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The removal of arsenic (As(III)) from acidic wastewater using neutralization or sulfide precipitation generates substantial arsenic-containing hazardous solid waste, posing significant environmental challenges. This study proposed an advanced ultraviolet (UV)/dithionite reduction method to recover As(III) in the form of valuable elemental arsenic (As(0)) from acidic wastewater, thereby avoiding hazardous waste production. The results showed that more than 99.9 % of As(III) was reduced to As(0) with the residual concentration of arsenic below 25.0 μg L -1 within several minutes when the dithionite/As(III) molar ratio exceeded 1.5:1 and the pH was below 4.0. The content of As(0) in precipitate reached 99.70 wt%, achieving the purity requirements for commercial As(0) products. Mechanistic investigations revealed that SO 2 ·‒ and H· radicals generated by dithionite photolysis under UV irradiation are responsible for reducing As(III) to As(0). Dissolved O 2 , Fe(III), Fe(II), Mn(II), dissolved organic matter (DOM), and turbidity slightly inhibited As(III) reduction via free radicals scavenging or light blocking effect, whereas other coexisting ions, such as Mg(II), Zn(II), Cd(II), Ni(II), F(-I), and Cl(-I), had limited influence on As(III) reduction. Moreover, the cost of treating real arsenic-containing (250.3 mg L -1 ) acidic wastewater was estimated to be as low as $0.668 m - 3 , demonstrating the practical applicability of this method. This work provides a novel method for the reductive recovery of As(III) from acidic wastewater., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

Dithionite remained in the foodstuff may pose a great threat to the health of consumers. Three xanthylium-based probes were synthesized and their responses to dithionite were explored. Probe SH-1 could respond to dithionite selectively in PBS buffer (15% DMSO, 10 mM, pH = 7.4). Upon the addition of dithionite, the fluorescent emission of SH-1 at 684 nm dropped quickly (within 10 s) and the fluorescence decline was proportional to the concentration of dithionite (0-7.0 μM). The limit of detection was determined to be 0.139 μM. Then, the sensing mechanism was tentatively presented and the structure of resulted adduct (SH-1-SO 3 - ) which was the reaction product of SH-1 and dithionite via a Micheal addition reaction followed by an oxidation reaction was verified. Moreover, white granulated sugar was subjected to the standard spike experiments and the results demonstrated a great potential of SH-1 for the quantitative monitoring of dithionite in foodstuffs., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023. Published by Elsevier Ltd.)

Accurate detection of labile analytes through activity based fluorogenic sensing is meaningful but remains a challenge because of nonrapid reaction kinetic. Herein, we present a signaling reporter engineering strategy to accelerate azoreduction reaction by positively charged fluorophore promoted unstable anion recognition for rapidly sensing sodium dithionite (Na 2 S 2 O 4 ), a kind of widespread used but harmful inorganic reducing agent. Its quick decomposition often impedes application reliability of traditional fluorogenic probes in real samples because of their slow responses. In this work, four azo-based probes with different charged fluorophores (positive, zwitterionic, neutral, and negative) were synthesized and compared. Among of them, with sequestration effect of positively charged anthocyanin fluorophore for dithionite anion via electrostatic attraction, the cationic probe Azo-Pos displayed ultrafast fluorogenic response (∼2 s) with the fastest response kinetic ( k pos ' = 0.373 s -1 ) that is better than other charged ones ( k zwi ' = 0.031 s -1 , k neu ' = 0.013 s -1 , k neg ' = 0.003 s -1 ). Azo-Pos was demonstrated to be capable to directly detect labile Na 2 S 2 O 4 in food samples and visualize the presence of Na 2 S 2 O 4 in living systems in a timely fashion. This new probe has potential as a robust tool to fluorescently monitor excessive food additives and biological invasion of harmful Na 2 S 2 O 4 . Moreover, our proposed accelerating strategy would be versatile to develop more activity-based sensing probes for quickly detecting other unstable analytes of interest.

Whereas dithionite has been extensively used as a reducing agent in soil and sediment remediation, here, we demonstrate that it can be used as a potential source of oxidizing radical in oxic soils with potential application in organic pollutant remediation. Benzoic acid was used as a probe compound and the generation of its oxidative product para-hydroxybenzoic acid ( p -HBA) was detected to quantify the production of oxidative radicals (ROS). By increasing the dithionite concentration from 2.5-10 Mm, the accumulated P-HBA concentration in 120 min increased from 15.0-27 µM. Whereas, above 10 mM, the p-HBA concentration decreased due to radical scavenging. Increasing soil dosage from 2.5-15 g/100 mL the accumulated p-HBA amount increased from 22.8-33.7 µM. Temperature 25-35 o C and pH 6.2-7.5 were favoured for p-HBA generation. Furthermore, we investigated the roles of different active intermediates in the reaction system and proposed the mechanism behind the ROS genearation. This study suggested that dithionite can be used as an active reagent for advanced oxidation remediation in oxic soil medium.

Determining the topology of membrane-inserted proteins and peptides often relies upon indirect fluorescent measurements. One such technique uses NBD, an environmentally sensitive fluorophore that can be covalently linked to proteins. Relative to a hydrophilic environment, NBD in a hydrophobic environment shows an increase in emission intensity and a shift to shorter wavelengths. To gain further insight, NBD fluorescence can be chemically quenched using dithionite. As dithionite is an anion, it is only expected to penetrate the outer leaflet interfacial region and should be excluded from the hydrocarbon core, the inner leaflet, and the lumen of LUV. This assumption holds at neutral pH, where a large number of NBD/dithionite experiments are carried out. Here, we report control experiments in which LUV were directly labeled with NBD-PE to assess dithionite quenching in acidic conditions. Results showed that at acidic pH, dithionite moved more freely across the bilayer to quench the inner leaflet. For the buffer conditions used, dithionite exhibited a sharp change in behavior between pH 5.5 and 6.0. Therefore, in acidic conditions, dithionite could not differentiate in which leaflet the NBD resided., (© 2021. The Author(s), under exclusive licence to Springer Science+Business Media, LLC, part of Springer Nature.)

[FeFe] hydrogenases are highly active enzymes for interconverting protons and electrons with hydrogen (H 2 ). Their active site H-cluster is formed of a canonical [4Fe-4S] cluster ([4Fe-4S] H ) covalently attached to a unique [2Fe] subcluster ([2Fe] H ), where both sites are redox active. Heterolytic splitting and formation of H 2 takes place at [2Fe] H , while [4Fe-4S] H stores electrons. The detailed catalytic mechanism of these enzymes is under intense investigation, with two dominant models existing in the literature. In one model, an alternative form of the active oxidized state H ox , named H ox H, which forms at low pH in the presence of the nonphysiological reductant sodium dithionite (NaDT), is believed to play a crucial role. H ox H was previously suggested to have a protonated [4Fe-4S] H . Here, we show that H ox H forms by simple addition of sodium sulfite (Na 2 SO 3 , the dominant oxidation product of NaDT) at low pH. The low pH requirement indicates that sulfur dioxide (SO 2 ) is the species involved. Spectroscopy supports binding at or near [4Fe-4S] H , causing its redox potential to increase by ∼60 mV. This potential shift detunes the redox potentials of the subclusters of the H-cluster, lowering activity, as shown in protein film electrochemistry (PFE). Together, these results indicate that H ox H and its one-electron reduced counterpart H red 'H are artifacts of using a nonphysiological reductant, and not crucial catalytic intermediates. We propose renaming these states as the "dithionite (DT) inhibited" states H ox -DT i and H red -DT i . The broader potential implications of using a nonphysiological reductant in spectroscopic and mechanistic studies of enzymes are highlighted.

