A simple and highly sensitive spectrophotometric determination of Cr(VI) in food samples by using 3,4-dihydroxybenzaldehydeisonicotinoylhydrazone (3,4-DHBINH)

A simple, rapid, sensitive and inexpensive method has been developed for the determination of trace amounts of chromium(VI) using 3,4-dihydroxybenzaldehydeisonicotinoylhydrazone (3,4-DHBINH). The metal ion gives a yellow coloured complex with 3,4-DHBINH in acetate buffer of pH 5.5 with 1:1 (metal:ligand) composition. The complex shows a maximum absorption at 400 nm. Beer’s law is obeyed in the range 0.5–7.7 ppm of Cr(VI). The molar absorptivity, Sandell’s sensitivity and detection limit were found to be 1.35 × 10⁴ L mol⁻¹ cm⁻¹, 0.0075 μg cm⁻² and 0.0045 μg mL⁻¹, respectively. The correlation co-efficient and regression co-efficient of the Cr(VI)–3,4-DHBINH complex were 0.99 and 0.12, respectively. Major cations and anions did not show any interference. The developed method has been successfully applied for the analysis of Cr(VI) in food samples (leafy vegetables), comparing the results simultaneously with those obtained using an Atomic Absorption Spectrophotometer, whereby the validity of the method has been tested.     

Spectrophotometric determination of zinc in foods using N-ethyl-3-carbazolecarboxaldehyde-3-thiosemicarbazone: Evaluation of a new analytical reagent

N-ethyl-3-carbazolecarboxaldehyde-3-thiosemicarbazone (ECCT) is proposed as a new sensitive reagent for the extractive spectrophotometric determination of zinc(II). The ECCT forms yellow colored species of zinc(II) at pH range 3.0–5.5 and the complex was extracted into benzene. The Zn(II)–ECCT complex shows maximum absorbance at 420 nm with molar absorptivity and Sandell’s sensitivity being 1.55 × 10⁴ lit mol⁻¹ cm⁻¹ and 4.212 × 10⁻³ μg cm⁻², respectively. The system obeys Beer’s law in the range of 0.4–6.0 mg/l, with an excellent linearity in terms of correlation coefficient value of 0.999. Most of the common metal ions generally found associated with zinc do not interfere. The repeatability of the method was checked by finding relative standard deviation (RSD). The developed method has been successfully employed for the determination of zinc(II) in foods. Various certified reference materials (NIST 1573, NBS 1572 and NIST SRM 8435) have been tested for the determination of zinc for the purpose of validation of the present method.     

Prediction of coagulation properties, titratable acidity, and pH of bovine milk using mid-infrared spectroscopy

This study investigated the potential application of mid-infrared spectroscopy (MIR 4,000-900 cm⁻¹) for the determination of milk coagulation properties (MCP), titratable acidity (TA), and pH in Brown Swiss milk samples (n = 1,064). Because MCP directly influence the efficiency of the cheese-making process, there is strong industrial interest in developing a rapid method for their assessment. Currently, the determination of MCP involves time-consuming laboratory-based measurements, and it is not feasible to carry out these measurements on the large numbers of milk samples associated with milk recording programs. Mid-infrared spectroscopy is an objective and nondestructive technique providing rapid real-time analysis of food compositional and quality parameters. Analysis of milk rennet coagulation time (RCT, min), curd firmness (a₃₀, mm), TA (SH°/50 mL; SH° = Soxhlet-Henkel degree), and pH was carried out, and MIR data were recorded over the spectral range of 4,000 to 900 cm⁻¹. Models were developed by partial least squares regression using untreated and pretreated spectra. The MCP, TA, and pH prediction models were improved by using the combined spectral ranges of 1,600 to 900 cm⁻¹, 3,040 to 1,700 cm⁻¹, and 4,000 to 3,470 cm⁻¹. The root mean square errors of cross-validation for the developed models were 2.36 min (RCT, range 24.9 min), 6.86 mm (a₃₀, range 58 mm), 0.25 SH°/50 mL (TA, range 3.58 SH°/50 mL), and 0.07 (pH, range 1.15). The most successfully predicted attributes were TA, RCT, and pH. The model for the prediction of TA provided approximate prediction (R² = 0.66), whereas the predictive models developed for RCT and pH could discriminate between high and low values (R² = 0.59 to 0.62). It was concluded that, although the models require further development to improve their accuracy before their application in industry, MIR spectroscopy has potential application for the assessment of RCT, TA, and pH during routine milk analysis in the dairy industry. The implementation of such models could be a means of improving MCP through phenotypic-based selection programs and to amend milk payment systems to incorporate MCP into their payment criteria.     

