Chalcogen Noncovalent Interactions between Diazines and Sulfur Oxides in Supramolecular Circular Chains.

The noncovalent chalcogen interaction between SO2/SO3 and diazines was studied through a dispersion-corrected DFT Kohn-Sham molecular orbital together with quantitative energy decomposition analyses. For this, supramolecular circular chains of up to 12 molecules were built with the aim of checking the capability of diazine molecules to detect SO2/SO3 compounds within the atmosphere. Trends in the interaction energies with the increasing number of molecules are mainly determined by the Pauli steric repulsion involved in these σ-hole/π-hole interactions. But more importantly, despite the assumed electrostatic nature of the involved interactions, the covalent component also plays a determinant role in its strength in the involved chalcogen bonds. Noticeably, π-hole interactions are supported by the charge transfer from diazines to SO2/SO3 molecules. Interaction energies in these supramolecular complexes are not only determined by the S···N bond lengths but attractive electrostatic and orbital interactions also determine the trends. These results should allow us to establish the fundamental characteristics of chalcogen bonding based on its strength and nature, which is of relevance for the capture of sulfur oxides.

Insight into the interaction between amino acids and SO2: Detailed bonding modes.

CONTEXT: Amino acids are a highly effective and environmentally friendly adsorbent for SO2. However, there has been no comprehensive study of the binding modes between amino acids and SO2 at the molecular level. In this paper, the binding modes of three amino acids (Asp, Lys, and Val) with SO2 are studied comprehensively and in detail using quantum chemical calculations. The results indicate that each amino acid has multiple binding modes: 22 for Asp, 49 for Lys, and 10 for Val. Both the amino and carboxyl groups in amino acids, as well as those in side chains, can serve as binding sites for chalcogen bonds. The binding energies range from - 6.42 to - 1.06 kcal/mol for Asp, - 12.43 to - 1.63 kcal/mol for Lys, and - 7.42 to - 0.60 kcal/mol for Val. Chalcogen and hydrogen bonds play a crucial role in the stronger binding modes. The chalcogen bond is the strongest when interacting with an amino group, with an adiabatic force constant of 0.475 mDyn/Å. Energy decomposition analysis indicates that the interaction is primarily electrostatic attraction, with the orbital and dispersive interactions dependent on the binding mode. METHODS: Amino acids and complexes of amino acids with SO2 were used to do semi-empirical MD using Molclus combined with xtb at the GFN2 level. Optimization and frequency calculations of the structures were conducted using density-functional theory (DFT) B3LYP/6-311G* (with DFT-D3 correction). Single-point energy calculations were performed for all structures using DLPNO-CCSD(T)/aug-cc-pVTZ with tightPNO. Further analysis of the structures was conducted using ESP, AIM, IGMH, and sob-EDA to gain a deeper understanding of the interactions between amino acids and SO2.

A mitochondria-specific NIR fluorescence probe for dual-detection of sulfur dioxide and viscosity in living cells and mice.

The level of sulfur dioxide (SO2) and viscosity in mitochondria play vital roles in various physiological and pathological processes. Abnormalities in mitochondrial SO2 and viscosity are closely associated with numerous biological diseases. It is of great significance to develop novel fluorescence probes for simultaneous detection of SO2 and viscosity within mitochondria. Herein, we have developed a water-soluble, mitochondrial-targeted and near-infrared fluorescent probe, CMBT, for the simultaneous detection of SO2 and viscosity. The probe CMBT incorporates benzothiazolium salt as a mitochondrial targeting moiety and 7-diethylaminocoumarin as a rotor for viscosity detection, respectively. Based on the prompt reaction between nucleophilic HSO3-/SO32- and the backbone of the benzothiazolium salt derivative, probe CMBT displayed high sensitivity and selectivity toward SO2 with a limit of detection as low as 0.17 µM. As viscosity increased, the twisted intramolecular charge transfer (TICT) process was restricted, resulting in fluorescence emission enhancement at 690 nm. Moreover, probe CMBT demonstrated exceptional mitochondrial targeting ability and was successfully employed to image variations of SO2 and viscosity in living cells and mice. The work highlights the great potential of the probe as a convenient tool for revealing the relationship between SO2 and viscosity in biological systems.