A facile and convergent procedure for the synthesis of azobenzene-based probe was reported, which could selectively release interested proteins conducted with sodium dithionite. Besides, the cleavage efficiency is closely associated with the structural features, in which an ortho-hydroxyl substituent is necessary for reactivity. In addition, the azobenzene tag applied in the Ac 4 GlcNAz-labled proteins demonstrated high efficiency and selectivity in comparison with Biotin-PEG 4 -Alkyne, which provides a useful platform for enrichment of any desired bioorthogonal proteomics., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

Transbilayer movement of phospholipids in biological membranes is mediated by a diverse set of lipid transporters. Among them are scramblases that facilitate a rapid bi-directional movement of lipids without metabolic energy input. Here, we established a new fluorescence microscopy-based assay for detecting phospholipid scramblase activity of membrane proteins upon their reconstitution into giant unilamellar vesicles formed from proteoliposomes by electroformation. The assay is based on chemical bleaching of fluorescence of a photostable ATTO-dye labeled phospholipid with the membrane-impermeant reductant sodium dithionite. We demonstrate that this new methodology is suitable for the study of the scramblase activity of the yeast endoplasmic reticulum at single vesicle level., (© 2021. The Author(s).)

Recent studies have identified the 8C alkyl chain methylimidazolium ionic liquid 1-octyl-3-methylimidazolium in the environment and its potential to trigger the auto-immune liver disease primary biliary cholangitis. The toxicity of a range of methylimidazolium ionic liquids were therefore examined. Oxygen consumption was rapidly inhibited, with potency increasing with alkyl chain length. This preceded caspase 3/7 induction and DNA fragmentation. Time- and dose-dependent loss of dye reduction capacities reflected these effects, with a >700 fold difference in potency between 2C and 10C alkyl chain liquids. None of the ionic liquids directly inhibited mitochondrial complexes I-IV or complex V (F 0 F 1 -ATPase). However, dithionite reduction and ESR spectroscopy studies indicate a one electron reduction of oxygen in the presence of a methylimidazolium ionic liquid, suggesting methylimidazolium ionic liquids function as mitochondrial electron acceptors. However, only longer chain ionic liquids form a non-aqueous phase or micelle under aqueous physiological conditions and lead to increases in reactive oxygen species in intact cells. These data therefore suggest that the longer chain methylimidazolium liquids are toxic in sensitive liver progenitor cells because they both readily integrate within the inner mitochondrial membrane and accept electrons from the electron chain, leading to oxidative stress., (Copyright © 2020 The Author(s). Published by Elsevier Ltd.. All rights reserved.)

This study focuses on assessing the possible impact of changes in hemoglobin (Hb) oxygenation on the state of water in its hydration shell as it contributes to red blood cell deformability. Microwave Dielectric Spectroscopy (MDS) was used to monitor the changes in interactions between water molecules and Hb, the number of water molecules in the protein hydration shell, and the dynamics of pre-protein water in response to the transition of Hb from the tense (T) to the relaxed (R) state, and vice versa. Measurements were performed for Hb solutions of different concentrations (5 g/dl-30 g/dl) in phosphate-buffered saline buffer. Cole-Cole parameters of the main water relaxation peak in terms of interactions of water molecules (dipole-dipole/ionic dipole) during the oxygenation-deoxygenation cycle were used to analyze the obtained data. The water mobility-represented by α as a function of ln τ-differed dramatically between the R (oxygenated) state and the T (deoxygenated) state of Hb at physiologically relevant concentrations (30 g/dl-35 g/dl or 4.5 mM-5.5 mM). At these concentrations, oxygenated hemoglobin was characterized by substantially lower mobility of water in the hydration shell, measured as an increase in relaxation time, compared to deoxyhemoglobin. This change indicated an increase in red blood cell cytosolic viscosity when cells were oxygenated and a decrease in viscosity upon deoxygenation. Information provided by MDS on the intraerythrocytic water state of intact red blood cells reflects its interaction with all of the cytosolic components, making these measurements powerful predictors of the changes in the rheological properties of red blood cells, regardless of the cause.

Jaggery is a non-centrifugal sweetener produced by thermo-chemical treatments of sugarcane juice. The traditional practices involved in making jaggery are usually tailored using chemicals to meet consumer requirements. Sodium hydrosulphite (hydros) is a commonly employed chemical in the jaggery industry to improve its colour. This article presents a comparative study of jaggery made with and without hydros treatments. The differences in properties, such as sorption behaviour, colour, polyphenols, flavonoids, minerals, and sulphur dioxide content, were measured. Hydros-treated jaggery was found to be brighter in colour with a lower browning index by 5-10. SO 2 content of hydros-treated jaggery was >70 ppm, while minerals, polyphenols, and flavonoids were less abundant compared to control jaggery, thereby compromising overall quality. Based on the experiments carried out, the optimum treatment of hydros can be employed to satisfy consumer demand while producing an acceptable quality of jaggery that conforms to norms., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

In this short note we describe the conversion of the widely used fluorescence quenching azo-dyes DABCYL and HABA to fluorophores. The dyes were conjugated to the proteins RNase and human serum albumin (HSA) and subsequently reduced using sodium dithionite (Na 2 S 2 O 4 ), thus forming amine-containing fluorophores. Since this chemical reaction can be applied to any azo-containing quencher compound, a great variety of substances can be readily obtained synthetically. This approach provides a promising tool in the use of fluorescence-based investigations of biomolecular interactions., (Copyright © 2019. Published by Elsevier Inc.)

Polycyclic aromatic hydrocarbons (PAHs), such as naphthalene, are potential health risks due to their carcinogenic and mutagenic effects. Bacteria from the genus Rhodococcus are able to metabolise a wide variety of pollutants such as alkanes, aromatic compounds and halogenated hydrocarbons. A naphthalene dioxygenase from Rhodococcus sp. strain NCIMB12038 has been characterised for the first time, using electron paramagnetic resonance (EPR) spectroscopy and UV-Vis spectrophotometry. In the native state, the EPR spectrum of naphthalene 1,2-dioxygenase (NDO) is formed of the mononuclear high spin Fe(III) state contribution and the oxidised Rieske cluster is not visible as EPR-silent. In the presence of the reducing agent dithionite a signal derived from the reduction of the [2Fe-2S] unit is visible. The oxidation of the reduced NDO in the presence of O 2 -saturated naphthalene increased the intensity of the mononuclear contribution. A study of the "peroxide shunt", an alternative mechanism for the oxidation of substrate in the presence of H 2 O 2 , showed catalysis via the oxidation of mononuclear centre while the Rieske-type cluster is not involved in the process. Therefore, the ability of these enzymes to degrade recalcitrant aromatic compounds makes them suitable for bioremediative applications and synthetic purposes.

