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A novel chemiluminescence (CL) system is introduced based on the oxidation of carminic acid by KMnO4 in acidic conditions. CdS quantum dots (QDs) were synthesized using a facile hydrothermal method which efficiently enhanced the intensity of the CL system. A possible mechanism for the proposed system is presented using the kinetic curves, CL spectra, photoluminescence (PL), and ultraviolet-visible (UV-Vis) analysis. The emission intensity of the KMnO4-carminic acid-CdS QDs system was quenched in the presence of a trace level of cloxacillin. Based on this quenching effect, a novel and sensitive flow injection CL method was developed for determining cloxacillin concentrations. At optimal experimental conditions, the decreased CL intensity had a good linear relation with the cloxacillin concentration in the range of 0.008 to 22.0 mg L(-1). The detection limit (3σ) was 5.8 µg L(-1). The precision of the method was calculated by analyzing samples containing 4.0 mg L(-1) of cloxacillin (n=11), and the relative standard deviations (RSD%) were 2.08%. The feasibility of the method is also demonstrated for determining cloxacillin concentrations in environmental water samples and a pharmaceutical formulation.

Using the carminic acid assay, we determined the concentration of boron in oilfield waters. We investigated the effect of high concentrations of salts and dissolved metals on the assay performance. The influence of temperature, development time, reagent concentration, and water volume was studied. Ten produced and flowback water samples of different origins were measured, and the method was successfully validated against ICP-MS measurements. In water-stressed regions, produced water is a potential source of fresh water for irrigation, industrial applications, or consumption. Therefore, boron concentration must be determined and controlled to match the envisaged waste water reuse. Fast, precise, and onsite measurements are needed to minimize errors introduced by sample transportation to laboratories. We found that the optimum conditions for our application were a 5:1 mixing volume ratio (reagent to sample), a 1 g L(-1) carminic acid concentration in 99.99% sulfuric acid, and a 30 min reaction time at ambient temperature (20 °C to 23 °C). Absorption values were best measured at 610 nm and 630 nm and baseline corrected at 865 nm. Under these conditions, the sensitivity of the assay to boron was maximized while its cross-sensitivity to dissolved titanium, iron, barium and zirconium was minimized, alleviating the need for masking agents and extraction methods.

We developed and validated a microfluidic instrument for interference-free determination of boron in produced water. The instrument uses a boron-specific chelating resin to separate the analyte from its complex matrix. Ten produced water samples were analyzed with the instrument and the results were successfully validated against ICP-MS measurements. Removing interference effects enables precise boron measurement for wastewater even with high total dissolved solid (TDS) levels. 1,4-Piperazinediethanesulfonic acid conditions the resin and maintains the optimum pH for boron adsorption from the sample. Boron is then eluted from the resin using a 10% sulfuric acid solution and its concentration measured with the colorimetric carminic acid assay in 95% sulfuric acid. The use of a microfluidic mixer greatly enhances the sensitivity and kinetics of the carminic acid assay, by factors of 2 and 7.5, respectively, when compared against the same assay performed manually. A maximum sensitivity of 2.5mg(-1)L, a precision of 4.2% over the 0-40.0mgL(-1) measuring range, a 0.3mgL(-1) limit of detection, and a sampling rate of up to four samples per hour were achieved. Automation and microfluidics reduce the operator workload and fluid manipulation errors, translating into safer and higher-quality measurements in the field.

Ternary mixtures of colorants E-123 (Amaranth), E-124 (Ponceau 4R) and E-120 (Carminic acid) are resolved by using the first derivative ratio spectrum-zero crossing method without the need for any separation step. Calibration graphs were linear up to 64 mg l−1 of carminic acid, 32 mg l−1 of Amaranth and 32 mg l−1 of Ponceau 4R. The method was applied to different commercial food products and results concordant with high performance liquid chromatography were obtained.

A quaternary mixture of carminic acid, riboflavine, curcumin and erythrosine can be resolved with a previous extraction step into metyl-isobutyl ketone and, resolving the binary mixtures obtained in the aqueous phase and organic phase, using derivative spectrophotometry on the basis of the zero-crossing measurements in the first derivative spectra as well as the first derivative of ratio spectra. The conditions of extraction established and the proposed methods have been tested to determine these colorants in several synthetic mixtures of four dyes, obtaining good recoveries. The methods have been applied in yoghurt samples spiked with the dyes.