Photochemistry of Imidazole-2-carbaldehyde in Droplets as a Potential Source of H2O2 and Its Oxidation of SO2.

Hydrogen peroxide (H2O2) plays a crucial role as an oxidizing agent within the tropospheric environment, making a substantial contribution to sulfate formation in hydrated aerosols and cloud and fog droplets. Field observations show that high levels of H2O2 are often observed in heavy haze events and polluted air. However, the source of H2O2 remains unclear. Here, using the droplets formed in situ by the deliquescence of hygroscopic compounds under a high relative humidity (RH), the formation of H2O2 by the photochemistry of imidazole-2-carbaldehyde (2-IC) under ultraviolet irradiation was explored. The results indicate that 2-IC produces IM-C•-OH and IM-C•═O radicals via H transfer itself to its excited triplet state and generates H2O2 and organic peroxides in the presence of O2, which has an evident oxidizing effect on SO2, suggesting the potential involvement of this pathway in the formation of atmospheric sulfate. H2O2 formation is limited in acidic droplets or droplets containing ammonium ions, and no H2O2 is detected in droplets containing nitrate, whereas droplets containing citric acid have an obvious promotion effect on H2O2 formation. These findings provide valuable insights into the behaviors of atmospheric photosensitizers, the source of H2O2, and the formation of sulfate in atmospheric droplets.

Kinetic study of isoprene hydroxy hydroperoxide radicals reacting with sulphur dioxide and their global-scale impact on sulphate formation.

Isoprene is the most relevant volatile organic compound emitted during the biosynthesis of metabolism processes. The oxidation of isoprene by a hydroxy radical (OH) is one of the main consumption schemes that generate six isomers of isoprene hydroxy hydroperoxide radicals (ISOPOOs). In this study, the rate constants of ISOPOOs + sulphur dioxide (SO2) reactions that eventually generate sulphur trioxide (SO3), the precursor of sulphate aerosol (SO42-(p)), are determined using microcanonical kinetic theories coupled with molecular structures and energies estimated by quantum chemical calculations. The results show that the reaction rates range from 10-27 to 10-20 cm3 molecule-1 s-1, depending on the atmospheric temperature and structure of the six ISOPOO isomers. The effect of SO3 formation from SO2 oxidation by ISOPOOs on the atmosphere is evaluated by a global chemical transport model, along with the rate constants obtained from microcanonical kinetic theories. The results show that SO3 formation is enhanced in regions with high SO2 or low nitrogen oxide (NO), such as China, the Middle East, and Amazon rainforests. However, the production rates of SO3 formation by ISOPOOs + SO2 reactions are eight orders of magnitude lower than that from the OH + SO2 reaction. This is indicative of SO42-(p) formation from the direct oxidation of SO2 by ISOPOOs, which is almost negligible in the atmosphere. The results of this study entail a detailed analysis of SO3 formation from gas-phase reactions of isoprene-derived products.

Insights into the Formation Mechanism of Reactive Oxygen Species in the Interface Reaction of SO2 on Hematite.

The interplay between sulfur and iron holds significant importance in their atmospheric cycle, yet a complete understanding of their coupling mechanism remains elusive. This investigation delves comprehensively into the evolution of reactive oxygen species (ROS) during the interfacial reactions involving sulfur dioxide (SO2) and iron oxides under varying relative humidity conditions. Notably, the direct activation of water by iron oxide was observed to generate a surface hydroxyl radical (•OH). In comparison, the aging of SO2 was found to markedly augment the production of •OH radicals on the surface of α-Fe2O3 under humid conditions. This augmentation was ascribed to the generation of superoxide radicals (•O2-) stemming from the activation of O2 through the Fe(II)/Fe(III) cycle and its combination with the H+ ion to produce hydrogen peroxide (H2O2) on the acidic surface. Moreover, the identification of moderate relative humidity as a pivotal factor in sustaining the surface acidity of iron oxide during SO2 aging underscores its crucial role in the coupling of iron dissolution, ROS production, and SO2 oxidation. Consequently, the interfacial reactions between SO2 and iron oxides under humid conditions are elucidated as atmospheric processes that enhance oxidation capacity rather than deplete ROS. These revelations offer novel insights into the mechanisms underlying •OH radical generation and oxidative potential within atmospheric interfacial chemistry.

