Suppression of thiol exchange reaction in the determination of reduced-form thiols by high-performance liquid chromatography with fluorescence detection after derivatization with fluorogenic benzofurazan reagent, 7-fluoro-2,1,3-benzoxadiazole-4-sulfonate and 4-aminosulfonyl-7-fluoro-2,1,3-benzoxadiazole

The derivatization of the reduced-form thiols with SBD-F (7-fluoro-2,1,3-benzoxadiazole-4-sulfonate) and ABD-F (4-aminosulfonyl-7-fluoro-2,1,3-benzoxadiazole) was studied. The yields of the derivatives of the reduced-form thiols (cysteine, homocysteine, reduced-form glutathione) with SBD-F at 60 degrees C for 45 min in the borate buffer (pH 9.3) were significantly decreased in the presence of the oxidized-form thiols (cystine, homocystine, oxidized-form glutathione) because of the thiol exchange reaction between the reduced-form and the oxidized-form thiols. The use of ABD-F at low temperature enabled the suppression of these thiol exchange reactions, and the recommended conditions were below 5 degrees C for 90 min in borate buffer (pH 9.3). These results suggest that ABD-F is a preferred derivatization reagent for the accurate determination of the reduced-form thiols in samples containing the oxidized-form thiols. In addition, it was also suggested that the derivatization of the reduced-form thiols should also be performed at low temperature when derivatization reagents such as o-phthalaldehyde (OPA) and monobromobimane (BrB) are used.     

Determination of thiols and disulfides in normal rat tissues and hamster pancreas treated with N-nitrosobis(2-oxopropyl)amine using 4-(aminosulfonyl)-7-fluoro-2,1,3-benzoxadiazole and ammonium 7-fluoro-2,1,3-benzoxadiazole-4-sulfonate

Biological thiols and disulfides in rat and hamster tissues were simultaneously determined by HPLC-fluorescence detection using 4-(aminosulfonyl)-7-fluoro-2,1,3-benzoxadiazole (ABD-F) and ammonium 7-fluoro-2,1,3-benzoxadiazole-4-sulfonate (SBD-F). The coefficients of variation (CV) of the method for reduced glutathione (GSH) and oxidized glutathione (GSSG) in liver and for cysteine (CySH) and cystine (CySSCy) in kidney were less than 3.1%. In 11 tissues of Wistar rats (liver, spleen, heart, lung, stomach, bladder, ovary, uterus, adrenal, kidney and pancreas), only CySH, CySSCy, GSH and/or GSSG were detected. Other thiols and disulfides were at extremely low levels in all samples. Both concentrations of CySH and CySSCy in the livers of old rats (111 weeks old, F344) were significantly higher than those of young rats (8 weeks old) (CySH, 0.246 +/- 0.099 vs 0.130 +/- 0.020 mumol/g; CySSCy, 0.051 +/- 0.027 vs 0.013 +/- 0.002 mumol/g). Administration of N-nitrosobis(2-oxopropyl)amine (BOP), a selective carcinogen of hamster pancreatic cancer, to Syrian golden hamsters (38 weeks old) resulted in the increase in the pancreas of GSH to a level 19 times as high and of GSSG to a level 14 times as high as those in untreated hamsters (GSH, 1.173 +/- 0.272 vs 0.062 +/- 0.017 mumol/g; GSSG, 0.155 +/- 0.063 vs 0.011 +/- 0.001 mumol/g).     

Determination of tetraiodothyronine in serum by HPLC and electrochemical detection

Tetraiodo-L -thyronine (T4) in human serum was determined by HPLC using a nonphysiological internal standard. For sample preparation, a cation exchange resin, RP-chromatography on C-18 or phenylphase, and electrochemical detection (Metrohm 656 or BAS-LC 4 A) were employed. The mobile phase (0.8 ml/min) was 10 mM H₃PO₄/CH₃OH (40/60 v/v) or 10 mM H₃PO₄/CH₃CN (70/30 v/v, 1.5 ml/min), the voltage applied 800 mV. The coefficient of variation (day to day) was 6.8% (N = 40); concentrations of T4 found were 11 to 20% lower than those obtained by two different commercially available immunoassays.     

