Your browser doesn't support javascript.
loading
Mostrar: 20 | 50 | 100
Resultados 1 - 20 de 766
Filtrar
1.
Environ Sci Technol ; 58(20): 8955-8965, 2024 May 21.
Artigo em Inglês | MEDLINE | ID: mdl-38718175

RESUMO

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.


Assuntos
Amônia , Catálise , Amônia/química , Dióxido de Enxofre/química , Compostos Férricos/química , Oxirredução
2.
Food Chem ; 449: 138944, 2024 Aug 15.
Artigo em Inglês | MEDLINE | ID: mdl-38613993

RESUMO

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.


Assuntos
Compostos de Sulfidrila , Vinho , Vinho/análise , Cinética , Compostos de Sulfidrila/química , Oxirredução , Dióxido de Enxofre/química , Cisteína/química , Cisteína/metabolismo , Acetaldeído/química , Sulfitos/química , Espectroscopia de Prótons por Ressonância Magnética , Espectroscopia de Ressonância Magnética , Glutationa/química , Glutationa/metabolismo
3.
Waste Manag ; 181: 101-113, 2024 May 30.
Artigo em Inglês | MEDLINE | ID: mdl-38603994

RESUMO

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.


Assuntos
Alismatales , Pirólise , Dióxido de Enxofre , Alismatales/química , Dióxido de Enxofre/química , Ácido Clorídrico/química , Termogravimetria , Oxigênio/química
4.
Chemosphere ; 355: 141809, 2024 May.
Artigo em Inglês | MEDLINE | ID: mdl-38548080

RESUMO

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.


Assuntos
Óxidos de Nitrogênio , Dióxido de Enxofre , Óxidos de Nitrogênio/química , Dióxido de Enxofre/química , Dióxido de Nitrogênio , Iodeto de Potássio , Reprodutibilidade dos Testes , Oxirredução
5.
Biomater Sci ; 12(9): 2341-2355, 2024 Apr 30.
Artigo em Inglês | MEDLINE | ID: mdl-38497292

RESUMO

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.


Assuntos
Glutationa , Estresse Oxidativo , Dióxido de Enxofre , Estresse Oxidativo/efeitos dos fármacos , Glutationa/metabolismo , Glutationa/química , Dióxido de Enxofre/química , Dióxido de Enxofre/farmacologia , Humanos , Animais , Camundongos , Nanopartículas/química , Terapia por Ultrassom , Camundongos Endogâmicos BALB C , Dióxido de Silício/química , Linhagem Celular Tumoral , Feminino
6.
J Agric Food Chem ; 72(4): 1885-1893, 2024 Jan 31.
Artigo em Inglês | MEDLINE | ID: mdl-36724455

RESUMO

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.


Assuntos
Vinho , Vinho/análise , Cromatografia Líquida , Compostos de Sulfidrila/química , Dióxido de Enxofre/química , Espectrometria de Massas em Tandem , Polifenóis/análise
7.
Acta Biomater ; 174: 91-103, 2024 Jan 15.
Artigo em Inglês | MEDLINE | ID: mdl-38092251

RESUMO

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.


Assuntos
Nanopartículas , Neoplasias , Pró-Fármacos , Animais , Dióxido de Enxofre/farmacologia , Dióxido de Enxofre/química , Dióxido de Enxofre/metabolismo , Pró-Fármacos/farmacologia , Pró-Fármacos/uso terapêutico , Pró-Fármacos/química , Neoplasias/tratamento farmacológico , Nanopartículas/uso terapêutico , Nanopartículas/química , Mamíferos/metabolismo , Microambiente Tumoral
8.
J Pharm Sci ; 113(5): 1239-1247, 2024 May.
Artigo em Inglês | MEDLINE | ID: mdl-38042342

RESUMO

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.


Assuntos
Antineoplásicos , Nanopartículas , Naftoquinonas , Neoplasias , Pró-Fármacos , Animais , Camundongos , Pró-Fármacos/química , Espécies Reativas de Oxigênio , Antineoplásicos/química , Dióxido de Enxofre/química , Neoplasias/tratamento farmacológico , Glutationa , Nanopartículas/química , Linhagem Celular Tumoral
9.
Anal Bioanal Chem ; 416(2): 533-543, 2024 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-38008784

RESUMO

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.