Mitochondria-targeted fluorescent probe for simultaneously imaging viscosity and sulfite in inflammation models.

Many diseases in the human body are related to the overexpression of viscosity and sulfur dioxide. Therefore, it is essential to develop rapid and sensitive fluorescent probes to detect viscosity and sulfur dioxide. In the present work, we developed a dual-response fluorescent probe (ES) for efficient detection of viscosity and sulfur dioxide while targeting mitochondria well. The probe generates intramolecular charge transfer by pushing and pulling the electron-electron system, and the ICT effect is destroyed and the fluorescence quenched upon reaction with sulfite. The rotation of the molecule is inhibited in the high-viscosity system, producing a bright red light. In addition, the probe has good biocompatibility and can be used to detect sulfite in cells, zebrafish and mice, as well as upregulation of viscosity in LPS-induced inflammation models. We expect that the dual response fluorescent probe ES will be able to detect viscosity and sulfite efficiently, providing an effective means of detecting viscosity and sulfite-related diseases.

Modulating the Activity and SO2 Resistance of α-Fe2O3 Catalysts for NH3-SCR of NOx via Crystal Facet Engineering.

The development of Fe-based catalysts for the selective catalytic reduction of NOx by NH3 (NH3-SCR of NOx) has garnered significant attention due to their exceptional SO2 resistance. However, the influence of different sulfur-containing species (e.g., ferric sulfates and ammonium sulfates) on the NH3-SCR activity of Fe-based catalysts as well as its dependence on exposed crystal facets of Fe2O3 has not been revealed. This work disclosed that nanorod-like α-Fe2O3 (Fe2O3-NR) predominantly exposing (110) facet performed better than nanosheet-like α-Fe2O3 (Fe2O3-NS) predominantly exposing (001) facet in NH3-SCR reaction, due to the advantages of Fe2O3-NR in redox properties and surface acidity. Furthermore, the results of the SO2/H2O resistance test at a critical temperature of 250 °C, catalytic performance evaluations on Fe2O3-NR and Fe2O3-NS sulfated by SO2 + O2 or deposited with NH4HSO4 (ABS), and systematic characterization revealed that the reactivity of ammonium sulfates on Fe2O3 catalysts to NO(+O2) contributed to their improved catalytic performance, while ferric sulfates showed enhancing and inhibiting effects on NH3-SCR activity on Fe2O3-NR and Fe2O3-NS, respectively; despite this, Fe2O3-NR showed higher affinity for SO2 + O2. This work set a milestone in understanding the NH3-SCR reaction on Fe2O3 catalysts in the presence of SO2 from the aspect of crystal facet engineering.

The relevant effect of marine salt and epiphytes on Posidonia oceanica waste pyrolysis: Removal of SO2/HCl emissions and promotion of O/HCOOH formation.

Significant quantities of Posidonia oceanica deposit on some beaches and coastlines every year, which generates high costs associated with the disposal of this waste. Pyrolysis may be an adequate way for its valorization. However, it would imply to know how the process takes place and if the removal of its natural detrital inorganic matter (epiphytes, marine salt and sand) is necessary, which are the objectives of this research. Pyrolysis by thermogravimetry-mass spectrometry was carried out on both the washed and unwashed samples. During this waste pyrolysis, the following occurs: (i) the high alkali metal chloride content promotes fragmentation reactions of carbohydrates and O formation, which increases HCOOH intensities at temperatures between 250 and 360 °C; (ii) from 500 °C to 650 °C, Fe2O3 and decomposition of carbonates seem to be involved in reactions that produce O release and steam and CO2 reforming of hydrocarbons and oxygenated organic compounds with H2 generation; (iii) from 650 °C to 750 °C, Fe2O3, high alkali metal content and carbonate decomposition generate char gasification, an increase in O release, SO2 capture and HCOOH formation. In general, the abundance of inorganic matter (chlorides, carbonates, etc.) minimizes the release of various compounds during pyrolysis, including SO2 and HCl, while increasing HCOOH production. Thus, this high content of inorganic matter may represent an advantage for its pyrolysis, producing value-added chemical products with a reduced environmental impact. Therefore, this study may be the starting point for defining the optimal pyrolysis conditions for this waste valorisation.

