Effect of storage time and natural corrosion inhibitor on carbohydrate and carboxylic acids content in canned tomato puree.

In this research compositional changes of tinplate-canned tomato purées, with or without the addition of essential onion oil were investigated. The study was focused on the analyses of carbohydrates and carboxylic acids in two groups of canned samples (with or without nitrates) to determine whether their chemical composition was affected with storage time. The measurements were performed by high performance liquid chromatography, during six months of storage. The contents of glucose, fructose and two major organic acids, citric and malic, were found in the concentration range 1.77-1.97%, 1.86-2.09%, 0.60-0.75% and 0.23-0.30%, respectively, in all canned samples. Compared to carbohydrates and organic acids, amino acids were found in minor quantities, among them, as most abundant ones were glutamic acid, arginine, aspartic and γ-amino butyric acids. The results show that contents of carbohydrates and carboxylic acids are significantly affected by the change of storage time in majority of analyzed samples. The results also indicated that the influence of essential onion oil on composition of canned tomato purée is within the range of changes due to storage time measured for all other types of cans. Therefore the addition of essential onion oil as natural efficient corrosion inhibitor, as it was found in our previous work, can be recommended for canned tomato purée.

Corrosion behaviour of tinplate cans in contact with tomato purée and protective (inhibiting) substances.

The dissolution of iron and tin from tinplate cans filled with tomato purée (pH 4.34) and dioctyl sebacate oil (DOS), essential onion oil (EOO) or potassium nitrate was studied using atomic absorption spectroscopy (AAS), while nitrate was determined using high-performance liquid chromatography (HPLC). The maximum values found in cans were up to 284 mg kg(-1) for tin and 513 mg kg(-1) for iron at elevated storage temperature. Results indicated that the addition of EOO to tomato purée prevents the corrosion process in the case of tin, where concentrations were lowered from 223 to 28 mg kg(-1) for cans with DOS oil and EOO at 20 degrees C, respectively (inhibition rate of 87%). On the other hand, the presence of EOO enhanced the corrosion process for iron increasing the concentration from 15 to 46 mg kg(-1) during 7 months of storage, although this value did not exceed maximum permitted value (50 mg kg(-1)). In cans with tomato purée and potassium nitrate, dissolution of tin started after 30 (36 degrees C) and 60 (20 degrees C) days of storage as a consequence of nitrate action, which act as a corrosion accelerator. Since the addition of EOO improves the taste of canned tomato purée, its potential use as a corrosion inhibitor would be of interest.

Influence of essential onion oil on tin and chromium dissolution from tinplate.

During food and beverage packaging in tinplate cans the dissolution of tin and chromium into food content may occur. To protect metallic surface different corrosion inhibitors are recommended, nowadays particularly a new group of natural products is of interest. In this work the influence of essential onion oil (EOO) on metals dissolution (tin and chromium) from tinplate sheets before food canning was investigated. The analyses were performed by galvanostatic method and atomic absorption spectroscopy. The values of tin obtained for the internal surface of tinplate covered with EOO (7.31-9.76 gm(-2)) are lower than the values when dioctyl sebacate oil (DOS), as a protective tinplate surface layer for food caning, was used (9.24-11.03 gm(-2)). Obviously, the presence of EOO diminished more efficiently then DOS oil the dissolution of tin in electrolyte during galvanostatic analyses. The efficiency of EOO as corrosion inhibitor was even more pronounced in the case of chromium where the dissolution from 1.8-2.5 mgm(-2) (DOS oil) was lowered to 1.0-1.3 mgm(-2) (EOO). Correlation of results obtained with two different physico-chemical methods was satisfying.

Use of a ruthenium(III), iron(II), and nickel(II) hexacyanometallate-modified graphite electrode with immobilized oxalate oxidase for the determination of urinary oxalate.

