Combining chemical reduction with an electrochemical technique for the simultaneous detection of Cr(VI), Pb(II) and Cd(II)

This work herein reports the approach for the simultaneous determination of heavy metal ions including cadmium (Cd(II)), lead (Pb(II)), and chromium (Cr(VI)) using a bismuth film electrode (BFE) by anodic stripping voltammertry (ASV). The BFE used was plated in situ. Due to the reduction of Cr(VI) with H2O2 in the acid medium, on one hand, the Cr(III) was produced and Cr(VI) was indirectly detected by monitoring the content of Cr(III) using square-wave ASV. On the other hand, Pb(II) was also released from the complex between Pb(II) and Cr(VI). Furthermore, the coexistence of the Cd(II) was also simultaneously detected with Pb(II) and Cr(VI) in this system as a result of the formation of an alloy with Bi. The detection limits of this method were 1.39 ppb for Cd(II), 2.47 ppb for Pb(II) and 5.27 ppb for Cr(VI) with a preconcentration time of 120 s under optimal conditions (S/N = 3), respectively. Furthermore, the sensitivity of this method can be improved by controlling the deposition time or by using a cation-exchange polymer (such as Nafion) modified electrode.

Electrochemical determination of plant-derived leuco-indigo after chemical reduction by glucose

Electrochemical determination of redox active dye species is demonstrated in indigo samples contaminated with high levels of organic and inorganic impurities. The use of a hydrodynamic electrode system based on a vibrating probe (250 Hz, 200 mu m lateral amplitude) allows time-independent diffusion controlled signals to be enhanced and reliable concentration data to be obtained under steady state conditions at relatively fast scan rates up to 4 V s-1In this work the indigo content of a complex plant-derived indigo sample (dye content typically 30%) is determined after indigo is reduced by addition of glucose in aqueous 0.2 M NaOH. The soluble leuco-indigo is measured by its oxidation response at a vibrating electrode. The vibrating electrode, which consisted of a laterally vibrating 500 mu m diameter gold disc, is calibrated with Fe(CN)(6) 3-/4- in 0.1 M KCl and employed for indigo determination at 55, 65, and 75 C in 0.2 M NaOH. Determinations of the indigo content of 25 different samples of plant-derived indigo are compared with those obtained by conventional spectrophotometry. This comparison suggests a significant improvement by the electrochemical method, which appears to be less sensitive to impurities.

Effects of high hydrostatic pressure and chemical reduction on the emulsification properties of gum arabic

Gum arabic is widely used in the food industry as an additive, both as a thickener and an emulsifier. This study has compared the emulsification properties of two types of gums, KLTA (Acacia senegal) and GCA (Acacia seyal), both in their native/untreated forms and after exposure to high pressure (800 MPa). Further studies were undertaken to chemically modify the disulphide linkages present and to investigate the effects of their reduction on the diffusion of the carbohydrate materials. The emulsification properties of the gum samples were examined by determining the droplet size distribution in a ‘‘model’’ oil-in-water system. Results showed that high pressure treatment and chemical reduction of gums changed the emulsification properties of both gums. The high molecular weight component in arabinogalactanproteins (AGP/GP), and more ‘‘branched’’ carbohydrates present in gum arabic, may be responsible for the emulsification properties of GCA gum, indicating that the emulsification mechanisms for KLTA and GCA were different.

Chemical reduction of carboxyl groups in heparin abolishes its vasodilatory activity

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Chemical reduction of carboxyl groups in heparin abolishes its vasodilatory activity

Previous studies have shown that heparin induces vascular relaxation via integrin-dependent nitric oxide (NO)-mediated activation of the muscarinic receptor. The aim of this study was to identify the structural features of heparin that are necessary for the induction of vasodilatation. To address this issue, we tested heparin from various sources for their vasodilatation activities in the rat aorta ring. Structural and chemical characteristics of heparin, such as its molecular weight and substitution pattern, did not show a direct correlation with the vasodilation activity. Principal component analysis (PCA) of circular dichroism (CD), 1H-nuclear magnetic resonance (NMR) and vasodilation activity measurements confirmed that there is no direct relationship between the physico-chemical nature and vasodilation activity of the tested heparin samples. To further understand these observations, unfractionated heparin (UFH) from bovine intestinal mucosa, which showed the highest relaxation effect, was chemically modified. Interestingly, non-specific O- and N-desulfation of heparin reduced its anticoagulant, antithrombotic, and antihemostatic activities, but had no effect on its ability to induce vasodilation. On the other hand, chemical reduction of the carboxyl groups abolished heparin-induced vasodilation and reduced the affinity of heparin toward the extracellular matrix (ECM). In addition, dextran and dextran sulfate (linear non-sulfated and highly sulfated polysaccharides, respectively) did not induce significant relaxation, showing that the vasodilation activity of polysaccharides is neither charge-dependent nor backbone unspecific. Our results suggest that desulfated heparin molecules may be used as vasoactive agents due to their low side effects. J. Cell. Biochem. 113: 13591367, 2012. (c) 2011 Wiley Periodicals, Inc.