1H NMR based sulfonation reaction kinetics of wine relevant thiols in comparison with known carbonyls.

Sulfite addition is a common tool for ensuring wines' oxidative stability via the activity of its free and weakly bound molecular fraction. As a nucleophile, bisulfite forms covalent adducts with wine's most relevant electrophiles, such as carbonyls, polyphenols, and thiols. The equilibrium in these reactions is often represented as dissociation rather than formation. Recent studies from our laboratory demonstrate, first, the acetaldehyde sulfonate dissociation, and second, the chemical stability of cysteine and epicatechin sulfonates under wine aging conditions. Thus, the objective of this study was to monitor by 1H NMR the binding specificity of known carbonyl-derived SO2 binders (acetaldehyde and pyruvic acid) in the presence of S-containing compounds (cysteine and glutathione). We report that during simulated wine aging, the sulfur dioxide that is rapidly bound to carbonyl compounds will be released and will bind to cysteine and glutathione, demonstrating the long-term sulfur dioxide binding potential of S-containing compounds. These results are meant to serve as a complement to existing literature reviews focused on molecular markers related to wines' oxidative stability and emphasize once more the importance of S-containing compounds in wine aging chemical mechanisms.

Lab- and pilot-scale wet scrubber study on the redox-mediated simultaneous removal of NOx and SO2 using a CaCO3-based slurry with KI as a redox catalyst.

This study presents a novel approach that integrates ozone-driven chemical oxidation to convert NO into soluble NO2, followed by the simultaneous absorption of NO2 and SO2 into a CaCO3-based slurry using the redox catalyst potassium iodide (KI). Using cyclic voltammetry, we demonstrate the redox properties of the I2/2I- couple, which facilitates NO2 reduction into soluble NO2- and catalyst regeneration through sulfite (SO32-)-driven reduction, thus establishing a closed catalytic cycle within the components of flue gas. In lab-scale wet-scrubbing tests, we explore the effect of various operational parameters (i.e., KI concentration, pH, and SO2 concentration), with a 15 h stability test demonstrating >60% NOx and >99% SO2 removal efficiency when the pH is controlled between 7.5 and 8.5. A successful pilot-scale implementation conducted at an inlet flow rate of 1000 m3 h-1 further confirmed the reproducibility of the proposed redox-catalytic cycle. Our study offers a cost-effective, sustainable, and scalable solution for effectively mitigating NOx and SO2 emissions at low temperatures.

Glutathione-triggered release of SO2 gas to augment oxidative stress for enhanced chemodynamic and sonodynamic therapy.

Recently, gas therapy has emerged as a promising alternative treatment for deep-seated tumors. However, some challenges regarding insufficient or uncontrolled gas generation as well as unclear therapeutic mechanisms restrict its further clinical application. Herein, a well-designed nanoreactor based on intracellular glutathione (GSH)-triggered generation of sulfur dioxide (SO2) gas to augment oxidative stress has been developed for synergistic chemodynamic therapy (CDT)/sonodynamic therapy (SDT)/SO2 gas therapy. The nanoreactor (designed as CCM@FH-DNs) is constructed by employing iron-doped hollow mesoporous silica nanoparticles as carriers, the surface of which was modified with the SO2 prodrug 2,4-dinitrobenzenesulfonyl (DNs) and further coated with cancer cell membranes for homologous targeting. The CCM@FH-DNs can not only serve as a Fenton-like agent for CDT, but also as a sonosensitizer for SDT. Importantly, CCM@FH-DNs can release SO2 for SO2-mediated gas therapy. Both in vitro and in vivo evaluations demonstrate that the CCM@FH-DNs nanoreactor performs well in augmenting oxidative stress for SO2 gas therapy-enhanced CDT/SDT via GSH depletion and glutathione peroxidase-4 enzyme deactivation as well as superoxide dismutase inhibition. Moreover, the doped iron ions ensure that the CCM@FH-DNs nanoreactors enable magnetic resonance imaging-guided therapy. Such a GSH-triggered SO2 gas therapy-enhanced CDT/SDT strategy provides an intelligent paradigm for developing efficient tumor microenvironment-responsive treatments.