This study investigates the removal of arsenite (As(III)) from water using dithionite activated by UV light. This work evaluated the removal kinetics of As(III) under UV light irradiation as affected by dithionite dose and light intensity, and characterized the nature of the precipitated solids using XPS and SEM-EDS. Photolysis of dithionite was observed by measuring dithionite concentration using UV absorbance at 315nm. This study also investigated the effect of UV light path length on soluble As concentrations to understand resolubilization mechanisms. Total soluble As concentrations were observed to decrease with reaction time due to reduction of arsenite to form solids having a yellow-orange color. The removal mechanism was found to be reductive precipitation that formed solids of elemental arsenic or arsenic sulfide. However, these solids were observed to resolubilize at later times after dithionite had been consumed. Resolubilization of As was prevented and additional As removal was obtained by frequent dosing of dithionite throughout the experiment. As(III) removal is attributed to photolysis of dithionite by UV light and production of reactive radicals that reduce As(III) and convert it to solid forms., (Copyright © 2018. Published by Elsevier B.V.)

Human manganese superoxide dismutase (MnSOD) is one of the most significant enzymes in preventing mitochondrial dysfunction and related diseases by combating reactive oxygen species (ROS) in the mitochondrial matrix. Mitochondria are the source of up to 90% of cellular ROS generation, and MnSOD performs its necessary bioprotective role by converting superoxide into oxygen and hydrogen peroxide. This vital catalytic function is conducted via cyclic redox reactions between the substrate and the active-site manganese using proton-coupled electron transfers. Owing to protons being difficult to detect experimentally, the series of proton transfers that compose the catalytic mechanism of MnSOD are unknown. Here, methods are described to discern the proton-based mechanism using chemical treatments to control the redox state of large perdeuterated MnSOD crystals and subsequent neutron diffraction. These methods could be applicable to other crystal systems in which proton information on the molecule in question in specific chemical states is desired., (open access.)

Magnetic micro-sized mesoporous silica particles were used for the preparation of a gated material able to release an entrapped cargo in the presence of an azo-reducing agent and, to some extent, at acidic pH. The magnetic mesoporous microparticles were loaded with safranin O and the external surface was functionalized with an azo derivative 1 (bearing a carbamate linkage) yielding solid S1 . Aqueous suspensions of S1 at pH 7.4 showed negligible safranin O release due to the presence of the bulky azo derivative attached onto the external surface of the inorganic scaffold. However, in the presence of sodium dithionite (azoreductive agent), a remarkable safranin O delivery was observed. At acidic pH, a certain safranin O release from S1 was also found. The pH-triggered safranin O delivery was ascribed to the acid-induced hydrolysis of the carbamate moiety that linked the bulky azo derivatives onto the mesoporous inorganic magnetic support. The controlled release behavior of S1 was also tested using a model that simulated the gastro intestinal tract., Competing Interests: The authors declare no conflict of interest.

DNA-encoded chemical libraries have emerged as a cost-effective alternative to high-throughput screening (HTS) for hit identification in drug discovery. A key factor for productive DNA-encoded libraries is the chemical diversity of the small molecule moiety attached to an encoding DNA oligomer. The library structure diversity is often limited to DNA-compatible chemical reactions in aqueous media. Herein, we describe a facile process for reducing aryl nitro groups to aryl amines. The new protocol offers simple operation and circumvents the pyrophoric potential of the conventional method (Raney nickel). The reaction is performed in aqueous solution and does not compromise DNA structural integrity. The utility of this method is demonstrated by the versatile synthesis of benzimidazoles on DNA.

A combined process of coagulation-catalytic ozonation-anaerobic sequencing batch reactor (ASBR)-SBR was developed at lab scale for treating a real sodium dithionite wastewater with an initial chemical oxygen demand (COD) of 21,760-22,450 mg/L. Catalytic ozonation with the prepared cerium oxide (CeO 2 )/granular activated carbon catalyst significantly enhances wastewater biodegradability and reduces wastewater microtoxicity. The results show that, under the optimum conditions, the removal efficiencies of COD and suspended solids are averagely 99.3% and 95.6%, respectively, and the quality of final effluent can meet the national discharge standard of China. The coagulation and ASBR processes remove a considerable proportion of organic matter, while the SBR plays an important role in post-polish of final effluent. The ecotoxicity of the wastewater is greatly reduced after undergoing the hybrid treatment. This work demonstrates that the hybrid system has the potential to be applied for the advanced treatment of high-strength industrial wastewater.

Large amounts of chromite ore processing residue (COPR) wastes have been deposited in many countries worldwide, generating significant contamination issues from the highly mobile and toxic hexavalent chromium species (Cr(VI)). In this study, sodium dithionite (Na 2 S 2 O 4 ) was used to reduce Cr(VI) to Cr(III) in COPR containing high available Fe, and then sodium phosphate (Na 3 PO 4 ) was utilized to further immobilize Cr(III), via a two-step procedure (TSP). Remediation and immobilization processes and mechanisms were systematically investigated using batch experiments, sequential extraction studies, X-ray diffraction (XRD) and X-ray Photoelectron Spectroscopy (XPS). Results showed that Na 2 S 2 O 4 effectively reduced Cr(VI) to Cr(III), catalyzed by Fe(III). The subsequent addition of Na 3 PO 4 further immobilized Cr(III) by the formation of crystalline CrPO 4 ·6H 2 O. However, addition of Na 3 PO 4 simultaneously with Na 2 S 2 O 4 (via a one-step procedure, OSP) impeded Cr(VI) reduction due to the competitive reaction of Na 3 PO 4 and Na 2 S 2 O 4 with Fe(III). Thus, the remediation efficiency of the TSP was much higher than the corresponding OSP. Using an optimal dosage in the two-step procedure (Na 2 S 2 O 4 at a dosage of 12× the stoichiometric requirement for 15 days, and then Na 3 PO 4 in a molar ratio (i.e. Na 3 PO 4 : initial Cr(VI)) of 4:1 for another 15 days), the total dissolved Cr in the leachate determined via Toxicity Characteristic Leaching Procedure (TCLP Cr) testing of our samples was reduced to 3.8 mg/L (from an initial TCLP Cr of 112.2 mg/L, i.e. at >96% efficiency)., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