Nitrone [2]rotaxanes: Simultaneous chemical protection and electrochemical activation of a functional group

We report on the use of the hydrogen bond accepting properties of neutral nitrone moieties to prepare benzylic-amide-macrocycle-containing [2]rotaxanes in yields as high as 70 %. X-Ray crystallography shows the presence of up to four intercomponent hydrogen bonds between the amide groups of the macrocycle and the two nitrone groups of the thread. Dynamic 1H NMR studies of the rates of macrocycle pirouetting in nonpolar solutions indicate that amide-nitrone hydrogen bonds are particularly strong, ~1.3 and ~0.2 kcal mol-1 stronger than similar amide-ester and amide-amide interactions, respectively. In addition to polarizing the N-O bond through hydrogen bonding, the rotaxane structure affects the chemistry of the nitrone groups in two significant ways: The intercomponent hydrogen bonding activates the nitrone groups to electrochemical reduction, a one electron reduction of the rotaxane being stablized by a remarkable 400 mV (8.1 kcal mol-1) with respect to the same process in the thread; encapsulation, however, protects the same functional groups from chemical reduction with an external reagent (and slows down electron transfer to and from the electroactive groups in cyclicvoltammetry experiments). Mechanical interlocking with a hydrogen bonding molecular sheath thus provides a route to an encapsulated polarized functional group and radical anions of significant kinetic and thermodynamic stability.

Decomposition of toxic chemical substance management in three U.S. manufacturing sectors from 1991 to 2008

This study analyzes toxic chemical substance management in three U.S. manufacturing sectors from 1991 to 2008. Decomposition analysis applying the logarithmic mean Divisia index is used to analyze changes in toxic chemical substance emissions by the following five factors: cleaner production, end-of-pipe treatment, transfer for further management, mixing of intermediate materials, and production scale. Based on our results, the chemical manufacturing sector reduced toxic chemical substance emissions mainly via end-of-pipe treatment. In the meantime, transfer for further management contributed to the reduction of toxic chemical substance emissions in the metal fabrication industry. This occurred because the environmental business market expanded in the 1990s, and the infrastructure for the recycling of metal and other wastes became more efficient. Cleaner production is the main contributor to toxic chemical reduction in the electrical product industry. This implies that the electrical product industry is successful in developing a more environmentally friendly product design and production process.

Silver nanocrystals modified microstructured polymer optical fibres for chemical and optical sensing

In-fibre chemical and optical sensors based on silver nanocrystals modified microstructured polymer optical fibres (MPOFs) were demonstrated. The silver nanocrystals modified MPOFs were formed by direct chemical reduction of silver ammonia complex ions on the templates of array holes in the microstructure polymer optical fibres. The nanotube-like and nanoisland-like Ag-modified MPOFs could be obtained by adjusting the conditions of Ag-formation in the air holes of MPOFs. SEM images showed that the higher concentration of the reaction solution (silver ammonia 0.5 mol/L, glucose 0.25 mol/L), gave rise to a tubular silver layer in MPOF, while the lower concentration (silver ammonia 0.1 M, glucose 0.05 M) produced an island-like Ag nanocrystal modified MPOF. The tubular Ag-MPOF composite fibre was conductive and could be directly used as array electrodes in electrochemical analyses. It displayed high electrochemical activity on sensing nitrate or nitrite ions. The enhanced fluorescence of dye molecules was observed when the island-like Ag-modified MPOF was inserted into a fluorescent dye solution. (C) 2007 Elsevier B.V. All rights reserved.

Reduction of NO by CO on Cu/ZrO(2)/Al(2)O(3) catalysts: Characterization and catalytic activities

ZrO(2), gamma-Al(2)O(3) and ZrO(2)/gamma-Al(2)O(3)-supported copper catalysts have been prepared, each with three different copper loads (1, 2 and 5 wt%), by the impregnation method. The catalysts were characterized by nitrogen adsorption (BET), X-ray diffraction (XRD), temperature programmed reduction (TPR) with H(2), Raman spectroscopy and electronic paramagnetic resonance (EPR). The reduction of NO by CO was studied in a fixed-bed reactor packed with these catalysts and fed with a mixture of 1% CO and 1% NO in helium. The catalyst with 5 wt% copper supported on the ZrO(2)/gamma-Al(2)O(3) matrix achieved 80% reduction of NO. Approximately the same rate of conversion was obtained on the catalyst with 2 wt% copper on ZrO(2). Characterization of these catalysts indicated that the active copper species for the reduction of NO are those in direct contact with the oxygen vacancies found in ZrO(2). (C) 2009 Published by Elsevier Ltd.