Utilisation of mid-infrared spectroscopy for determination of the geographic origin of Gruyère PDO and L’Etivaz PDO Swiss cheeses

The potential of mid-infrared spectroscopy (MIR), using an attenuated total reflectance (ATR) cell, was evaluated for the authentication of 25 Gruyère PDO and L’Etivaz PDO cheeses produced at different altitudes in Switzerland. In order to test the ability of MIR to authenticate the investigated cheeses, chemometric tools, such as principal component analysis (PCA) and factorial discriminant analysis (FDA), were applied to the three spectral regions of the MIR (e.g. 3000–2800 cm⁻¹, 1700–1500 cm⁻¹, and 1500–900 cm⁻¹). By applying the FDA to the first 10 principal components (PCs) of the PCA applied to each spectral regions, the best rate of correct classification was obtained in the 3000–2800 cm⁻¹ and 1500–900 cm⁻¹ spectral regions, since 90.5% and 90.9% were achieved, respectively. It can be concluded that these two spectral regions could be considered as valuable tools for the determination of the geographical origin of the investigated cheeses.     

Analytical applications of 2,6-diacetylpyridine bis-4-phenyl-3-thiosemicarbazone and determination of Cu(II) in food samples

New synthesized reagent 2,6-diacetylpyridine bis-4-phenyl-3-thiosemicarbazone (2,6-DAPBPTSC) is proposed as a sensitive and selective analytical reagent for the spectrophotometric determination of copper(II) at pH 3.0 to form a yellowish orange colored 1:1 chelate complex. The maximum absorbance was measured at 370 nm. This method obeys Beer’s law in the concentration range 0.63–6.30 g ml⁻¹ and the correlation coefficient of Cu(II)–2,6-DAPBPTSC complex is 0.942, which indicates an adequate linearity between the two variables with good molar absorptivity and Sandell’s sensitivity, 0.847 × 10⁴ l mol⁻¹ cm⁻¹ and 0.0075 g cm⁻², respectively. The instability constant of complex calculated from Asmus′ method is 1.415 × 10⁻⁴ at room temperature. The precision and accuracy of the method is checked with calculation of relative standard deviation (n = 5), 0.777% and the detection limit value is 0.0056 g ml⁻¹. The interfering effect of various cations and anions has also been studied. The method was successfully applied for the determination of Cu(II) in food samples. The performance of present method was evaluated in terms of Student ‘t’ test and Variance ‘f’ test, which is indicates the significance of present method is an inter comparison of the experimental values, using atomic absorption spectrometer (AAS).     

Measurement of integrated absorption cross-section,oscillator strength and number density of caffeine in coffee beans by integrated absorption coefficient technique

Integrated absorption cross-section and oscillator strength of caffeine in water and dichloromethane were reported by UV–Vis spectrometer in the wave number regions of 20,000–39,062 cm⁻¹ at room temperature. The integrated absorption cross-section of caffeine in water and dichloromethane in these wave number regions were (4.44 ± 0.18) × 10⁷ and (4.32 ± 0.11) × 10⁷ L mol⁻¹ cm⁻², respectively. The corresponding calculated value for oscillator strength of caffeine in water and dichloromethane were 0.19 ± 0.01 and 0.18 ± 0.01, respectively. In addition number densities of caffeine in different coffee beans were reported using integrating absorption coefficient technique. The calculated number density of caffeine for different coffee varieties were varying from (3.53–4.76) × 10⁻⁵ mol L⁻¹. The new applied technique has an advantage over other techniques in that it provides additional information about the nature of the absorbing molecules and establishes accurate evaluation of the UV–Vis absorption intensity.     