Soil washing is a promising way to remediate arsenic-contaminated soils. Most research has mostly focused on seeking efficient extractants for removing arsenic, but not concerned with any changes in soil properties when using this technique. In this study, the removal of arsenic from a heavily contaminated soil employing different washing solutions including H 3 PO 4 , NaOH and dithionite in EDTA was conducted. Subsequently, the changes in soil physicochemical properties and phytotoxicity of each washing technique were evaluated. After washing with 2 M H 3 PO 4 , 2 M NaOH or 0.1 M dithionite in 0.1 M EDTA, the soil samples' arsenic content met the clean-up levels stipulated in China's environmental regulations. H 3 PO 4 washing decreased soil pH, Ca, Mg, Al, Fe, and Mn concentrations but increased TN and TP contents. NaOH washing increased soil pH but decreased soil TOC, TN and TP contents. Dithionite in EDTA washing reduced soil TOC, Ca, Mg, Al, Fe, Mn and TP contents. A drastic color change was observed when the soil sample was washed with H 3 PO 4 or 0.1 M dithionite in 0.1 M EDTA. After adjusting the soil pH to neutral, wheat planted in the soil sample washed by NaOH evidenced the best growth of all three treated soil samples. These results will help with selecting the best washing solution when remediating arsenic-contaminated soils in future engineering applications., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

Sorafenib and regorafenib are small-molecule kinase inhibitors approved for the treatment of locally recurrent or metastatic, progressive, differentiated thyroid carcinoma, renal cell carcinoma, and hepatocellular carcinoma (sorafenib) and of colorectal cancer (regorafenib). As of now, the mechanisms, which are responsible for their antitumor activities, are not completely understood. Given the lipophilic nature of the molecules, it can be hypothesized that the pharmacological impact is mediated by the interaction with cellular membranes as it is true for many pharmacologically active molecules. However, an interaction of sorafenib or regorafenib with lipid membranes has not yet been investigated in detail. Here, we characterized the interaction of both drugs with lipid membranes by applying a variety of biophysical approaches including nuclear magnetic resonance, electron spin resonance, and fluorescence spectroscopy. We found that sorafenib and regorafenib bind to lipid membranes by inserting into the lipid-water interface of the bilayer. This membrane embedding causes a disturbance of bilayer structure leading to an increased permeability of the membrane for polar molecules. One approach shows that the extent of the effects depends on the membrane lipid composition underlining a particular role of phosphatidylcholine and cholesterol. Our data for the first time characterize the impact of sorafenib and regorafenib on the lipid membrane structure and dynamics, which may contribute to a better understanding of their effectiveness in the treatment of malignancies as well as of their side effects., (Copyright © 2016 Elsevier B.V. All rights reserved.)

A convenient two-step method is described for the detection of nitrotyrosine-containing proteins. First, nitrotyrosines are reduced to aminophenols using sodium dithionite. Following this, an oxidative coupling reaction is used to attach anilines bearing fluorescence reporters or affinity probes. Features of this approach include fast reaction times, pmol-level sensitivity, and excellent chemoselectivity.

In direct experiments, rate constants of photochemical (kP) and non-photochemical (kP(+)) fluorescence quenching were determined in membrane fragments of photosystem II (PSII), in oxygen-evolving PSII core particles, as well as in core particles deprived of the oxygen-evolving complex. For this purpose, a new approach to the pulse fluorometry method was implemented. In the "dark" reaction center (RC) state, antenna fluorescence decay kinetics were measured under low-intensity excitation (532 nm, pulse repetition rate 1 Hz), and the emission was registered by a streak camera. To create a "closed" [P680(+)QA(-)] RC state, a high-intensity pre-excitation pulse (pump pulse, 532 nm) of the sample was used. The time advance of the pump pulse against the measuring pulse was 8 ns. In this experimental configuration, under the pump pulse, the [P680(+)QA(-)] state was formed in RC, whereupon antenna fluorescence kinetics was measured using a weak testing picosecond pulsed excitation light applied to the sample 8 ns after the pump pulse. The data were fitted by a two-exponential approximation. Efficiency of antenna fluorescence quenching by the photoactive RC pigment in its oxidized (P680(+)) state was found to be ~1.5 times higher than that of the neutral (P680) RC state. To verify the data obtained with a streak camera, control measurements of PSII complex fluorescence decay kinetics by the single-photon counting technique were carried out. The results support the conclusions drawn from the measurements registered with the streak camera. In this case, the fitting of fluorescence kinetics was performed in three-exponential approximation, using the value of τ1 obtained by analyzing data registered by the streak camera. An additional third component obtained by modeling the data of single photon counting describes the P680(+)Pheo(-) charge recombination. Thus, for the first time the ratio of kP(+)/kP = 1.5 was determined in a direct experiment. The mechanisms of higher efficiency for non-photochemical antenna fluorescence quenching by RC cation radical in comparison to that of photochemical quenching are discussed.

Two grams of delignified substrate at 10% (w/v) level was subjected to biphasic dilute acid hydrolysis using phosphoric acid, hydrochloric acid and sulfuric acid separately at 110 °C for 10 min in phase-I and 121 °C for 15 min in phase-II. Combinations of acid concentrations in two phases were varied for maximum holocellulose hydrolysis with release of fewer inhibitors, to select the suitable acid and its concentration. Among three acids, sulfuric acid in combination of 1 & 2% (v/v) hydrolyzed maximum holocellulose of 25.44±0.44% releasing 0.51±0.02 g/L of phenolics and 0.12±0.002 g/L of furans, respectively. Further, hydrolysis of delignified substrate using selected acid by varying reaction time and temperature hydrolyzed 55.58±1.78% of holocellulose releasing 2.11±0.07 g/L and 1.37±0.03 g/L of phenolics and furans, respectively at conditions of 110 °C for 45 min in phase-I & 121 °C for 60 min in phase-II., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

Specific membrane proteins, termed lipid flippases, play a central role in facilitating the movement of lipids across cellular membranes. In this protocol, we describe the reconstitution of ATP-driven lipid flippases in liposomes and the analysis of their in vitro flippase activity based on the use of fluorescent lipid derivatives. Working with purified and reconstituted systems provides a well-defined experimental setup and allows to directly characterize these membrane proteins at the molecular level.

Wastewaters containing Cu(II) along with ligands are ubiquitous in various industrial sectors. Efficacy of treatment processes for copper removal, especially precipitation, is greatly debilitated by ligands. Chemical reduction being commonly employed for production of metal nanoparticles has also been used for removing copper. Addition of ammonia was reported to be essential for improving copper reduction efficiency by increasing copper solubility at alkaline pH values. In this study, chemical reduction was employed to treat ligand-containing wastewater, exploiting the fact that ligands and metals are coexisted in many wastewaters. Result shows that copper ions were removed by either reduction or precipitation mechanisms depending on pH, type of ligands, and mixing condition. Complete copper reduction/removal was achieved under optimal condition. The lowest removal efficiency observed at pH 9.0 for ammonia system is due to formation of nano-sized particles, which are readily to pass through 0.45μm filter used for sample pretreatment before copper analysis. Instead of producing metallic copper, cuprous and copper oxide are identified in the samples collected from ammonia system and EDTA system, respectively. Re-oxidation of metallic copper particles by atmospheric oxygen during sample handling or incomplete reduction of Cu(II) ions during reduction process might be the cause. Finally, reduction process was applied to treat real wastewater, achieving complete removal of copper but only 10% of nickel., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