Chemical Stability of Thiol and Flavanol Sulfonation Products during Wine Aging Conditions.

Bisulfite (HSO3-) is the predominant form of sulfur dioxide, present as free and bound to wine relevant electrophiles under wine acidic pH. While sulfonation reactions of flavanols and thiols have been recently reported as key for wine preservation against oxidation, the transient mechanisms and physicochemical parameters responsible for that remain unknown. In the present study, sulfonation reaction kinetics of thiols and flavanols were monitored under simulated wine aging conditions. The reaction products were then characterized by liquid chromatography-tandem mass spectrometry (LC-MS/MS) analysis, and their chemical stability during time was determined by 1H NMR spectroscopy. Thiol and flavanol sulfonation reaction yields were both promoted by the presence of iron and oxygen, while their chemical stability was confirmed under the same conditions. The sulfonation derivatives of epicatechin and cysteine were synthesized and quantified in young and aged wines. Higher concentrations were reported for both metabolites in older wines, indicating their participation on the strongly bound sulfur dioxide fraction. These findings offer new prospects for more precise use of sulfur dioxide in winemaking.

Recent advances in sulfur dioxide releasing nanoplatforms for cancer therapy.

Sulfur dioxide (SO2), long considered to be a harmful atmospheric pollutant, has recently been posited as the fourth gasotransmitter, as it is produced endogenously in mammals and has important pathophysiological effects. The field of tumor therapy has witnessed a paradigm shift with the emergence of SO2-based gas therapy. This has been possible because SO2 is a potent glutathione consumer that can promote the production of reactive oxygen species, eventually leading to oxidative-stress-induced cancer cell death. Nevertheless, this therapeutic gas cannot be directly administrated in gaseous form. Thus, various nano formulations incorporating SO2 donors or prodrugs capable of storing and releasing SO2 have been developed in an attempt to achieve active/passive intratumoral accumulation and SO2 release in the tumor microenvironment. In this review article, the advances over the past decade in nanoplatforms incorporating sulfur SO2 prodrugs to provide controlled release of SO2 for cancer therapy are summarized. We first describe the synthesis of polypeptide SO2 prodrugs to overcome multiple drug resistance that was pioneered by our group, followed by other macromolecular SO2 prodrug structures that self-assemble into nanoparticles for tumor therapy. Second, we describe nanoplatforms composed of various small-molecule SO2 donors with endogenous or exogenous stimuli responsiveness, including thiol activated, acid-sensitive, and ultraviolet or near-infrared light-responsive SO2 donors, which have been used for tumor inhibition. Combinations of SO2 gas therapy with photodynamic therapy, chemotherapy, photothermal therapy, sonodynamic therapy, and nanocatalytic tumor therapy are also presented. Finally, we discuss the current limitations and challenges and the future outlook for SO2-based gas therapy. STATEMENT OF SIGNIFICANCE: Gas therapy is attracting increasing attention in the scientific community because it is a highly promising strategy against cancer owing to its inherent biosafety and avoidance of drug resistance. Sulfur dioxide (SO2) is recently found to be produced endogenously in mammals with important pathophysiological effects. This review summarizes recent advances in SO2 releasing nanosystems for cancer therapy, including polymeric prodrugs, endogenous or exogenous stimulus-activated SO2 donors delivered by nanoplatform and combination therapy strategies.

A rationally designed fluorescent probe for sulfur dioxide and its derivatives: applications in food analysis and bioimaging.