Assuntos
Corantes Fluorescentes , Dióxido de Enxofre , Humanos , Animais , Camundongos , Dióxido de Enxofre/análise , Dióxido de Enxofre/química , Corantes Fluorescentes/química , Peixe-Zebra , Análise de Alimentos , Células HeLa , Açúcares
10.
J Environ Sci (China) ; 138: 153-166, 2024 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-38135384

RESUMO

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.


Assuntos
Derivados de Benzeno , Dióxido de Enxofre , Dióxido de Enxofre/química , Oxirredução , Catálise , Estresse Oxidativo , Amônia/química
11.
Anal Chem ; 95(33): 12427-12434, 2023 08 22.
Artigo em Inglês | MEDLINE | ID: mdl-37560995

RESUMO

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.


Assuntos
Espaço Intracelular , Espaço Intracelular/química , Enxofre/química , Humanos , Linhagem Celular Tumoral , Prata/química , Nanopartículas Metálicas , Dióxido de Enxofre/química
12.
Chemosphere ; 338: 139503, 2023 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-37453522

RESUMO

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.


Assuntos
Alumínio , Dióxido de Enxofre , Dióxido de Enxofre/química , Alumínio/química , Óxidos , Hidróxido de Alumínio , Zinco , Temperatura , Peróxido de Hidrogênio , Hidróxidos , Ácidos , Adsorção
13.
J Agric Food Chem ; 71(23): 9062-9069, 2023 Jun 14.
Artigo em Inglês | MEDLINE | ID: mdl-37253187

RESUMO

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.


Assuntos
Vinho , Vinho/análise , Dióxido de Enxofre/química , Acetaldeído , Diacetil , Odorantes/análise
14.
J Mol Graph Model ; 122: 108463, 2023 07.
Artigo em Inglês | MEDLINE | ID: mdl-37004418

RESUMO

An effort has been made to explore the adsorption potential of activated carbon (AC) structures for adsorption of hydrogen sulfide (H2S) and sulfur dioxide (SO2) employing density functional theory (DFT) at GGA level. 2-ring, 3-ring, 6-ring, and 9-ring carbon structures are used as adsorbent surfaces. The above mentioned rings are examined by creation of defect and inclusion of hydrogen as well to get the clear view close to experimental observations of adsorption properties of activated carbon. The adsorption properties depend upon many factors including whether adsorbate adsorbs in planer or non-planer mode, defect creation in the adsorbent substrate, atomic hydrogen insertion in the system and size of the adsorbent system. Our calculations show that side by side (planer) interaction binds the molecules much more strongly in comparison with molecules adsorbed upon the surface in non-planer mode. If vacancy is created at the central position of the surface, the molecules bind with substantial binding energy. However, overall Eads of the molecules varies randomly and no consistency could be achieved. Additionally, smaller sized structures are favorable relative to the bigger surfaces. The highest Eads for both the molecules is -2.97 eV, though not on the same substrate system. Finally, it can be argued that activated carbon is very useful material for adsorbing the noxious gases.


Assuntos
Carvão Vegetal , Sulfeto de Hidrogênio , Carvão Vegetal/química , Adsorção , Sulfeto de Hidrogênio/química , Dióxido de Enxofre/química , Hidrogênio
15.
Environ Sci Pollut Res Int ; 30(18): 52013-52025, 2023 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-36823467

