The mechanism of bacterial indigo reduction

The reduction of water-insoluble indigo by the recently isolated moderate thermophile, Clostridium isatidis, has been studied with the aim of developing a sustainable technology for industrial indigo reduction. The ability to reduce indigo was not shared with C. aurantibutyricum, C. celatum and C. papyrosolvens, but C. papyrosolvens could reduce indigo carmine (5,5-indigosulfonic acid), a soluble indigo derivative. The supernatant from cultures of C. isatidis, but not from cultures of the other bacteria tested, decreased indigo particle size to one-tenth diameter. Addition of madder powder, anthraquinone-2,6-disulfonic acid, and humic acid all stimulated indigo reduction by C. isatidis. Redox potentials of cultures of C. isatidis were about 100 mV more negative than those of C. aurantibutyricum, C. celatum and C. papyrosolvens, and reached –600 mV versus the SCE in the presence of indigo, but potentials were not consistently affected by the addition of the quinone compounds, which probably act by modifying the surface of the bacteria or indigo particles. It is concluded that C. isatidis can reduce indigo because (1) it produces an extracellular factor that decreases indigo particle size, and (2) it generates a sufficiently reducing potential.

The development of indigo reduction methods and pre-reduced indigo products

The continuing importance of blue denim maintains indigo as an important vat dye industrially. In this review, we examine the various methods that have been used in the past and are currently used to reduce and dissolve indigo for dyeing. We discuss recent insights into the bacterial fermentation technology, the advantages and disadvantages of the direct chemical methods that have predominated for the last century and potentially cleaner technologies of catalytic hydrogenation and electrochemistry, which are becoming increasingly important. With considerations of environmental impact high on the dyeing industry's agenda, we also discuss the developments that have led to the production of pre-reduced indigo.

Anthraquinone catalysis in the glucose-driven reduction of indigo to leuco-indigo

Anthraquinone immobilised onto the surface of indigo microcrystals enhances the reductive dissolution of indigo to leuco-indigo. Indigo reduction is driven by glucose in aqueous NaOH and a vibrating gold disc electrode is employed to monitor the increasing leuco-indigo concentration with time. Anthraquinone introduces a strong catalytic effect which is explained by invoking a molecular "wedge effect'' during co-intercalation of Na+ and anthraquinone into the layered indigo crystal structure. The glucose-driven indigo reduction, which is in effective in 0.1 M NaOH at 65 degrees C, becomes facile and goes to completion in the presence of anthraquinone catalyst. Electron microscopy of indigo crystals before and after reductive dissolution confirms a delamination mechanism initiated at the edges of the plate-like indigo crystals. Catalysis occurs when the anthraquinone-indigo mixture reaches a molar ratio of 1:400 (at 65 degrees C; corresponding to 3 mu M anthraquinone) with excess of anthraquinone having virtually no effect. A strong temperature effect ( with a composite E-A approximate to 120 kJ mol(-1)) is observed for the reductive dissolution in the presence of anthraquinone. The molar ratio and temperature effects are both consistent with the heterogeneous nature of the anthraquinone catalysis in the aqueous reaction mixture.

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.

Electrochemical and sonoelectrochemical monitoring of indigo reduction by glucose

The reduction of indigo (dispersed in water) to leuco-indigo (dissolved in water) is an important industrial process and investigated here for the case of glucose as an environmentally benign reducing agent. In order to quantitatively follow the formation of leuco-indigo two approaches based on (i) rotating disk voltammetry and (ii) sonovoltammetry are developed. Leuco-indigo, once formed in alkaline solution, is readily monitored at a glassy carbon electrode in the mass transport limit employing hydrodynamic voltammetry. The presence of power ultrasound further improves the leuco-indigo determination due to additional agitation and homogenization effects. While inactive at room temperature, glucose readily reduces indigo in alkaline media at 65 degrees C. In the presence of excess glucose, a surface dissolution kinetics limited process is proposed following the rate law d eta(leuco-indigo)/dt = k x c(OH-) x S-indigo where eta(leuco-indigo) is the amount of leuco-indigo formed, k = 4.1 x 10(-9) m s(-1) (at 65 degrees C, assuming spherical particles of I gm diameter) is the heterogeneous dissolution rate constant,c(OH-) is the concentration of hydroxide, and Sindigo is the reactive surface area. The activation energy for this process in aqueous 0.2 M NaOH is E-A = 64 U mol(-1) consistent with a considerable temperature effects. The redox mediator 1,8-dihydroxyanthraquinone is shown to significantly enhance the reaction rate by catalysing the electron transfer between glucose and solid indigo particles. (c) 2006 Elsevier Ltd. All fights reserved.

A rotating disc voltammetry study of the 1,8-dihydroxyanthraquinone mediated reduction of colloidal indigo

Colloidal indigo is reduced to an aqueous solution of leuco-indigo in a mediated two-electron process converting the water-insoluble dye into the water-soluble leuco form. The colloidal dye does not interact directly with the electrode surface, and to employ an electrochemical process for this reduction, the redox mediator 1,8-dihydroxyanthraquinone (1,8-DHAQ) is used to transfer electrons from the electrode to the dye. The mediated reduction process is investigated at a (500-kHz ultrasound-assisted) rotating disc electrode, and the quantitative analysis of voltammetric data is attempted employing the Digisim numerical simulation software package. At the most effective temperature, 353 K, the diffusion coefficient for 1,8-DHAQ is (0.84 +/- 0.08)x10(-9) m(2) s(-1), and it is shown that an apparently kinetically controlled reaction between the reduced form of the mediator and the colloidal indigo occurs within the diffusion layer at the electrode surface. The apparent bimolecular rate constant k (app)=3 mol m(-3) s(-1) for the rate law d[leuco-indigo]/dt = k(app) x [mediator] x [indigo] is determined and attributed to a mediator diffusion controlled dissolution of the colloid particles. The average particle size and the number of molecules per particles are estimated from the apparent bimolecular rate constant and confirmed by scanning electron microscopy.

Public sector applications of the system dynamics approach

The article discusses various reports published within the issue, including one by Carmine Bianchi on understanding public sector from different levels and perspectives, one by Mauro Lo Tennero on the aspiration and structure of Sicily to enforce public policy, and one by Nuno Videira and colleagues on the use of group model building in the public sector to concur sustainable policies.