samples.

Human peripheral blood mononuclear cells targeted multidimensional switch for selective detection of HSO3− anion

A new ratiometric π-conjugated luminophore with donor-acceptor (D- π- A) network CM {(E)-2-(4-(2-(9-butyl-9H-carbazol-3-yl)vinyl)benzylidine)malononitrile} has been synthesized by malononitrile conjugated carbazole dye with an intervening p-styryl spacer. Here, p-styryl conjugated malononitrile is used as a recognition site for the detection of HSO3− with a fast response time (within 50 s). In a mixed aqueous solution, CM reacts with HSO3− to give a new product 1-(9-butyl-9H-carbazol-3-yl)-2-(4-(2, 2-dicyanovinyl)phenyl)ethane-1-sulfonic acid. The probe exhibits positive solvatofluorochromism with solid state red fluorescence. The restriction of intermolecular rotation of p-styryl conjugated malononitrile unit enhances the typical solid state fluorescence properties. The probe (CM and its corresponding aldehyde CA) also demonstrates a strong solvent dependence yielding blue to green to pink and even red fluorescence in commonly used organic solvents like n-hexane, toluene, diethyl ether (DEE), THF, DCM, Dioxane, CH3CN and MeOH. The chemodosimetric approach of HSO3− selectively takes place at the olefinic carbon exhibiting a prominent chromogenic as well as ratiometric fluorescence change with a 147 nm blue-shift in the fluorescence spectrum. CM can detect HSO3− as low as 1.21 × 10−8 M. Moreover, the CM can be successfully applied to detect intrinsically generated intracellular HSO3− in human peripheral blood mononuclear cells (PBMCs). CM has shown sharp intensities (2628 ± 511.8) when the cells are HSO3− untreated. At green channel (at 486 nm) almost negligible fluorescence intensities are found (423 ± 127.5) for HSO3− untreated samples. However, the green fluorescence (2863 ± 427.5) increases significantly (p < 0.05), and simultaneously the red fluorescence gets significantly (p < 0.05) diminished (515 ± 113.2) after addition of HSO3−. The CM has been effectively utilized for evaluating the bisulfite ions in food samples as well. The concentrations of HSO3− in diluted sugar samples have been determined with the recovery of 97.6–9.12%.

Determination of hypochlorite and bisulfite in water by bifunctional colorimetric sensor based on octupolar conjugated merocyanine dyes

In this study, we developed a bifunctional colorimetric fluorescent sensor based on three merocyanine structures for the detection of hypochlorite (ClO−) and bisulfite (HSO3−). In MeOH solution and under special conditions, this sensor shows high selectivity on fluorescence and UV–Vis spectra for the detection of ClO− and HSO3−, respectively. The sensor solution exhibits a strong red fluorescence emission at 638 nm, which was quenched and the blue color turned to purple pink rapidly upon the addition of ClO−. The mechanism of the detection of ClO− was confirmed via ESI-MS that the CC groups were induced to produce ethylene oxide and ethylene glycol derivatives by hypochlorite. The fluorescence emission at 638 nm in the concentration range of ClO− from 0 to 24 μM showed a good linear relationship (R2 = 0.9919), and the LOD of the sensor for ClO− was 0.42 μM. Interestingly, the sensor can also detect HSO3− in acid condition (pH less than 7.4). The blue shift of UV–Vis spectra of the solution of sensor were observed after addition of HSO3− and irradiation with visible light for about 4 min. The HSO3− concentration showed a good linear relationship (R2 = 0.9987) at 275 nm in the range of 12–42 μM, and thus its LOD was calculated to be 1.14 μM. Finally, the sensor has important value for detecting ClO− and HSO3− in tap water and lake water.