RESUMO

SO2, an air pollutant, is harmful to human health and causes air pollution; therefore, numerous studies have focused on the development of SO2 control technologies. Although limestone- and ammonia-based absorbents have been widely used in wet desulfurization, they are difficult to regenerate and do not enable the recycling of SO2, which is a useful resource. Recently, amino acids have attracted attention as reversible SO2 absorbents because they are eco-friendly and have excellent reactivity with SO2, as well as high regeneration performance. Glycine, L-alanine, ß-alanine, 4-aminobutyric acid, 5-aminovaleric acid, and 6-aminohexanoic acid were analyzed to investigate the relationship between SO2 absorption and the amino acid molecular structure using the simulated actual flue gas (200 ppmv SO2 + 13% CO2 in N2 balance). The SO2 absorption of amino acids (with the molecular structure of glycine and alkyl chains of various lengths) improved as the alkyl chain length increased, possibly owing to a decrease in the inductive effect in the molecular structure of the amino acid. Furthermore, 13C-nuclear magnetic resonance spectroscopy was conducted to analyze the SO2 absorption reaction mechanism (including the possible generation of irreversible species), and experiments involving a number of consecutive absorption-desorption cycles were used to confirm the reusability of the amino acids. The tested amino acids exhibited higher cyclic capacities compared to those of deep eutectic solvents and ionic liquids reported in the literature, thereby exhibiting excellent potential as SO2 absorbents. Thus, this study can guide the future design and development of eco-friendly SO2 absorbents.


Assuntos
Poluentes Atmosféricos , Poluição do Ar , Humanos , Dióxido de Enxofre/química , Aminoácidos , Poluentes Atmosféricos/química , Glicina
16.
Anal Bioanal Chem ; 415(4): 715-724, 2023 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-36520201

RESUMO

It is highly desirable to develop high-performance ratiometric fluorescent probes for SO2 derivative detection and realize their application in biological imaging. In this study, we report the rational design of a novel negative photochromic spiropyran derivative, spiro[azahomoadamantane-pyran] (MAHD-SP), with notable orange fluorescence in its stable ring-opened state without UV regulation. The unsaturated double bond of MAHD-SP underwent the Michael addition reaction of the SO2 derivative, making the fluorescence quenching of MAHD-SP obvious. Then, MAHD-SP, a fluorescent conjugated polymer PFO and a polymeric surfactant PEO113-b-PS49 were used to construct a ratiometric fluorescent polymeric nanoprobe (RFPN) via a coprecipitation method. The probe exhibited high sensitivity and selectivity for the ratiometric detection of SO2 derivatives in pure aqueous solutions. Moreover, the good biocompatibility of RFPN can be used to visualize exogenous and endogenous SO2 derivative generation in living cells.


Assuntos
Benzopiranos , Dióxido de Enxofre , Humanos , Dióxido de Enxofre/química , Indóis , Microscopia de Fluorescência/métodos , Corantes Fluorescentes/química , Células HeLa
17.
Anal Chem ; 95(2): 1376-1384, 2023 01 17.
Artigo em Inglês | MEDLINE | ID: mdl-36562538

RESUMO

As a momentous gas signal molecule, sulfur dioxide (SO2) participates in diverse physiological activities. Excess SO2 will cause an apparent decrease in the level of intracellular glutathione (GSH), thereby damaging the body's antioxidant defense system. In addition, endogenous SO2 can be generated from GSH by reacting with thiosulfate (S2O32-) and enzymatically reduced to cysteine (Cys), a synthetic precursor of GSH. In view of their close correlation, a two-photon (TP) mitochondria-targeted multifunctional fluorescence sensor Mito-Na-BP was rationally designed and synthesized for detecting SO2 and GSH simultaneously. Under single-wavelength excitation, the sensor responded to GSH-SO2 and SO2-GSH continuously with blue-shifted and green fluorescence-enhanced signal modes, respectively, not just to GSH (enhanced) and SO2 (quenched) at 638 nm with a completely converse response tendency. Given its favorable spectral performance (high sensitivity, superior selectivity, and fast response rate) at physiological pH, Mito-Na-BP has been successfully applied in monitoring the level fluctuation of GSH affected from high-dose SO2 and visualizing in real time the metabolic process of GSH to SO2 by TP imaging. It is expected that this research will provide a convenient and efficient tool for elucidating intricate relationships of GSH and SO2 and facilitate further exploration of their functions in biomedicine.


