Ratiometric electrochemical molecular switch for sensing hypochlorous acid: Applicable in food analysis and real-time in-situ monitoring.

A ratiometric electrochemical molecular sensing platform for real-time quantification of extracellular hypochlorous acid (HClO) production has been developed based on a latent electrochemical probe aminoferrocene thiocarbamate (AFTC 3). The substrate AFTC consist of a masked redox reporter amino ferrocene (AF 4) linked with a dimethylthiocarbamate trigger via hydroxyl benzyl alcohol. The conceptual idea behind the probe design is based on a specific chemical interaction between HClO and dimethylthiocarbamate, which allows only HClO to unmask the probe to releases AF. The scheme was manipulated to establish a highly selective (in presence of various reactive oxygen species, anions and other biological interfering species) and sensitive (detection limit 75 nM) sensing platform not only in lab samples but also in real samples (food samples, and live cells). Real-time in situ quantification platform was developed to profile HClO productions in macrophages, and it did so with great consistency.

An Endeavor in the Reaction-Based Approach to Fluorescent Probes for Biorelevant Analytes: Challenges and Achievements.

The promising features of fluorescence spectroscopy have inspired a quest for fluorescent probes for analysis and monitoring of molecular interactions in biochemical, medical, and environmental sciences. To overcome the competitive supramolecular interactions in aqueous media encountered with conventional molecular-recognition-based probes, the use of reaction-based probes that involve making or breaking of covalent bonds has emerged as a complementary sensing strategy to realize higher selectivity and sensitivity with larger spectroscopic changes. In spite of the enormous efforts, the development of reaction-based fluorescent probes meets with certain challenges in terms of their practical applications, demanding "intelligent design" of probes with an appropriate fluorophore attached to an efficient reactive moiety at the right place. This Account summarizes the results of our efforts made in the development and fine-tuning of reaction-based fluorescent probes toward those goals, classified by the type of analyte (anions, metal cations, and biomolecules) with notes on the challenges and achievements. The reaction-based approach was demonstrated to be powerful for the selective sensing of anions (cyanide and (amino)carboxylates) for the first time, and later it was extended to develop two-photon probes for bisulfite and fluoride ions. The reaction-based approach also enabled selective sensing of noble metal ions such as silver, gold, and palladium along with toxic (methyl)mercury species and paramagnetic copper ions. Furthermore, microscopic imaging and monitoring of biologically relevant species with reaction-based two-photon probes were explored for hydrogen sulfide, hypochlorous acid, formaldehyde, monoamine oxidase enzyme, and ATP.

Optimization of microwave-assisted extraction of polyphenols from herbal teas and evaluation of their in vitro hypochlorous acid scavenging activity.

Hypochlorous acid (HOCl) is an important reactive oxygen species (ROS) and non-radical and is taking part in physiological processes concerned with the defense of the organism, but there has been limited information regarding its scavenging by polyphenols. This study was designed to examine the HOCl scavenging activity of several polyphenols and microwave-assisted extracts of herbal teas. HOCl scavenging activity has usually been determined spectrophotometrically by a KI/taurine assay at 350 nm. Because some polyphenols (i.e., apigenin and chrysin) have a strong ultraviolet (UV) absorption in this range, their HOCl scavenging activity was alternatively determined without interference using resorcinol (1,3-dihydroxybenzene) as a fluorogenic probe. In the present assay, HOCl induces the chlorination of resorcinol into its non-fluorescent products. Polyphenols as HOCl scavengers inhibit the chlorination of the probe by this species. Thus, the 25% inhibitive concentration (IC25) value of polyphenols was determined using the relative increase in fluorescence intensity of the resorcinol probe. The HOCl scavenging activities of the test compounds decreased in the order: epigallocatechin gallate > quercetin > gallic acid > rutin > catechin > kaempferol. The present study revealed that epigallocatechin gallate (IC25 = 0.1 µM) was the most effective scavenging agent. In addition to polyphenols, four herbal teas were evaluated for their HOCl activity using the resorcinol method. The proposed spectrofluorometric method was practical, rapid, and less open to interferences by absorbing substances in the range of 200-420 nm. The results hint to the possibility of polyphenols having beneficial effects in diseases, such as atherosclerosis, in which HOCl plays a pathogenic role.