Exogenous sulfur dioxide (SO2) and its derivatives (SO32-/HSO3-) have been extensively utilized in food preservation and endogenous SO2 is recognized as a significant gaseous signaling molecule that can mediate various physiological processes. Overproduction and/or extensive intake of these species can trigger allergic reactions and even tissue damage. Therefore, it is highly desirable to monitor SO2 and its derivatives effectively and quantitatively both in vitro and in vivo. Herein, a new mitochondria-targeted fluorescent probe (PIB) had been constructed, which could ratiometrically recognize SO2 and its derivatives with excellent sensitivity (DL = 15.9 nM) and a fast response time (200 s). The obtained high selectivity and good adaptability of this SO2-specific probe in a wide pH range (6.5-10.0) allowed for quantitatively tracking of SO2 and its derivatives in real food samples (granulated sugar, crystal sugar, and white wine). In addition, PIB could locate at mitochondrion and was capable of imaging exogenous/endogenous SO2 in the cells and zebrafish. In particular, our findings represented one of the rare examples that have demonstrated endogenous SO2 is closely related with the apoptosis of cells. Importantly, probe PIB was successfully employed for in situ metabolic localization in mouse organs, implying the potential applications of our probe in further exploration on SO2-releated pathological and physiological processes.

A Novel Polyamino Acid Sulfur Dioxide Prodrug Synergistically Elevates ROS with ß-Lapachone in Cancer Treatment.

Due to the distorted redox balance, cancer cells are considered more vulnerable to excessive reactive oxygen species (ROS). In a variety of oxidative stress-related therapies, gas therapy has emerged as a new therapeutic strategy owing to its efficacy and biosafety. Herein, a newly-discovered gasotransmitter sulfur dioxide (SO2) and a tumor specific ROS generation agent ß-lapachone (Lapa) were firstly combined for anticancer therapy. Firstly, amphiphilic glutathione (GSH) responsive polypeptide SO2 prodrug PEG-b-poly(Lys-DNs) was synthesized by ring opening polymerization of SO2-containing N-carboxyanhydride. Then, Lapa was encapsulated into the polymeric micelles with loading content of 8.6 % and loading efficiency of 51.6 %. The obtained drug-loaded nanoparticles (NPs(Lapa)) exhibited a fast release of Lapa and SO2 in the stimuli of 10 mM GSH in PBS. Subsequently, in vitro experiment showed that NPs(Lapa) exhibited obvious cytotoxicity towards 4 T1 cancer cells at a concentration of 2.0 µg/mL, which may be attributed to the depletion of intracellular GSH and upregulation of ROS level both by SO2 release and by the ROS generation from lapachone transformation. In vivo fluorescence imaging showed that the NPs were gradually enriched in tumor tissues in 24 h, probably due to the enhanced permeability and retention effect of NPs. Finally, NPs(Lapa) showed the best anticancer effect in 4 T1 tumor bearing mice with a tumor inhibiting rate (IRT) of 61 %, whereas IRT for free Lapa group was only 23.6 %. This work may be a new attempt to combine SO2 gas therapy with ROS inducer for anticancer therapy through oxidative stress.

PdPtVOx/CeO2-ZrO2: Highly efficient catalysts with good sulfur dioxide-poisoning reversibility for the oxidative removal of ethylbenzene.

The PdPtVOx/CeO2-ZrO2 (PdPtVOx/CZO) catalysts were obtained by using different approaches, and their physical and chemical properties were determined by various techniques. Catalytic activities of these materials in the presence of H2O or SO2 were evaluated for the oxidation of ethylbenzene (EB). The PdPtVOx/CZO sample exhibited high catalytic activity, good hydrothermal stability, and reversible sulfur dioxide-poisoning performance, over which the specific reaction rate at 160°C, turnover frequency at 160°C (TOFPd or Pt), and apparent activation energy were 72.6 mmol/(gPt⋅sec) or 124.2 mmol/(gPd⋅sec), 14.2 sec-1 (TOFPt) or 13.1 sec-1 (TOFPd), and 58 kJ/mol, respectively. The large EB adsorption capacity, good reducibility, and strong acidity contributed to the good catalytic performance of PdPtVOx/CZO. Catalytic activity of PdPtVOx/CZO decreased when 50 ppm SO2 or (1.0 vol.% H2O + 50 ppm SO2) was added to the feedstock, but was gradually restored to its initial level after the SO2 was cut off. The good reversible sulfur dioxide-resistant performance of PdPtVOx/CZO was associated with the facts: (i) the introduction of SO2 leads to an increase in surface acidity; (ii) V can adsorb and activate SO2, thus accelerating formation of the SOx2- (x = 3 or 4) species at the V and CZO sites, weakening the adsorption of sulfur species at the PdPt active sites, and hence protecting the PdPt active sites to be not poisoned by SO2. EB oxidation over PdPtVOx/CZO might take place via the route of EB â†’ styrene â†’ phenyl methyl ketone â†’ benzaldehyde â†’ benzoic acid â†’ maleic anhydride â†’ CO2 and H2O.