General, fast, and high yield oxidation of thiols and disulfides to sulfonic and sulfinic acids using HOF·CH3CN

Thiols and disulfides are oxidized to the corresponding sulfonic and sulfinic acids using HOF·CH₃CN. This oxidation is suitable for a variety of thiols and disulfides and proceeds under mild conditions, in short reaction times and with high yields.     

Fluorogenic and fluorescent labeling reagents with a benzofurazan skeleton

Fluorogenic and fluorescent labeling reagents having a benzofurazan (2,1,3-benzoxadiazole) skeleton such as 4-fluoro-7-nitro-2,1,3-benzoxadiazole (NBD-F), 4-N,N-dimethylaminosulfonyl-7-fluoro-2,1,3-benzoxadiazole (DBD-F), 4-aminosulfonyl-7-fluoro-2,1,3-benzoxadiazole (ABD-F), ammonium 7-fluoro-2,1,3-benzoxadiazole-4-sulfonate (SBD-F), 4-hydrazino-7-nitro-2,1,3-benzoxadiazole (NBD-H), 4-N,N-dimethylaminosulfonyl-7-hydrazino-2,1,3-benzoxadiazole (DBD-H), 4-nitro-7-N-piperazino-2,1,3-benzoxadiazole (NBD-PZ), 4-N,N-dimethylaminosulfonyl-7-N-piperazino-2,1,3-benzoxadiazole (DBD-PZ), 4-(N-chloroformylmethyl-N-methyl)amino-7-N,N-dimethylaminosulfonyl-2,1,3-benzoxadiazole (DBD-COCl) and 7-N,N-dimethylaminosulfonyl-4-(2,1,3-benzoxadiazolyl) isothiocyanate (DBD-NCS) are reviewed in terms of synthetic method, reactivity, fluorescence characteristics, sensitivity and application to analytes.     

Benzimidazolium-based new simple ratiometric fluorescent sensor for selective detection of dihydrogenphosphate

A series of pyridine-coupled benzimidazolium-based receptors 1, 2 and 3 have been designed and synthesised. In the series, only receptor 1 is structurally appealing in the selective recognition of H₂PO₄^?  in CHCl₃ as well as in CH₃CN over a series of other anions. The ratiometric change in emission with a triplet band at 420 nm is the distinctive feature of selective recognition of H₂PO₄^?  in CHCl₃. In CH₃CN, a ‘turn on’ response is selectively observed. Binding studies have been carried out using fluorescence, UV–vis, ¹H NMR and ³¹P NMR spectroscopic techniques. Experimental results have been correlated with the theoretical findings.     

Experimental Evidence of CO2 Photoreduction Activity of SnO2 Nanoparticles

Tin dioxide (SnO₂) has intrinsic characteristics that do not favor its photocatalytic activity. However, we evidenced that surface modification can positively influence its performance for CO₂ photoreduction in the gas phase. The hydroxylation of the SnO₂ surface played a role in the CO₂ affinity decreasing its reduction potential. The results showed that a certain selectivity for methane (CH₄), carbon monoxide (CO), and ethylene (C₂H₄) is related to different SnO₂ hydrothermal annealing. The best performance was seen for SnO₂ annealed at 150 °C, with a production of 20.4 μmol g⁻¹ for CH₄ and 16.45 μmol g⁻¹ for CO, while for SnO₂ at 200 °C the system produced more C₂H₄, probably due to a decrease of surface −OH groups.     