This paper describes the performance of a biosensor with an Ru(III), Ni(II), and Fe(II) hexacyanometallate-modified graphite electrode and immobilized oxalate oxidase for the determination of urinary oxalate. The addition of ruthenium enhances the electrochemical reversibility and chemical stability of the electrocrystallized layer and improves the sensitivity of the biosensor. Hydrogen peroxide, produced by the enzyme-catalyzed oxidation of oxalate, was measured at -50 mV vs an Hg Hg2CI2 3M KCl electrode in a solution of pH 3.6 succinic buffer, 0.1 M KCl, and 5.4mM ethylenediaminetetraacetic acid. The linear concentration range for the determination of oxalate was 0.18-280 microM. The recoveries of added oxalate (10-35 microM) from aqueous solution ranged from 99.5 to 101.7%, whereas from urine samples without oxalate (or with a concentration of oxalate below the detection limit) the recoveries of added oxalate ranged from 91.4 to 106.6%. The oxalate in 24 h urine samples, taken during their daily routine from 35 infants and children, was measured and found to range from 0.6 to 121.7 mg/L. There were no interferences from uric acid, acetylsalicylic acid, and urea in the concentration range investigated, but paracetamol and ascorbic acid did interfere. A good correlation (R2 = 0.9242) was found between values obtained for oxalate in real urine samples by 2 laboratories, with the proposed biosensor and ion chromatography, respectively.

Determination of oxalate in urine, using an amperometric biosensor with oxalate oxidase immobilized on the surface of a chromium hexacyanoferrate-modified graphite electrode.

A novel enzymatic amperometric method is described for the determination of oxalic acid in urine. An amperometric biosensor was made by immobilizing oxalate oxidase on the surface of a chromium(III) hexacyanoferrate-modified graphite electrode by using a bovine serum albumin and glutaraldehyde cross-linking procedure. The enzyme biocatalyzes oxalate decomposition in the presence of oxygen into carbon dioxide and hydrogen peroxide. The oxalate concentration, which is proportional to the amount of hydrogen peroxide, was determined amperometrically by measuring the current resulting in the reduction of hydrogen peroxide at a very low working potential (0.05 V versus the Hg ¿Hg2Cl2¿ 3M KCl electrode), which minimized the influence of the possible interferences present in human urine. All experiments were performed with succinic buffer, pH 3.8, containing 0.1M KCl and 5.4mM ethylenediaminetetraacetic acid. In an aqueous solution of pure oxalic acid, the biosensor showed good linearity in a concentration range of 2.5-100 microM without the use of a dialysis membrane. For untreated urine samples, a high correlation (R2 = 0.9949) was obtained between oxalate concentrations added to urine samples and oxalate recoveries calculated for determinations with the described oxalate biosensor.

Improved signals ratio resolution method by optimization of resolution function--simultaneous determination of Cu(II) and Cd(II) in water samples.

From an ecological and economical point of view, it is important to design analytical procedures for monitoring heavy metals in the environment and industrial processes in a way to minimize the use of hazardous reagents and reduce the analysis time. In this paper, a well-known dithizonate extraction-based method for the determination of many metal ions was improved by using chemometrical selectivity of the strongly overlapped spectra of copper and cadmium dithizonates in CCl4 for their simultaneous determination from a single extraction at pH 10. The individual absorption spectra, having absorption maxima difference of only 20 nm, were separated, and the metal ions were quantified by using an improved procedure for optimizing the resolving function in a recently proposed signals ratio method. The procedure consists of using many different resolving functions and plotting the difference of the mean of absolute and nonabsolute mean values of pseudosignals [PDMMV (PS)] against analyte concentrations obtained with each of the resolving functions, thus obtaining 2 straight lines having intersections that give a unique and reliable value of the unknown concentration of the individual analyte in mixture giving strongly overlapped spectra. In this way, the main drawback of the signals ratio resolution method, that is, the visual estimation of optimal resolving function, is eliminated. The proposed parameter, PDMMV (PS), was tested by using both simulated and experimental spectra. Copper was determined in the mixture with ca 20-fold excess of cadmium, and cadmium was determined in ca 10-fold excess of copper at submicromolar concentration levels.

Direct determination of zirconium and chromium by first-derivative spectrophotometry.

The solution properties of zirconium complex with the Schiff's base 2-(2-pyridylmethyl-eneamino)phenol have been studied by zero-order absorption spectrophotometry. The influence of pH, stability of the complexes with time and stability constants were investigated. The use of first-derivative spectrometry eliminates the interference of chromium and enables the simultaneous determination of zirconium and chromium without previous separation. The relative overall standard errors, of five independent simultaneous determinations of zirconium and chromium at the 1.0 mug/ml concentration level, were 2 and 4%, respectively. The proposed method has been successfully applied to the analysis of some real samples of zirconium/chromium bronzes.