Sensitive quantitative image analysis of bisulfite based on near-infrared upconversion luminescence total internal reflection platform

Bisulfite (HSO3−), serves as an important additive in food industry, is one of the most widely distributed environmental pollutants. Herein, a fast and efficient quantitative image analysis method for the determination of HSO3− has been developed. The method builds a luminescence energy transfer (LET) system utilized upconversion nanoparticles (UCNPs) as an energy donor and cyanine dye molecules as an energy acceptor. The upconversion luminescence is quenched a lot on the addition of dye molecules and gets recovered well with the addition of HSO3−. All the phenomena can be recorded via traditional luminescence spectrometer and near-infrared upconversion luminescence total internal reflection platform. The quantitative image analysis performed on the near-infrared upconversion luminescence total internal reflection platform can significantly reduce sample consumption (10 μL) as well as make a quick and efficient analysis (0.1 s) with a large amout of data become easy. Meanwhile, it shows a wider linear range (1–120 μM), lower detection limit (0.070 μM) and higher detection speed than that of the classical luminescence spectrometer.

Bisulfite-induced drastic enhancement of bisphenol A degradation in Fe3+-H2O2 Fenton system

The present work aimed at using bisulfites (HSO3−) to enhance the oxidative degradation of bisphenol A (BPA) in a Fenton process based on the Fe3+-H2O2 reagents. It was confirmed that both the degradation and mineralization of BPA were drastically enhanced by the addition of HSO3−. Typically, the use of 0.1 mmol L−1 Fe3+, 0.3 mmol L−1 HSO3− and 10 mmol L−1 H2O2 achieved a complete degradation of BPA (0.05 mmol L−1) in only 2 min. The addition of HSO3− increased the BPA degradation rate constant from 0.045 min−1 in the Fe3+-H2O2 system to 2.71 min−1 in the Fe3+-HSO3−-H2O2 system by 60 times. This drastic enhancement effect of HSO3− was attributed to its complexing and reducing abilities. The formation of FeSO3+ complex prevented the precipitation of Fe3+ and accelerated the cycling of Fe3+/Fe2+; the reducing ability of HSO3− further favored the transformation of Fe3+ to Fe2+. Several reactive species, including OH, SO3− and SO4− were responsible for the degradation of BPA, among which OH was the dominant one. The proposed Fe3+-HSO3−-H2O2 system is suggested be able to act as the followed stage of a traditional Fe2+-H2O2 system in the engineering setting.

Differentiate bisulfite from sulfite by a new cycloruthenated 2-(2-thienyl)pyridine complex in pure water

A new cycloruthenated 2-(2-thienyl)pyridine complex (1) with a benzo[e]indolium block was successfully synthesized and characterized, which has good water-solubility and displays a maximum absorption band centered at 730 nm (ε = 6.3 × 103 M−1 cm−1) in water. Moreover, its absorption edge can extend to 1000 nm. When either HSO3– or SO32– ions were added to the buffer solutions of 1, obvious color changes from dark-red to purplish-red were observed. However, it is noticeable that the addition of HSO3– ions resulted in the solution color of this complex changing from dark-red to colorless other than purplish-red. The different solution color changes displayed that 1 can be used as an optical chemo-sensor to distinguish HSO3– from SO32– in pure water.

Reaction-based fluorescent sensor for detection of bisulfite through 1,4-addition reaction in water

Reaction-based fluorescent sensor (L) based upon a conjugated benzothiazol structure was synthesized and used for detection of bisulfite (HSO3−) in water. L displayed large change in both fluorescence and absorption spectra immediately after the addition of HSO3−. It can be easily observed about the fading of the solution’s color through the naked eye. The HSO3− underwent a 1,4-addition reaction with the C-4 atom in the ethylene group. The detection limit of L for HSO3− was measured to be 0.45 μmol/L. The live cell fluorescent experiments proved the potential application of the L in tracing the HSO3− in future biological systems.