Microperoxidase-11 (MP11) is an undecapeptide derived from horse heart cytochrome c (cyt c) and characterized by a covalently-linked solvent-exposed heme group. Here, kinetics of the NO2(-)-mediated nitrosylation of ferrous MP11 (MP11-Fe(II)) is reported. Data were obtained between pH6.4 and 8.2, at 20.0°C. The NO2(-)-mediated conversion of MP11-Fe(II) to MP11-Fe(II)-NO requires one proton; accordingly, values of the apparent second-order rate constant (kon) decrease by about two orders of magnitude from (2.9±0.3)×10(1)M(-1)s(-1) to (5.0±0.6)×10(-1)M(-1)s(-1) upon increasing pH from 6.4 to pH8.2. The slope of the linear fitting of Logkon versus pH is -1.00±0.06. Values of kon for the NO2(-)-mediated nitrosylation of MP11-Fe(II) are similar to those of penta-coordinated cardiolipin-bound horse heart cyt c, exceeding by about two orders of magnitude those of wild-type horse heart cyt c. Present results highlight the role of heme distal residues in modulating horse heart cyt c reactivity., (Copyright © 2015 Elsevier Inc. All rights reserved.)

A simple and low cost flow injection colorimetric system has been developed for determination of paraquat in natural water. The developed method is based on the reduction of paraquat by using sodium dithionite as a reducing agent in an alkaline medium to produce a blue free radical ion that can be detected by a simple light emitting diode-light dependent resistor (LED-LDR) colorimeter. The standard or sample solution was injected via a set of 3-way solenoid valves into a water carrier stream and flowed to merge with reagent to generate a colored product which is proportional to the concentration of paraquat ion in the solution. Under the optimum condition of the system, i.e., mixing coil length 30 cm, flow rate 2.0 mL min(-1), sample volume 100 μL, concentrations of dithionite 0.1% (w/v) and sodium hydroxide 0.06 mol L(-1), a linear calibration graph in the range of 0.2-10.0 mg L(-1) with a correlation coefficient of 0.9996, and a limit of detection of 0.15 mg L(-1) were achieved. Relative standard deviation for 9 replicate injections of 1 mg L(-1) paraquat is 3.7%. A sample throughput of 40 injections h(-1) was achieved. The limit of detection can be improved by off-line preconcentration of paraquat employing a column packed with Dowex 50WX8-100 (H) cation exchange resin and eluted with 10% (w/v) ammonium chloride in ammonium buffer solution pH 10. The eluting solution was then injected into the FI system for paraquat determination. The proposed system did not suffer from interferences of some possible ions in natural water and other herbicides. Recoveries obtained by spiking 0.5 and 5.0 mg L(-1) paraquat standard into water samples were in the range of 104-110% and 101-105%, respectively. The developed system can be conveniently applied for screening of paraquat contaminated in natural water., (Copyright © 2015 Elsevier B.V. All rights reserved.)

Iron oxide minerals are the most important sinks of arsenic in arsenic contaminated soils. Therefore, the effective extraction of arsenic bound to the iron oxides is essential to increase the efficiency of arsenic removal from soils. In this study, the reductive extraction of arsenic from contaminated soils was studied with a combination of dithionite and oxalate in order to remediate arsenic-contaminated soils via the reductive dissolution of arsenic associated iron oxides. The addition of oxalate greatly enhanced the reductive arsenic extraction by forming strong complexes with iron, which could prevent the precipitation of a new iron oxide phase and also enhance the iron oxide dissolution via a non-reductive dissolution pathway. Iron in soils can either be extracted as a soluble Fe(C2O4)2(2-) or remain in the soil as a solid Fe(C2O4) precipitation depending on the oxalate to iron molar ratio. Arsenic extraction was hindered by an excess of dithionite, and the optimum dithionite concentration was affected by the arsenic concentrations and the speciations present in the soils. Relatively high arsenic extraction could be obtained by a combination of dithionite and oxalate at a wide range of pH conditions., (Copyright © 2014 Elsevier B.V. All rights reserved.)

Research has suggested that exposure to sub-micellar concentrations of bile salts (BS) increases the permeability of lipid bilayers in a time-dependent manner. In this study, incubation of soy phosphatidylcholine small unilamellar vesicles (liposomes) with sub-micellar concentrations of cholate (C), deoxycholate (DC), 12-monoketocholate (MKC) or taurocholate (TC) in pH 7.2 buffer increased membrane fluidity and negative zeta potential in the order of increasing BS liposome-pH 7.2 buffer distribution coefficients (MKC < C ≈ TC < DC). In liposomes labeled with the dithionite-sensitive fluorescent lipid N-(7-nitrobenz-2-oxa-1,3-diazol-4-yl)phosphatidylethanolamine (NBD-PE) in both leaflets and equilibrated with sub-micellar concentrations of BS, fluorescence decline during continuous exposure to dithionite was biphasic involving a rapid initial phase followed by a slower second phase. Membrane permeability to dithionite as measured by the rate of the second phase increased in the order control < MKC < TC ∼ C < DC. In liposomes labeled with NBD-PE in the inner leaflet only and incubated with the same concentrations of C, DC and MKC, membrane permeability to dithionite initially increased very rapidly in the order MKC < C < DC before impermeability to dithionite was restored after which fluorescence decline was consistent with NBD-PE flip-flop. For liposomes incubated with TC, membrane permeability to dithionite was only slightly increased and the decline in fluorescence was mainly the result of NBD-PE flip-flop. These results provide evidence that BS interact with lipid bilayers in a time-dependent manner that is different for conjugated and unconjugated BS. MKC appears to cause least disturbance to liposomal membranes but, when the actual MKC concentration in liposomes is taken into account, MKC is actually the most disruptive.

Chemical reduction was firstly employed to treat synthetic wastewaters of various compositions prepared to simulate the retentate stream of polyelectrolyte enhanced ultrafiltration (PEUF). With fixed Cu:polyethylenimine (PEI) monomer:dithionite molar ratio, increasing copper concentration increases copper removal efficiency. Under fixed Cu:dithionite molar ratio and fixed Cu concentration, increasing PEI monomer:copper molar ratio decreases copper removal efficiency. The formation of nano-sized copper particles, which readily pass through 0.45 μm filter used for sample pretreatment before residual copper analysis, might be the reason behind the decreasing copper removal efficiency observed. Particle size analysis shows that the size of copper particles, which are formed through reduction reaction, increases with decreasing pH value and increasing reaction time. As ultrafiltration is capable of removing these nano-sized particles, integration of chemical reduction and PEUF is proposed to simultaneously achieve regeneration of polyelectrolyte and recovery of copper in one process. Results show that the proposed process could achieve almost complete copper removal without being affected by reaction pH.