Identification and Detection of Intracellular Reactive Sulfur Species Using a Reaction-Mediated Dual-Recognition Strategy.

Reactive sulfur species (RSS) are emerging as a potential key gasotransmitter in diverse physiological processes linking two signaling molecules H2S and SO2. However, the exact roles of H2S and SO2 remain unclear. A major hurdle is the shortage of accurate and robust approaches for sensing of H2S and SO2 in biological systems. Herein, we report a reaction-mediated dual-recognition strategy-based nanosensor, silver nanoparticles (AgNPs)-loaded MIL-101 (Fe) (ALM) hybrids, for the simultaneous detection of H2S and SO2 in a living cell. Upon exposure to H2S, AgNPs can be oxidized to form Ag2S, causing a decrease of surface enhanced Raman spectroscopy (SERS) signals of p,p'-dimercaptoazobenzene. Moreover, SO2 reacts with the amino moiety of MIL-101 to form charge-transfer complexes, resulting in an increment of fluorescent (FL) intensity. The ALM with dual-modal signals can simultaneously analyze H2S and SO2 at a concentration as low as 2.8 × 10-6 and 0.003 µM, respectively. Most importantly, the ALM sensing platform enables targeting mitochondria and detection multiple RSS simultaneously in living cells under external stimulation, as well as displays indiscernible crosstalk between SERS and FL signals, which is very beneficial for the comprehension of physiological issues related with RSS.

Zinc-aluminum layered double hydroxide and double oxide for room-temperature oxidation of sulfur dioxide gas.

Sulfur dioxide (SO2) gas at trace levels challenges the consumption of fuel gases and cleaning of flue gases originating from diverse anthropogenic sources. We have demonstrated Zn-Al layered double hydroxide (LDH) and layered double oxide (LDO) as low-cost and effective adsorbents in removing lowly concentrated SO2 gas at room temperature. Water in the adsorbent bed significantly improved the performance, where the maximum adsorption capacity of 38.0 mg g-1 was achieved for LDO. Based on the spectroscopic findings, the adsorbed gas molecules were oxidized to surface-bound sulfate/bisulfate species, showing complete mineralization of SO2 molecules. By employing an inexpensive NaOH-H2O2 solution-based regeneration strategy, we successfully regenerated the spent LDO, significantly restoring its gas uptake capacity. The regenerated oxide exhibited an increased gas uptake capacity ranging from 38.0 to 98.5 mg g-1, highlighting the practicality and economic feasibility of our approach. LDH/LDO materials are promising regenerable adsorbents for removing low concentrations of SO2 gas in ambient conditions.

Sensory Specificities Involving Acetaldehyde and Diacetyl in Wines Produced without Added Sulfur Dioxide.

Nowadays, the development of naturality concept is illustrated in the oenological field by the development of wine produced without the addition of SO2. Among its chemical properties, SO2 is able to react with carbonyl compounds to form carbonyl bisulfites. Acetaldehyde and diacetyl are the main carbonyl compounds of red wines, which could influence product perception. The goal of this paper was to evaluate their chemical and sensory impact in red wines produced without any addition of SO2. A first quantification approach revealed a lower concentration of these compounds in wines without added SO2 than in those produced with SO2. A sensory approach involving aromatic reconstitutions in wines in the presence or absence of SO2 revealed that analytical differences observed for acetaldehyde and diacetyl were able to impact wine freshness, with diacetyl being, moreover, involved in wine fruity aroma changes.