A study of HPLC separation and spectrophotometric, polarographic and voltammetric detection of 4-substituted derivatives of N-nitroso-N-methylaniline

Optimised conditions have been found for the separation of N-nitroso-N-methylaniline derivatives substituted in the position 4 (4-R-NMA, where R =- H,- CH₃, - OCH₃, - Cl, - CN, - OH and - NO₂), using reversed phase HPLC with a C18 chemically bonded stationary phase. Suitable mobile phases are mixtures of aqueous 0.01 mol l^–1 KH₂PO₄ with methanol (4+6) or acetonitrile (7+3), or a mixture of water, methanol, acetonitrile and 80% H₃PO₄ (200+200+200+3). Four detection techniques have been investigated: Direct UV photometry, polarography on a hanging mercury drop electrode, anodic voltammetry on a glassy carbon fibre array electrode and indirect anodic voltammetric detection after photolytic denitrosation of the analytes. The UV photometry is the most universal and yields limits of detection around 10^–6 mol l^–1. Polarography exhibits the poorest sensitivity (with a limit of detection of ca. 10^–5 mol l^–1) but it can be used for selective detection of 4-NO₂-NMA. Direct voltammetric detection is selective for the oxidizable derivatives and the limits of detection attained are lower than those obtained by UV photometry (for 4-OH-NMA) or comparable with (for 4-OCH₃-NMA). When the analytes are photolytically denitrosated to yield oxidizable derivatives, the voltammetric detection of 4-H-NMA, 4-Cl-NMA, 4-CH₃-NMA and 4-NO₂-NMA has limits of detection one order of magnitude lower than those obtained UV photometrically.     

Hydrocarbon production by addition of Cu-ZnO on g-C3N4 for CO2 conversion

In this study, copper/zinc oxide/graphite nitrogen carbide (Cu/ZnO/g-C₃N₄) is prepared using a hydrothermal method and applied as a photocatalyst for CO₂ photoreduction. The morphology and structural properties of the obtained Cu/ZnO/g-C₃N₄ are systematically characterized through X-ray powder diffraction, ultraviolet–visible absorption spectroscopy, transmission electronic microscopy, and photoluminescence spectroscopy. A 3 wt% Cu/ZnO/g-C₃N₄ photocatalyst exhibits high CH₄ (40.7 μmol g⁻¹ hr⁻¹), CO (65.1 μmol g⁻¹ hr⁻¹), and CH₃OH (92.5 μmol g⁻¹ hr⁻¹) production rates, which are 38.3, 77.1, and 58.1 fold higher than the pure g-C₃N₄. The production rate is higher than those for bulk g-C₃N₄ and ZnO/g-C₃N₄. Finally, the reaction mechanism of Cu/ZnO/C₃N₄ is proposed in this study.     

The determination of low lead levels in the bone of lead-depleted mice by graphite furnace atomic absorption spectrometry

Low lead levels in the femurs of mice fed with a lead-depleted diet have been determined by use of electrothermal atomic absorption spectrometry with Zeeman-effect background correction. The method is based on the use of Mg(NO₃)₂/Pd as matrix modifier which enables significant reduction of the spectral interferences prevalent if chemical modifiers based on NH₄H₂PO₄ with either Ca or Mg are used for samples rich in Ca₃(PO₄)₂ matrix. The method was developed and validated by use of the NIST standard reference material 1486 bone. Bones were decomposed in a pressurized microwave-heated system using 70% nitric acid. Forty-three mice femurs, with a mass of 74.62 ± 12.54 mg, were dissolved in concentrated nitric acid. The lead results found in SRM 1486 (1.25 ± 0.15 μg g^–1, n = 9) were in good agreement with the certificate (1.335 ± 0.014 μg g^–1). Recoveries of 200 ng lead added to the SRM before or after digestion were 99.0 ± 1.4% and 98.5 ± 1.6%, respectively. The lead detection limit in bone samples is 0.06 μg g^–1 dry mass. This method is, therefore, suitable for the determination of very low lead levels (0.06–0.20 μg Pb kg^–1 bone) in the femurs of mice fed a diet with lead level of < 20μg kg^–1.     