Wastewaters containing Cu(II) and ligands are ubiquitous in various industrial sectors, and efficacy of copper removal processes, especially precipitation, is greatly compromised by ligands. Chemical reduction, being commonly employed for production of metal nanoparticles, is also effective for metal removal. Adjustment of pH and addition of ligands are important to control the particle size in metallic nanoparticle production. Exploiting the fact that ligands and metals coexist in many wastewaters, chemical reduction was employed to treat ligand-containing wastewater in this study. The experimental result shows that depending on pH, type of ligands, and copper:ligand molar ratio, copper could be removed by either the reduction or precipitation mechanism. Almost complete copper removal could be achieved by the reduction mechanism under optimal condition for solutions containing either EDTA (ethylenediaminetetraacetic acid) or citrate ligands. For solutions containing ammonia, depending on pH and Cu:ammonia molar ratio, copper was removed by both precipitation and reduction mechanisms. At pH of 9.0, formation of nano-sized particles, which readily pass through a 0.45 μm filter used for sample pretreatment before residual copper analysis, results in the lowest copper removal efficiency. Both cuprous oxide and metallic copper are identified in the solids produced, and the possible explanations are provided.

Abiotic reductive extraction of arsenic from contaminated soils was studied with various reducing agents and combinations of reducing and chelating agents in order to remediate arsenic-contaminated soils. Oxalate and ascorbic acid were effective to extract arsenic from soil in which arsenic was associated with amorphous iron oxides, but they were not effective to extract arsenic from soils in which arsenic was bound to crystalline oxides or those in which arsenic was mainly present as a scorodite phase. An X-ray photoelectron spectroscopy study showed that iron oxides present in soils were transformed to Fe(II,III) or Fe(II) oxide forms such as magnetite (Fe3O4, Fe(II)Fe2(III)O4) by reduction with dithionite. Thus, arsenic extraction by dithionite was not effective due to the re-adsorption of arsenic to the newly formed iron oxide phase. Combination of chelating agents with reducing agents greatly improved arsenic extraction from soil samples. About 90% of the total arsenic could be extracted from all soil samples by using a combination of dithionite and EDTA. Chelating agents form strong complexation with iron, which can prevent precipitation of a new iron oxide phase and also enhance iron oxide dissolution via a non-reductive dissolution pathway., (Copyright © 2014 Elsevier B.V. All rights reserved.)

Bioorthogonal cleavable linkers are attractive building blocks for compounds that can be manipulated to study biological and cellular processes. Sodium dithionite sensitive azobenzene-containing (Abc) peptides were applied for the temporary stabilization of recombinant MHC complexes, which can then be employed to generate libraries of MHC tetramers after exchange with a novel epitope. This technology represents an important tool for high-throughput studies of disease-specific T cell responses., (© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Electron Paramagnetic Resonance (EPR) monitored redox titrations are a powerful method to determine the midpoint potential of cofactors in proteins and to identify and quantify the cofactors in their detectable redox state. The technique is complementary to direct electrochemistry (voltammetry) approaches, as it does not offer information on electron transfer rates, but does establish the identity and redox state of the cofactors in the protein under study. The technique is widely applicable to any protein containing an electron paramagnetic resonance (EPR) detectable cofactor. A typical titration requires 2 ml protein with a cofactor concentration in the range of 1-100 µM. The protein is titrated with a chemical reductant (sodium dithionite) or oxidant (potassium ferricyanide) in order to poise the sample at a certain potential. A platinum wire and a Ag/AgCl reference electrode are connected to a voltmeter to measure the potential of the protein solution A set of 13 different redox mediators is used to equilibrate between the redox cofactors of the protein and the electrodes. Samples are drawn at different potentials and the Electron Paramagnetic Resonance spectra, characteristic for the different redox cofactors in the protein, are measured. The plot of the signal intensity versus the sample potential is analyzed using the Nernst equation in order to determine the midpoint potential of the cofactor.

The cytochrome b6f complex, a member of the cytochrome bc family that mediates energy transduction in photosynthetic and respiratory membranes, is a hetero-oligomeric complex that utilizes two pairs of b-hemes in a symmetric dimer to accomplish trans-membrane electron transfer, quinone oxidation-reduction, and generation of a proton electrochemical potential. Analysis of electron storage in this pathway, utilizing simultaneous measurement of heme reduction, and of circular dichroism (CD) spectra, to assay heme-heme interactions, implies a heterogeneous distribution of the dielectric constants that mediate electrostatic interactions between the four hemes in the complex. Crystallographic information was used to determine the identity of the interacting hemes. The Soret band CD signal is dominated by excitonic interaction between the intramonomer b-hemes, bn and bp, on the electrochemically negative and positive sides of the complex. Kinetic data imply that the most probable pathway for transfer of the two electrons needed for quinone oxidation-reduction utilizes this intramonomer heme pair, contradicting the expectation based on heme redox potentials and thermodynamics, that the two higher potential hemes bn on different monomers would be preferentially reduced. Energetically preferred intramonomer electron storage of electrons on the intramonomer b-hemes is found to require heterogeneity of interheme dielectric constants. Relative to the medium separating the two higher potential hemes bn, a relatively large dielectric constant must exist between the intramonomer b-hemes, allowing a smaller electrostatic repulsion between the reduced hemes. Heterogeneity of dielectric constants is an additional structure-function parameter of membrane protein complexes.

Many enzymes involved in bioenergetic processes contain chains of redox centers that link the protein surface, where interaction with electron donors or acceptors occurs, to a secluded catalytic site. In numerous cases these redox centers can transfer only single electrons even when they are associated to catalytic sites that perform two-electron chemistry. These chains provide no obvious contribution to enhance chemiosmotic energy conservation, and often have more redox centers than those necessary to hold sufficient electrons to sustain one catalytic turnover of the enzyme. To investigate the role of such a redox chain we analyzed the transient kinetics of fumarate reduction by two flavocytochromes c3 of Shewanella species while these enzymes were being reduced by sodium dithionite. These soluble monomeric proteins contain a chain of four hemes that interact with a flavin adenine dinucleotide (FAD) catalytic center that performs the obligatory two electron-two proton reduction of fumarate to succinate. Our results enabled us to parse the kinetic contribution of each heme towards electron uptake and conduction to the catalytic center, and to determine that the rate of fumarate reduction is modulated by the redox stage of the enzyme, which is defined by the number of reduced centers. In both enzymes the catalytically most competent redox stages are those least prevalent in a quasi-stationary condition of turnover. Furthermore, the electron distribution among the redox centers during turnover suggested how these enzymes can play a role in the switch between respiration of solid and soluble terminal electron acceptors in the anaerobic bioenergetic metabolism of Shewanella., (Copyright © 2014 Elsevier B.V. All rights reserved.)