A highly sensitive spectrophotometric method is described for the determination of trace amounts of osmium(VIII), based on its catalytic effect on the oxidation of carminic acid by hydrogen peroxide. The reaction was monitored spectrophotometrically by measuring the decrease in absorbance of carminic acid at 540 nm after 3 min of mixing the reagents. The optimum reaction conditions were 1x10(-4) mol l(-1) carminic acid, 0.013 mol l(-1) hydrogen peroxide and pH 10 at 25 degrees C. By using the recommended procedure, the calibration graph was linear from 0.1 to 1.5 ng ml(-1) of osmium; the detection limit was 0.02 ng ml(-1); the RSD for five replicate determinations of 0.2-1.4 ng ml(-1) was in the range of 1.8-4.7%. The influence of several foreign ions on osmium determination were studied and the effect of interfering ions were removed by extracting osmium into isobuthyl methyl ketone and back extracting into sodium hydroxide solution.

A highly sensitive and selective method is described for the determination of trace amounts of nitrite based on its effect on the oxidation of carminic acid with bromate. The reaction was monitored spectrophotometrically by measuring the decrease in absorbance of carminic acid at 490 nm after 3 min of mixing the reagents. The optimum reaction conditions were 1.8×10 −1 mol l −1 H 2 SO 4 , 3.8×10 −3 mol l −1 KBrO 3 , and 1.2×10 −4 mol l −1 carminic acid at 30°C. By using the recommended procedure, the calibration graph was linear from 0.2 to 14 ng ml −1 of nitrite; the detection limit was 0.04 ng ml −1 ; the R.S.D. for six replicate determinations of 6 ng ml −1 was 1.7%. The method is mostly free from interference, especially from large amounts of nitrate and ammonium ions. The proposed method was applied to the determination of nitrite in rain and river water.

A method has been developed for the determination of microgram amounts of boron in nitrate solutions. Nitrate is destroyed with formic acid and sulphuric acid under reflux conditions. As much as 3 millimoles of nitrate are reduced completely by refluxing 1 ml of the nitrate solution with 1 ml of 88% formic acid for 15 minutes. Boron is determined by the carminic acid method after forming the colored complex in situ. This method has been applied to the determination of boron in uranyl nitrate solutions after extraction of uranium with tri-n-octylphosphine oxide dissolved in cyclohexane.

The sample is dissolved in methanol and bromine. Boron is distilled out and collected in sodium hydroxide and methanol, then determined spectrophotometrically as the carminic acid complex.

A method is described for the spectrofluorimetric determination of molybdenum in mild steel down to 0.01 %. After dissolution of the sample, molybdenum is separated from the bulk of iron by extraction of molybdenum(V) thiocyanate with isoamyl acetate. It is then determined with carminic acid as described in Part I.

Boric acid at mug ml or ng ml level can be extracted from 1-6M hydrochloric acid into 2,2,4-trimethyl-1,3-pentanediol solution in chloroform and thus separated from many ions which interfere in the usual spectrophotometric methods. The boron is determined directly in the organic phase without back-extraction into water, by adding a solution of carminic acid in a mixture of sulphuric and glacial acetic acids (1+2 v v ) and measuring the absorbance at 549 nm. The molar absorptivity is 2.58 x 10(4) l.mole(-1).cm(-1) and Beer's law is valid for the 0.05-0.4 mug ml boron range. In the fluorimetric method, 509 or 547 nm can be used as the excitation wavelength and 567 nm for emission measurement, giving a linear response in the 8-120 ng ml boron range. Both methods have been applied to determination of boron in plants and natural waters with good precision and accuracy.

Carminic acid forms red fluorescent complexes with molybdenum(VI) and tungsten(VI) which provide spectrofluorimetric methods for the determination of these metals in the range 0.1–0.9 ppm and 0.4–0.36 ppm at pH 5.2 and 4.6 respectively. The optimum conditions for the analytical procedures have been established, and the effects of a wide range of cations and anions have been investigated. The reagent forms 1:1 complexes with both molybdenum and tungsten, and the conditional stability constants have been evaluated.