Assuntos
Diagnóstico por Imagem , Dióxido de Enxofre , Humanos , Fluorescência , Dióxido de Enxofre/química , Glutationa/metabolismo , Corantes Fluorescentes/química , Células HeLa
18.
Food Chem ; 407: 135031, 2023 May 01.
Artigo em Inglês | MEDLINE | ID: mdl-36473352

RESUMO

Preservative sulfur dioxide (SO2) and bleach hydrogen peroxide (H2O2) were widely used in the food industry, at the same time, they were also a redox pair in biological systems. Therefore, the reversible sensing SO2/H2O2 was of great significance in food safety and biology. In this paper, a colorimetric and NIR fluorescent dual channels response probe (DCA-Bba) for SO2/H2O2 based on chromene-barbiturate was developed. DCA-Bba exhibited a rapid and sensitive recognition of SO2, and the adduct DCA-Bba-HSO3- could detect H2O2 in PBS (with 10 % DMSO, v/v, pH 7.4) solution. The reversible response of DCA-Bba was implemented by HSO3- involved 1,4-addition and H2O2 induced elimination reaction. DCA-Bba showed a strong red fluorescence based on the intramolecular charge transfer (ICT) process, after the recognition of SO2, the fluorescence of the adduct was quenched based on the photoinduced electron transfer (PET) process. And importantly, DCA-Bba had been applied for imaging SO2/H2O2 redox cycles in living cells, as well as could detect the levels of SO2 in white sugar, biscuit, Chinese liquor and red wine samples.


Assuntos
Corantes Fluorescentes , Peróxido de Hidrogênio , Humanos , Peróxido de Hidrogênio/química , Corantes Fluorescentes/química , Colorimetria/métodos , Células HeLa , Oxirredução , Dióxido de Enxofre/química
19.
Org Lett ; 24(41): 7560-7565, 2022 Oct 21.
Artigo em Inglês | MEDLINE | ID: mdl-36222520

RESUMO

An iron-catalyzed four-component sulfonylthiocyanation between α,ß-unsaturated amides/esters, TMSNCS, aryldiazonium tetrafluoroborates, and sulfur dioxide (from SOgen) is demonstrated. This protocol is characterized by mild reaction conditions, good functional group compatibility, broad substrate scope, and good to excellent yields, providing a feasible method for the preparation of ß-thiocyanated sulfone compounds. The preliminary mechanism investigation shows that a radical pathway may be involved in the process.


Assuntos
Amidas , Ésteres , Ésteres/química , Amidas/química , Dióxido de Enxofre/química , Ferro/química , Catálise , Sulfonas
20.
J Mol Graph Model ; 117: 108302, 2022 12.
Artigo em Inglês | MEDLINE | ID: mdl-36049401

RESUMO

In this project, we have investigated the possibility of mimicking the natural photosynthesis, as well as sensing and adsorption application of aluminum decorated graphitic C3N4 (Al-g-C3N4) QDs (toward some air pollutants containing CO, CO2, and SO2). The results of the potential energy surface (PES) studies show that in all three adsorption processes, the energy changes are negative (-10.70 kcal mol-1, -16.81 kcal mol-1, and -79.97 kcal mol-1 for CO, CO2, and SO2 gasses, respectively). Thus, all of the adsorption processes (mainly SO2) are spontaneous. Moreover, the frontier molecular orbital (FMO) investigations indicate that the Al-g-C3N4 QD could be used as a suitable semiconductor sensor for detection of CO, and CO2 (as carbon oxides) in one hand, and SO2 gaseous species on the other hand. Finally, the results reveal that those QDs could be applied for artificial photosynthesis (in presence of CO2; Δµh-e = 1.43 V), and for water splitting process for the H2 generation (Δµh-e = 1.23 V) as a clean fuel for near future.


Assuntos
Poluentes Atmosféricos , Poluição do Ar/prevenção & controle , Alumínio/química , Grafite , Fotossíntese , Adsorção , Carbono , Dióxido de Carbono/química , Dióxido de Carbono/metabolismo , Monóxido de Carbono/química , Monóxido de Carbono/metabolismo , Catálise , Nitrogênio , Óxidos , Dióxido de Enxofre/química , Dióxido de Enxofre/metabolismo , Água
SELEÇÃO DE REFERÊNCIAS
DETALHE DA PESQUISA
...