Colloids may facilitate the transport of trace elements and nutrients like phosphate in soil. In this study, we characterized soil colloids (<0.45 μm), extracted from four agricultural soils by Na-bicarbonate and Na-pyrophosphate, by two complementary analytical techniques; asymmetric flow field-flow fractionation (AF4) and X-ray absorption spectroscopy (XAS). The combined results from AF4 and XAS show that colloidal Fe is present as (i) free Fe-(hydr)oxide nanoparticles, (ii) Fe-(hydr)oxides associated with clay minerals, and (iii) Fe in clay minerals. Free Fe-(hydr)oxide nanoparticles, which can be as small as 2-5 nm, are extracted with Na-pyrophosphate but not with Na-bicarbonate, except for one soil. In contrast, Fe-(hydr)oxides associated with clay minerals are dispersed by both extractants. XAS results show that the speciation of Fe in the colloidal fractions closely resembles the speciation of Fe in the bulk soil, indicating that dispersion of colloidal Fe from the studied soils was rather unselective. In one Fe-rich soil, colloidal Fe was dominantly dispersed in the form of free Fe-(hydr)oxide nanoparticles. In the other three soils, dispersed Fe-(hydr)oxides were dominantly associated with clay minerals, suggesting that their dispersion as free nanoparticles was inhibited by strong attachment. However, in these soils, Fe-(hydr)oxides can be dispersed as oxide-clay associations and may as such facilitate the transport of trace elements.

This paper describes the regio- and stereoselective reduction of △⁴-3-keto moiety in certain steroids using Na₂S₂O₄/NaHCO₃ and CuCl/NaBH₄, respectively. Using either one of the two reduction agents in the reaction, the 17-substituents in the D ring were observed to have clearly influenced the stereoselective reduction of 4-ene in the A ring by the so-called conformational transmission effect. Na₂S₂O₄/NaHCO₃ regioselectively reduced CC at 4-position of 17-substituted-androst-4-en-3-one derivatives to 5α-H-3-one as the main isomer. And as an extended application, Epiandrosterone (11) was further synthesized from androst-4-en-3,17-dione (AD) via four steps. The total yield from this was about 45%. In the presence of CuCl/NaBH₄, △⁴-3-keto conjugated reduction of 17-spirocyclic ethylene ketal protected androst-4-en-3-one derivatives mainly produced 3α-hydroxy-5β-H isomers, at a yield around 81%. Considering the scaffold configuration of 3α-hydroxy-5β-H moiety coincided with that of bile acid analogs, this selective reduction could also be used as an alternative method for the synthetic study of bile acids using AD and its derivatives, which are from the microorganism degradation of natural sterols, as the potential materials. Meanwhile, configurations of the reductive compounds 5b, 6b, 9, 10 and 17e were identified by X-ray diffraction., (Copyright © 2013 Elsevier Inc. All rights reserved.)

Considering the confusing biodistribution data through the literature and few reported alerts as well as our preliminary biodistribution results, we decided to evaluate the interaction and interference of the commonly present (99m) Tc (technetium-99m)-stannic oxide colloid during the direct stannous chloride (99m) Tc-labeling procedure and to assess its influence on the biodistribution pattern of amphiphilic poly(lactic-co-glycolic acid) nanoparticles. In order to confirm our thesis, beside stannous chloride, we employed two different reducing agents that don't form colloidal particles. The use of sodium borohydride was previously reported in the literature, whereas sodium dithionite was adapted for the first time in the (99m) Tc direct labeling procedure for nanoparticles. The results in our paper clearly differentiate among samples with and without colloidal impurities originating from the labeling procedure with a logical follow up of the radiochemical, physicochemical evaluation, and biodistribution studies clarifying previously reported data on stannic oxide colloidal interference. (99m) Tc-nanoparticle complex labeled with sodium dithionite as reducing agent illustrated appropriate labeling efficacy, stability, and potential for further use in biodistribution studies thus providing solution for the problem of low-complex stability when sodium borohydride is used and colloidal stannic oxide interference for stannous chloride procedure., (Copyright © 2013 John Wiley & Sons, Ltd.)

We studied the kinetics of reactions of cob(I)alamin and cob(I)inamide with thiosulfate, sulfite, and dithionite by UV-Visible (UV-Vis) and stopped-flow spectroscopy. We found that the two Co(I) species were oxidized by these sulfur-containing compounds to Co(II) forms: oxidation by excess thiosulfate leads to penta-coordinate complexes and oxidation by excess sulfite or dithionite leads to hexa-coordinate Co(II)-SO2(-) complexes. The net scheme involves transfer of three electrons in the case of oxidation by thiosulfate and one electron for oxidation by sulfite and dithionite. On the basis of kinetic data, the nature of the reactive oxidants was suggested, i.e., HS2O3(-) (for oxidation by thiosulfate), S2O5(2-), HSO3(-), and aquated SO2 (for oxidation by sulfite), and S2O4(2-) and SO2(-) (for oxidation by dithionite). No difference was observed in kinetics with cob(i)alamin or cob(i)inamide as reductants.

Short-term (3 d and 28 d) and long-term (1 a) stabilization effects of Cr contaminated soil were investigated through nature curing, using four amendments including ferrous sulfide, ferrous sulfate, zero-valent iron and sodium dithionite. The results indicated that ferrous sulfide and zero-valent iron were not helpful for the stabilization of Cr(VI) when directly used because of their poor solubility and immobility. Ferrous sulfate could effectively and rapidly decrease total leaching Cr and Cr(VI) content. The stabilization effect was further promoted by the generation of iron hydroxides after long-term curing. Sodium dithionite also had positive effect on soil stabilization. Appropriate addition ratio of the two chemicals could help maintain the soil pH in range of 6-8.

The reactivity of coordinated nitroxyl (HNO) has been explored with the [Fe(II)(CN)(5)HNO](3-) complex in aqueous medium, pH 6. We discuss essential biorelevant issues as the thermal and photochemical decompositions, the reactivity toward HNO dissociation, the electrochemical behavior, and the reactions with oxidizing and reducing agents. The spontaneous decomposition in the absence of light yielded a two-electron oxidized species, the nitroprusside anion, [Fe(II)(CN)(5)NO](2-), and a negligible quantity of N(2)O, with k(obs)≈5×10(-7)s(-1), at 25.0°C. The value of k(obs) represents an upper limit for HNO release, comparable to values reported for other structurally related L ligands in the [Fe(II)(CN)(5)L](n-) series. These results reveal that the FeN bond is strong, suggesting a significant σ-π interaction, as already postulated for other HNO-complexes. The [Fe(II)(CN)(5)HNO](3-) ion showed a quasi-reversible oxidation wave at 0.32 V (vs normal hydrogen electrode), corresponding to the [Fe(II)(CN)(5)HNO](3-)/[Fe(II)(CN)(5)NO](3-),H(+) redox couple. Hexacyanoferrate(III), methylviologen and the nitroprusside ion have been selected as potential oxidants. Only the first reactant achieved a complete oxidation process, initiated by a proton-coupled electron transfer reaction at the HNO ligand, with nitroprusside as a final oxidation product. Dithionite acted as a reductant of [Fe(II)(CN)(5)HNO](3-), in a 4-electron process, giving NH(3). The high stability of bound HNO may resemble the properties in related Fe(II) centers of redox active enzymes. The very minor release of N(2)O shows that the redox conversions may evolve without disruption of the FeN bonds, under competitive conditions with the dissociation of HNO., (Copyright © 2012 Elsevier Inc. All rights reserved.)