A highly conductive porous graphene electrode prepared via in situ reduction of graphene oxide using Cu nanoparticles for the fabrication of high performance supercapacitors

Herein, a new graphene/Cu nanoparticle composite was prepared via the in situ reduction of GO in the presence of Cu nanoparticles which was then utilized as a sacrificing template for the formation of flexible and porous graphene capacitor electrodes by the dissolution of the intercalated Cu nanoparticle in a mixed solution of FeCl3 and HCl. The porous RGO electrode was characterized by atomic force microscopy (AFM), Fourier transform infrared (FTIR) spectroscopy, X-ray diffraction (XRD), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS) and thermogravimetric analysis (TGA). The as-prepared graphene/Cu nanoparticle composite and the pure graphene film after removal of Cu nanoparticles possessed high conductivity of 3.1 × 10³ S m^-1 and 436 S m^-1 respectively. The porous RGO can be used as the electrode for the fabrication of supercapacitors with high gravimetric specific capacitances up to 146 F g^-1, good rate capability and satisfactory electrochemical stability. This environmentally friendly and efficient approach to fabricating porous graphene nanostructures could have enormous potential applications in the field of energy storage and nanotechnology.

Electrochemical Reduction as a Powerful Tool to Highlight the Possible Formation of By-Products More Toxic Than Sudan III Dye

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Reduction of dissolved oxygen in water: Hydrazine and its organic substitutes

In industrial processes using aqueous solutions, corrosion of metal surfaces may occur at various locations. Much of the damage to steam generators and boilers is caused by corrosion. Dissolved oxygen in water is one of the most potent corrosion-causing factors, and therefore oxygen should be eliminated from steam-generating systems' feedwater. Chemical reduction, by reagents such as hydrazine or organic compounds, generally is used for the deoxygenation of water. This article reviews the major oxygen scavengers currently available.

Electrochemical Reduction as a Powerful Tool to Highlight the Possible Formation of By-Products More Toxic Than Sudan III Dye

The present work describes the electrochemical reduction of the azo dye Sudan III in methanol/0.01 mol l(-1) Bu4NBF4 at applied potential of -1.2V, which promotes 98% discoloration of the commercial sample. The reduction products were analyzed by high performance liquid chromatography, after optimized conditions for 20 aromatic amines with carcinogenic potentiality. The harmful compounds such as: aniline, benzidine, o-toluidine, 2,6-dimethylaniline, 4,4'-oxydianiline, 4,4'-metileno-bis-2-methylaniline and 4-aminobiphenyl are formed after azo bond cleavage. The electrochemical reduction is compared with chemical reduction by using sodium thiosulfate. Our findings illustrates that commercial Sudan III under reductive condition can forms a number of products, which some are known active genotoxins. The technique could be used to mimic important redox reactions in human metabolism or environment, highlighting the possible formation of by-products more toxic than the original dyes.

Environmentally friendly reduction of a platinum catalyst precursor supported on polypyrrole

Supported metals are traditionally prepared by impregnating a support material with the metal precursor solution, followed by reduction in hydrogen at elevated temperatures. In this study, a polymeric support has been considered. Polypyrrole (PPy) has been chemically synthesized using FeCl3 as a doping agent, and it has been impregnated with a H2PtCl6 solution to prepare a catalyst precursor. The restricted thermal stability of polypyrrole does not allow using the traditional reduction in hydrogen at elevated temperature, and chemical reduction under mild conditions using sodium borohydride implies environmental concerns. Therefore, cold RF plasma has been considered an environmentally friendly alternative. Ar plasma leads to a more effective reduction of platinum ions in the chloroplatinic complex anchored onto the polypyrrole chain after impregnation than reduction with sodium borohydride, as has been evidenced by XPS. The increase of RF power enhanced the effectiveness of the Ar plasma treatment. A homogeneous distribution of platinum nanoparticles has been observed by TEM after the reduction treatment with plasma. The Pt/polypyrrol catalyst reduced by Ar plasma at 200 watts effectively catalyzed the aqueous reduction of nitrates with H2 to yield N2, with a very low selectivity to undesired nitrites and ammonium by-products.