Solvent Effect on the Photoinduced Electron Transfer Reaction Between Thioxanthen-9-one and Diphenylamine

Photoinduced chemical reaction between thioxanthen-9-one (TX) and diphenylamine (DPA) were investigated by the nanosecond laser flash photolysis. With photolysis at 355 nm, the triplet TX (³TX^*) is produced via a Franck-Condon excitation and intersystem crossing. In the transient absorption spectra of the reduction of ³TX^* by DPA in pure and aqueous CH₃CN, four bands are clearly observed and assigned to absorption of ³TX^*, TXH^·, TX^·- and DPA^·+, respectively. With the increase of solvent polarity, the blue-shift was observed for all absorption bands of the intermediates. With the aid of dynamic decay curves, an electron transfer followed by a protonation process is confirmed for the reduction of ³TX^* by DPA. The quenching rate constants of ³TX^* by DPA very slightly decrease from 9.7×10⁹ L/(mol·s) in pure CH₃CN, to 8.7×10⁹ L/(mol·s) in CH₃CN:H₂O (9:1), 8.0×10⁹ L/(mol·s) in CH₃CN:H₂O (4:1) and 7.5×10⁹ L/(mol·s) in CH₃CN:H₂O (1:1). Therefore water plays a minor role in the title reaction, and moreover no obvious medium effect of solvent polarity is observed for the electron transfer between ³TX^* and DPA, indicating that the ³nπ^* and ³ππ^* states of TX have the approximate ability to attract an electron from DPA.     

Synthesis and characterization of cyclophane: The highly selective recognition of Fe3+ in aqueous solution and H2PO4− in acetonitrile solution

In this work, we report a series of cyclophane fluorescent sensors based on acridine combining with imidazolium through ether linkages. X-ray crystal structures demonstrated the self-assembly behavior of these cyclophanes in the solid state driven by hydrogen bond and π–π interactions. Sensors showed excellent selectivity towards Fe³⁺ in aqueous solution (H₂O/CH₃CN?=?49:1, v/v) and H₂PO₄^? in acetonitrile solution with notable color change under UV light, evident changes were also noticed in fluorescence spectra. In fluorescence emission, the obvious turn-off was induced by Fe³⁺ in aqueous solution and the obvious turn-on as well as bathochromic-shift was induced by H₂PO₄^? in acetonitrile solution.     

Non-Interacting Ni and Fe Dual-Atom Pair Sites in N-Doped Carbon Catalysts for Efficient Concentrating Solar-Driven Photothermal CO2 Reduction

Solar-to-chemical energy conversion under weak solar irradiation is generally difficult to meet the heat demand of CO₂ reduction. Herein, a new concentrated solar-driven photothermal system coupling a dual-metal single-atom catalyst (DSAC) with adjacent Ni−N₄ and Fe−N₄ pair sites is designed for boosting gas-solid CO₂ reduction with H₂O under simulated solar irradiation, even under ambient sunlight. As expected, the (Ni, Fe)−N−C DSAC exhibits a superior photothermal catalytic performance for CO₂ reduction to CO (86.16 μmol g⁻¹ h⁻¹), CH₄ (135.35 μmol g⁻¹ h⁻¹) and CH₃OH (59.81 μmol g⁻¹ h⁻¹), which are equivalent to 1.70-fold, 1.27-fold and 1.23-fold higher than those of the Fe−N−C catalyst, respectively. Based on theoretical simulations, the Fermi level and d-band center of Fe atom is efficiently regulated in non-interacting Ni and Fe dual-atom pair sites with electronic interaction through electron orbital hybridization on (Ni, Fe)−N−C DSAC. Crucially, the distance between adjacent Ni and Fe atoms of the Ni−N−N−Fe configuration means that the additional Ni atom as a new active site contributes to the main *COOH and *HCO₃ dissociation to optimize the corresponding energy barriers in the reaction process, leading to specific dual reaction pathways (COOH and HCO₃ pathways) for solar-driven photothermal CO₂ reduction to initial CO production.     