Facile meso-BODIPY annulation and selective sensing of hypochlorite in water.

Annulated BODIPY chalcogenide (Se, Te) systems were synthesized from their respective bis(o-formylphenyl)dichalcogenide intermediates. The annulated BODIPY selenide product was confirmed by X-ray diffraction. The red-shifted telluride version was found to be sensitive and selective for hypochlorite detection, reversible upon treatment with biothiols.

A near-infrared fluorescent probe for selective detection of HClO based on Se-sensitized aggregation of heptamethine cyanine dye.

A Se-containing heptamethine cyanine dye based fluorescent probe was successfully developed and used for HClO detection with rapid response and high selectivity based on aggregation behavior. The probe could react with HClO with significant change in its fluorescence profile, which makes it practical for detecting HClO in fetal bovine serum and in living mice.

A reversible fluorescent probe for detecting hypochloric acid in living cells and animals: utilizing a novel strategy for effectively modulating the fluorescence of selenide and selenoxide.

Based on a novel strategy for modulating the fluorescence of selenide and selenoxide, we have designed and developed a reversible fluorescent probe for hypochloric acid. And the synthesis, characterization, fluorescence properties, as well as the biological applications in living cells and animals, have all been described.

Chemiluminescent analysis of plasma antioxidant capacity in uremic patients undergoing hemodialysis.

OBJECTIVE: Hemodialysis is a common therapeutic strategy for patients with end stage renal failure. During the hemodialytic process, the neutrophils are activated (neutrophil burst) due to the hemoincompatibility induced by hemodialysis. As a result, the activated neutrophils release reactive oxygen species (ROS), such as hydrogen peroxide, singlet oxygen, and hypochlorite, into the bloodstream and cause oxidative damage. METHODS: This study investigated the antioxidant alteration of plasma in uremic patients undergoing hemodialysis by chemiluminescent analysis. The antioxidant capacities of plasma in scavenging hydrogen peroxide, singlet oxygen, and hypochlorite were investigated in this experiment. In addition, investigation of the ferric-reducing ability of plasma (FRAP) would be covered in this study as well. RESULTS: This study found that after hemodialysis, the antioxidant capacities of plasma in scavenging hydrogen peroxide, singlet oxygen, and hypochlorite decreases 7.9%, 18.8%, and 18.9%, respectively. Moreover, the FRAP is reduced by 56%. We speculate that the loss of dialyzable solutes (such as uremic solutes and antioxidants with small molecular weight) in plasma resulted in its decrease in antioxidant capacity. CONCLUSION: We therefore suggest that the supplement of antioxidants with small molecular weight is capable of regaining antioxidant defense in plasma and preventing oxidative damage induced by hemodialysis.

Ablation of the inflammatory enzyme myeloperoxidase mitigates features of Parkinson's disease in mice.

Parkinson's disease (PD) is characterized by a loss of ventral midbrain dopaminergic neurons, which can be modeled by the neurotoxin 1-methyl-4-phenyl-1,2,3,6-tetrahydropyridine (MPTP). Inflammatory oxidants have emerged as key contributors to PD- and MPTP-related neurodegeneration. Here, we show that myeloperoxidase (MPO), a key oxidant-producing enzyme during inflammation, is upregulated in the ventral midbrain of human PD and MPTP mice. We also show that ventral midbrain dopaminergic neurons of mutant mice deficient in MPO are more resistant to MPTP-induced cytotoxicity than their wild-type littermates. Supporting the oxidative damaging role of MPO in this PD model are the demonstrations that MPO-specific biomarkers 3-chlorotyrosine and hypochlorous acid-modified proteins increase in the brains of MPTP-injected mice. This study demonstrates that MPO participates in the MPTP neurotoxic process and suggests that inhibitors of MPO may provide a protective benefit in PD.