Electrocatalysis and sensitive determination of Sudan I at the single-walled carbon nanotubes and iron(III)-porphyrin modified glassy carbon electrodes

Iron-porphyrin (5,10,15,20-tetraphenyl-21H, 23H-porphine iron(III) chloride) was used in combination with single-wall carbon nanotubes (SWNTs) to modify a glassy carbon electrode (GCE). The electrochemical behavior of Sudan I on the iron-porphyrin-SWNT-DMF (N,N-dimethylformamide) modified GCE was studied by the cyclic voltammetry and square wave voltammetry. In pH 7.0 Tris–HCl buffers, Sudan I has a sensitive catalytic reduction peak at −0.08 V on the iron-porphyrin-SWNT-DMF modified GCE. Using square wave voltammetry, the linear relationship of Sudan I is 5.03 × 10⁻⁸ mol L⁻¹–2.01 × 10⁻⁶ mol L ⁻¹ with the tropics equation: Δ_iP = 3.40C + 3.43 × 10⁻⁶, and the detection limit is 1 × 10⁻⁸ mol L⁻¹. And the iron-porphyrin-SWNT-DMF modified GCE was applied successfully in the determination of Sudan I in real samples.     

Water absorption and starch gelatinization in whole rice grain during soaking

Hydration of rough rice grain in hot water as a function of time was studied at temperature range 25-90 °C. A simple model which considers simultaneous unsteady-state water diffusion and first-order irreversible water-starch reaction phenomenon, was used to evaluate the kinetics parameters from experimental curves. The values of the diffusion coefficients and reaction rate constants were between 1.40×10⁻¹¹ and 9.36×10⁻¹¹ m² s⁻¹ and 2.29×10⁻¹⁰ and 3.72×10⁻⁵ s⁻¹, respectively. Both parameters followed a Arrhenius-type equation with distinct activation energies below and above a break temperature of 60 °C. It was 25.4 and 289.3 kJ mol⁻¹ for the activation energies of diffusion and reaction, respectively, below 60 °C. Above this temperature the respective values of the activation energies of diffusion and reaction were 30.0 and 16.6 kJ mol⁻¹. This break temperature was in agreement with the gelatinization temperature determined experimentally.     

Evaluation of a chitosan-based edible film as carrier of natamycin to improve the storability of Saloio cheese

The purpose of this study was to evaluate the effects of the application of chitosan coating containing natamycin on the physicochemical and microbial properties of semi-hard cheese. Three cheese groups were prepared: samples without coating, samples coated with chitosan and with chitosan containing 0.50 mg mL⁻¹ of natamycin, whose minimum inhibitory concentration was previously determinated on cheese surface. Microbiological analyses showed that natamycin coated samples presented a decrease on moulds/yeasts of 1.1 log (CFU g⁻¹) compared to control after 27 days of storage. Addition of natamycin also affected O₂ and CO₂ permeability, increasing from 7.12 to 7.68 × 10⁻¹⁵ g·(Pa s m)⁻¹, and from 10.69 to 64.58 × 10⁻¹⁴ g·(Pa s m)⁻¹, respectively. The diffusion coefficient values of natamycin from the film to phosphate buffered saline solution and to the cheese were 3.60 × 10⁻¹⁰ and 1.29 × 10⁻¹² cm² s⁻¹, respectively. This study demonstrated that chitosan-based coating/films can be used as release system containing natamycin to create an additional hurdle for moulds/yeasts in cheese thus contributing to extend its shelf-life.     

Sensor-containing microspheres of chitosan crosslinked with 8-hydroxyquinoline-5-sulphonic acid for determination of Cu(II) in instant coffee

A novel carbon paste electrode containing chitosan microspheres for the determination of Cu(II) in instant coffee by anodic stripping voltammetry was developed. Chitosan was crosslinked with the chelating agent 8-hydroxyquinoline-5-sulphonic acid and glutaraldehyde. The microspheres of the crosslinked chitosan biopolymer were obtained by the spray drying technique and employed in the construction of the sensor. In acetate buffer solution (0.1 mol L⁻¹, pH 6.0), the calibration curve obtained was linear for concentrations of 5.0 × 10⁻⁷ to 1.4 × 10⁻⁵ mol L⁻¹ (r = 0.9990); the detection limit was 5.5 × 10⁻⁸ mol L⁻¹. The relative standard deviation (n = 8) was lower than 3.0% for solutions containing 6.0 × 10⁻⁶, 5.0 × 10⁻⁵ and 1.5 × 10⁻⁴ mol L⁻¹ of Cu(II). The method was successfully employed for determination of Cu(II) in instant coffee and the results obtained showed good agreement when compared with those using electrothermal atomic absorption spectrometry.     