Two water-soluble two-photon fluorescence probes for ratiometric imaging endogenous SO2 derivatives in mitochondria

Rational and convenient design water-soluble two-photon excited fluorescence (TPEF) probes for monitoring SO2 derivatives with specificity at subcellular level remain a challenge. Herein, two low molecular weight, ratiometric fluorescence probes, bearing α, β-unsaturated benzoindolium moiety (EIM and EIS), are designed for monitoring endogenously SO2 derivatives in mitochondria using two-photon microscopy (TPM). The two probes not only showed >100nm blue-shift emission with two well-resolved bands upon addition of HSO3−/SO32−, but also displayed rapid response, high selectivity and sensitivity for monitoring and quantifying HSO3−/SO32− over other species in living cells. Further studies indicated that probes EIM and EIS can highly discern HSO3−/SO32− with two different nucleophilic addition mechanisms, respectively, just by structural fine-tuning, which were confirmed by both theoretical calculation and experimental technique. It is suggested that probes EIM/EIS with two-photon absorption property in the NIR region, large Stocks shift, high selectivity and signal ratio, are promising molecular tool for bisulfite/sulfite biology.

A ratiometric fluorescent probe for sensing bisulphate and its application in living cells and zebrafish

A novel near-infrared fluorescent probe for detection of bisulfite was designed and developed based on a conjugated naphthopyran-indolium system. The sensor showed excellent selectivity, high sensitivity and a rapid response toward bisulfite in aqueous solution. Upon the addition of HSO3−, the sensor displayed 21.6-fold ( I 520/ I 653) fluorescence intensity enhancement, accompanied with an apparent color change from violet to colorless, suggesting that the sensor can be used to detect HSO3− with “naked-eye”. The lowest detection limit for the above measurement was found to be 76 nM, and it was sensitive enough for the detection of endogenously produced bisulfite in biological system. Furthermore, the sensing mechanism was confirmed by high-resolution mass spectroscopy analysis and 1H NMR spectrometry analysis, which was based on the strong nucleophilic addition reaction of bisulfite towards the sensor. Moreover, as a biocompatible molecule, the probe was successfully used for fluorescence imaging of bisulfite in MCF-7 cells and zebrafish, demonstrating that the probe is a novel ratiometric fluorescent probe to image SO2 derivatives in biosystem.

Reversible Ratiometric Fluorescent Probe for Sensing Bisulfate/H2O2 and Its Application in Zebrafish.

Herein, a novel near-infrared fluorescent probe for ratiometric detection of bisulfate was designed and developed based on a conjugation of naphthopyran-benzothiazolium system. The sensor showed excellent selectivity, high sensitivity and a rapid response toward bisulfite in aqueous solution. Upon the addition of HSO3-, the sensor displayed 37-fold (I520/I630) fluorescence intensity enhancement, accompanied by an apparent color change from violet to colorless, suggesting that the sensor can be used to detect HSO3- with "naked-eye". Notably, the addition product can be applied to the design of regenerative chemodosimeters based on the H2O2 promoted elimination of bisulfite and recovery of probe 1. Further cell and zebrafish imaging experiment demonstrated that the sensor could image the bisulfite/H2O2 redox cycle in biological system with ratiometric manners.

A TICT based two-photon fluorescent probe for bisulfite anion and its application in living cells

A two-photon fluorescent probe (DMPCA) for the detection of bisulfite anion in water was developed based on twisted-intramolecular-charge-transfer (TICT) mechanism. Fluorescence intensity of DMPCA increased dramatically (65 fold) upon the addition of HSO3−. The two-photon absorption cross-section of DMPCA was found to be 725 GM at 700nm upon the addition of HSO3−. The fluorescent probe showed an excellent selectivity for bisulfite anion over other anions. The nucleophilic addition reaction mechanism with aldehyde was confirmed with NMR and MALDI-TOF. The TICT detection mechanism was confirmed by viscosity-dependent fluorescence spectra and time resolved fluorescence spectra. Moreover, DMPCA was successfully applied to the detection of bisulfite anion in HeLa cells with low cytotoxicity under two-photon excitation.