Arsenic-contaminated rice grain may threaten human health globally. Since H₃AsO₃⁰ is the predominant As species found in paddy pore-waters, and H₄SiO₄⁰ and H₃AsO₃⁰ share an uptake pathway, silica amendments have been proposed to decrease As uptake and consequent As concentrations in grains. Here, we evaluated the impact of two silicate mineral additions differing in solubility (+Si(L), diatomaceous earth, 0.29 mM Si; +Si(H), Si-gel, 1.1 mM Si) to soils differing in mineralogy on arsenic concentration in rice. The +Si(L) addition either did not change or decreased As concentration in pore-water but did not change or increased grain-As levels relative to the (+As--Si) control. The +Si(H) addition increased As in pore-water, but it significantly decreased grain-As relative to the (+As--Si) control. Only the +Si(H) addition resulted in significant increases in straw- and husk-Si. Total grain- and straw-As was negatively correlated with pore-water Si, and the relationship differed between two soils exhibiting different mineralogy. These differing results are a consequence of competition between H₄SiO₄⁰ and H₃AsO₃⁰ for adsorption sites on soil solids and subsequent plant-uptake, and illustrate the importance of Si mineralogy on arsenic uptake.

Carbon monoxide-releasing molecules (CO-RMs) emulate the beneficial (e.g., anti-inflammatory) effects of CO in biology. CO release from CO-RMs is routinely determined in the presence of reduced deoxy-myoglobin by measuring the formation of carboxy-myoglobin (Mb-CO). Previous studies have highlighted discrepancies between the apparent CO release rates of some CO-RMs established using this assay versus other experimental data where a slower or more complex mechanism of release is suggested. It has been hypothesized that some CO-RMs require a CO acceptor, believed to be reduced myoglobin in Mb-CO assays, in order to facilitate the release of CO. Here, we show, for the first time, that CO is not liberated from the ruthenium (Ru)-based [Ru(CO)(3)Cl(2)](2) (CORM-2) and [Ru(CO)(3)Cl(glycinate)] (CORM-3) at an appreciable rate in the presence of reduced myoglobin alone. Rather, we confirm that it is the reducing agent sodium dithionite that facilitates release of CO from these CO-RMs. Other sulfite compounds, namely sodium sulfite and potassium metabisulfite, also promote the liberation of CO from CORM-3. We describe an alternative oxy-hemoglobin assay that eliminates dithionite and suggest that the efficacy of CO-RMs results from intracellular interactions with anions that facilitate CO delivery to therapeutic targets., (Copyright © 2012 Elsevier Inc. All rights reserved.)

Current strategies for identification and quantification of 3-nitrotyrosine (3NT) post-translationally modified proteins (PTM) generally rely on biotin/avidin enrichment. Quantitative approaches have been demonstrated which employ isotopic labeling or isobaric tagging in order to quantify differences in the relative abundances of 3NT-modified proteins in two or potentially eight samples, respectively. Here, we present a novel strategy which uses combined precursor isotopic labeling and isobaric tagging (cPILOT) to increase the multiplexing capability of quantifying 3NT-modified proteins to 12 or 16 samples using commercially available tandem mass tags (TMT) or isobaric tags for relative and absolute quantification (iTRAQ), respectively. This strategy employs "light" and "heavy" labeled acetyl groups to block both N-termini and lysine residues of tryptic peptides. Next, 3NT is reduced to 3-aminotyrosine (3AT) using sodium dithionite followed by derivatization of light and heavy labeled 3AT-peptides with either TMT or iTRAQ multiplex reagents. We demonstrate the proof-of-principle utility of cPILOT with in vitro nitrated bovine serum albumin (BSA) and mouse splenic proteins using TMT(0), TMT(6), and iTRAQ(8) reagents and discuss limitations of the strategy.

A simple and sensitive chemiluminescence (CL) method coupled with flow-injection technique is proposed to determine naproxen (NAP). The method is based upon the enhancement of the weak CL signal arising from the reaction of Ce(IV) and Na(2)S(2)O(4) with Eu(3+) to form the Eu(3+)-Ce(IV)-Na(2)S(2)O(4) system. The CL intensity was significantly increased by the introduction of NAP into this system in the presence of silver nanoparticles (Ag NPs). Examination of the recorded UV-vis spectra and fluorescence spectra indicated that the energy of the intermediate SO(2)*, which originated from the redox reaction of Ce(IV) and Na(2)S(2)O(4), was transferred to Eu(3+) via NAP and that the process was accelerated by Ag NPs due to their catalytic activity. Under the optimum conditions, the CL intensity was increased with increasing NAP concentration and the correlation was linear (r = 0.9992) over the NAP concentration range of 1-420 ng mL(-1). The limit of detection (LOD) was 0.11 ng mL(-1) with a relative standard deviation (RSD) of 1.15% for 5 replicate determinations of 200 ng mL(-1) NAP. The method was successfully applied to determine NAP in pharmaceutical and biological samples.

A new concept of a chemically deactivatable quencher is proposed for a FRET-based probe that turns-on its fluorescence by either an enzymatic cleavage or a chemical reagent (sodium dithionite). This concept allowed us to quantify the caspase-3 cleavage activity in solution and to reveal unreacted probes in cell experiments., (This journal is © The Royal Society of Chemistry 2012)

Cellular autofluorescence can affect the sensitivity of fluorescence microscopic or flow cytometric assays by interfering with or even precluding the detection of low-level specific fluorescence. Here we developed a method to detect and quantify bacterial autofluorescence in the green region of the spectrum at the single-cell level using a laboratory-built high-sensitivity flow cytometer (HSFCM). The detection of the very weak bacterial autofluorescence was confirmed by analyzing polystyrene beads of comparable and larger size than bacteria in parallel. Dithionite reduction and air re-exposure experiments verified that the green autofluorescence mainly originates from endogenous flavins. Bacterial autofluorescence was quantified by calibrating the fluorescence intensity of nanospheres with known FITC equivalents, and autofluorescence distribution was generated by analyzing thousands of bacterial cells in 1 min. Among the eight bacterial strains tested, it was found that bacterial autofluorescence can vary from 80 to 1400 FITC equivalents per cell, depending on the bacterial species, and a relatively large cell-to-cell variation in autofluorescence intensity was observed. Quantitative measurements of bacterial autofluorescence provide a reference for the background signals that can be expected with bacteria, which is important in guiding studies of low-level gene expression and for the detection of low-abundance biological molecules in individual bacterial cells. This paper presents the first quantification of bacterial autofluorescence in FITC equivalents., (© 2012 American Chemical Society)

A low-spin, macrocyclic iron(II) complex in an aqueous solution responds to the addition of a chemical reactant (dithionite) by transformation into a high-spin complex, detectable by measurement of the longitudinal relaxation time (T(1)) of surrounding water hydrogen nuclear spins. The initial compound does not modify T(1) of pure water at concentrations as high as 4 mM. The response is pH-dependent, and the complex is robust at a variety of conditions.