Hydrogen production and photocatalytic activity of g-C3N4/Co-MOF (ZIF-67) nanocomposite under visible light irradiation

Herein, cobalt (Co)-based metal–organic zeolitic imidazole frameworks (ZIF-67) coupled with g-C₃N₄ nanosheets synthesized via a simple microwave irradiation method. SEM, TEM and HR-TEM results showed that ZIF-67 were uniformly dispersed on g-C₃N₄ surfaces and had a rhombic dodecahedron shape. The photocatalytic properties of g-C₃N₄/ZIF-67 nanocomposite were evaluated by photocatalytic dye degradation of crystal violet (CV), 4-chlorophenol (4-CP) and photocatalytic hydrogen (H₂) production. In presence of visible light illumination, the photocatalytic dye results showed that 95% CV degradation and 53% 4-CP degradation within 80 min. The H₂ production of the g-C₃N₄/ZIF-67 composite was 2084 μmol g⁻¹, which is 3.84 folds greater than that of bare g-C₃N₄ (541 μmol g⁻¹).     

(NH4)6Mo7O24·4H2O as an Efficient,Selective, and Reusable Catalyst for the Oxidation of Thiols to Disulfides Using Potassium Bromate

Abstract

Ammonium molybdate, (NH₄)₆Mo₇O₂₄·4H₂O, is found to be an efficient and selective catalyst for the oxidation of thiols to corresponding disulfides using potassium bromate in aqueous acetonitrile as the solvent. Among various solvents tested, CH₃CN/H₂O showed better results in terms of the reaction yield and rate. In the absence of (NH₄)₆Mo₇O₂₄·4H₂O, the oxidation reaction is not selective for the formation of disulfides. The catalyst can be easily recovered after completion of the reaction and reused without any significant loss of its activity.

[Supplementary materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfer, and Silicon and the Related Elements for the following free supplemental files: Additional text and figures.]     

Reduced Graphene Oxide–Ag3PO4 Heterostructure: A Direct Z‐Scheme Photocatalyst for Augmented Photoreactivity and Stability

A visible light driven, direct Z‐scheme reduced graphene oxide–Ag₃PO₄ (RGO–Ag₃PO₄) heterostructure was synthesized by means of a simple one‐pot photoreduction route by varying the amount of RGO under visible light illumination. The reduction of graphene oxide (GO) and growth of Ag₃PO₄ took place simultaneously. The effect of the amount of RGO on the textural properties and photocatalytic activity of the heterostructure was investigated under visible light illumination. Furthermore, total organic carbon (TOC) analysis confirmed 97.1 % mineralization of organic dyes over RGO–Ag₃PO₄ in just five minutes under visible‐light illumination. The use of different quenchers in the photomineralization suggested the presence of hydroxyl radicals ( ^. OH), superoxide radicals ( ^. O₂^?), and holes (h⁺), which play a significant role in the mineralization of organic dyes. In addition to that, clean hydrogen fuel generation was also observed with excellent reusability. The 4 RGO–Ag₃PO₄ heterostructure has a high H₂ evolution rate of 3690 μmol h^?1 g^?1, which is 6.15 times higher than that of RGO.     

Estimation of the specific content and nature of sorption sites of iron(<Emphasis Type="SmallCaps">III</Emphasis>) and zirconium(<Emphasis Type="SmallCaps">IV</Emphasis>) oxyhydroxides

The sorption of anions H₂PO₄ ⁻, HPO₄ ²⁻, PO₄ ³⁻, [Fe(CN)₆]³⁻, and [Fe(CN)₆]⁴⁻ from aqueous solutions on the surface of Fe^III and Zr^IV oxyhydroxide hydrogels freshly precipitated at pH 4–13 was studied. The region of sorbate concentrations was from 0.00025 to 0.06 mol L⁻¹. The plots of the anion uptakes vs. their equilibrium concentrations are represented by isotherms of the first type, which are well described by the Langmuir equation if the quantity of the amount adsorbed is expressed as mol-site g⁻¹. The maximum uptakes and constants of the Langmuir equation were calculated. The phosphate anions occupy the same number of sorption sites on the sorbents precipitated at different pH. The average specific content of sorption sites for the ferro- and zirconogels in the metastability period is independent of the pH of their precipitation, being 3.1·10⁻³ and 3.2·10⁻³ mol-site g⁻¹, respectively. The [Fe(CN)₆]³⁻ and [Fe(CN)₆]⁴⁻ anions are sorbed only on the positively charged sites of the hydrogels and occupy not more than 2·10 mol-site g⁻¹ in the studied interval of pH of precipitation. __________ Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1736—1741, August, 2005.     

Novel Copolymers of Styrene and Some Ring‐Substituted 2‐Cyano‐N,N‐Dimethyl‐3‐Phenyl‐2‐Propenamides

Electrophilic trisubstituted ethylene monomers, ring‐substituted 2‐cyano‐N,N‐dimethyl‐3‐phenyl‐2‐propenamides, RC₆H₄CH?C(CN)CON(CH₃)₂ (where R is 4‐(CH₃)₂N, 4‐CH₃CO₂, 4‐CH₃CONH, 2‐CN, 3‐CN, 4‐CN, 4‐(C₂H₅)₂N) were synthesized by potassium hydroxide catalyzed Knoevenagel condensation of ring‐substituted benzaldehydes and N,N‐dimethyl cyanoacetamide, and characterized by CHN elemental analysis, IR, ¹H‐ and ¹³C‐NMR. Novel copolymers of the ethylenes and styrene were prepared at equimolar monomer feed composition by solution copolymerization in the presence of a radical initiator, ABCN at 70°C. The composition of the copolymers was calculated from nitrogen analysis, and the structures were analyzed by IR, ¹H and ¹³C NMR, GPC, DSC, and TGA. High T_g of the copolymers in comparison with that of polystyrene indicates a substantial decrease in chain mobility of the copolymer due to the high dipolar character of the trisubstituted ethylene monomer unit. The gravimetric analysis indicated that the copolymers decompose in the 300–450°C range.     

Design and synthesis of azaindole heterocycle decorated new scaffold in fluorometric sensing of F− and H2PO4−

7-Azaindole has been used in designing new molecular structure 1 on enediyne spacer for its application in anion sensing. New structure 1 has been established as efficient fluorescent sensor of H₂PO₄⁻ and F⁻ ions in CH₃CN containing 1% DMSO. While in presence of H₂PO₄⁻ the emission at 418 nm is decreased to the significant extent in nonratiometric fashion, a ratiometric response in presence of F⁻ is noted with a sharp isoemissive point and two anions are effectively distinguished over a series of other anions tested. A similar study on model compound 2 with indole motifs is done to prove the pivotal role of extra ring nitrogen in azaindole of 1 in the binding process.     

Ruthenium piano-stool complexes bearing imidazole-based PN ligands

A variety of piano-stool complexes of cyclopentadienyl ruthenium(II) with imidazole-based PN ligands have been synthesized starting from the precursor complexes [CpRu(C₁₀H₈)]PF₆, [CpRu(NCMe)₃]PF₆ and [CpRu(PPh₃)₂Cl]. PN ligands used are imidazol-2-yl, -4-yl and -5-yl phosphines.Depending on the ligand and precursor different types of coordination modes were observed; in the case of polyimidazolyl PN ligands these were κ¹P-monodentate, κ²P,N-, κ²N,N- and κ³N,N,N- chelating and μ-κP:κ²N,N-brigding. The solid-state structures of [CpRu(1a)₂Cl ]·H₂O (5^.H₂O) and [{CpRu(μ-κ²-N,N-κ’¹-P-2b)}₂](C₆H₅PO₃H)₂(C₆H₅PO₃H₂)_2, a hydrolysis product of the as well determined [{CpRu(2b)}₂](PF₆)₂^.2CH₃CN (7b^.2CH₃CN) were determined (1a = imidazol-2-yldiphenyl phosphine, 2b = bis(1-methylimidazol-2-yl)phenyl phosphine, 3a = tris(imidazol-2-yl)phosphine). Furthermore, the complexes [CpRu(L)₂]PF₆ (L = imidazol-2-yl or imidazol-4-yl phosphine) have been screened for their catalytic activity in the hydration of 1-octyne.