Release kinetics of nisin from biodegradable poly(butylene adipate-co-terephthalate) films into water

The release kinetics of nisin from poly(butylene adipate-co-terephthalate) (PBAT) to distilled water was studied at of 5.6, 22 and 40 °C. The release kinetics of nisin from PBAT film was described using Fick’s second law of diffusion, partition coefficient, and Weibull model. The diffusion coefficients (D) determined were 0.93, 2.29, and 5.78 × 10⁻¹⁰ cm²/s at 5.6, 22, and 40 °C, respectively. The partition coefficients (K) calculated were 0.84, 3.89, and 5.2 × 10³ at 5.6, 22, and 40 °C, respectively. The nisin release data at selected temperatures were fitted with the Weibull model (R² > 0.97) with b and n values ranging from 0.02 to 0.98 and from 0.28 to 0.45, respectively. The temperature dependence of D, K, and Weibull model parameter b was modeled using the Arrhenius equation giving values of activation energy (E_a) of 38.3 kJ mol⁻¹ (for D), 38.5 kJ mol⁻¹ (for K), and 79.5 kJ mol⁻¹ (for b).     

Chemical characterization and antioxidant activity of sulfated polysaccharide from the red seaweed Gracilaria birdiae

Hydrocolloids from seaweeds have interesting functional properties, such as antioxidant activity and gelling ability. A polysaccharide was isolated by aqueous extraction at 90 °C from the red seaweed Gracilaria birdiae (Gb), with a yield of 27.2% of the seaweed dry weight. The sulfate content of the polysaccharide was 8.4% and the main sugars present were galactose (65.4 mol%), 3,6-anhydrogalactose (25.1 mol%) and 6-O-methylgalactose (9.2 mol%). Gel permeation chromatography showed that Gb polysaccharide is a heterogeneous system, with molar mass at the main peak of 3.7 × 10⁵ g mol⁻¹ and a shoulder of 2.6 × 10⁶ g mol⁻¹. The sulfated polysaccharide of Gb characterized by FTIR exhibits the characteristic bands of agarocolloids (at 1375 and 770 cm⁻¹).     

Drying description of cylindrical pieces of bananas in different temperatures using diffusion models

Three diffusion models were used to describe drying of bananas cut into cylindrical pieces. Analytical solutions of the diffusion equation with boundary conditions of the first and third kind were used to describe the process. In the drying experiments using hot air, the cylindrical pieces had the following dimensions: length of about 21 mm and radius of 15 mm, on average. The drying air temperatures were 40, 50, 60 and 70 °C. To determine the process parameters, an optimizer was coupled to the analytical solutions. For the best model, the effective mass diffusivities were 2.53 × 10⁻⁸; 3.12 × 10⁻⁸; 6.19 × 10⁻⁸ and 7.32 × 10⁻⁸ m² min⁻¹, while the convective mass transfer coefficients were 1.93 × 10⁻⁵; 3.04 × 10⁻⁵; 3.18 × 10⁻⁵ and 4.97 × 10⁻⁵ m min⁻¹. The determination coefficients were greater than 0.9990 and the chi-squares were less than 5.3 × 10⁻³ for all simulations of the experiments.     

Migration of α-tocopherol and resveratrol from poly(L-lactic acid)/starch blends films into ethanol

Poly(L-lactic acid) (PLLA)/starch blends with various concentrations of two natural antioxidants, α-tocopherol (α-TOC) and resveratrol, were fabricated by a melt blending and compression molding processes. The effects of the two antioxidants on the optical (color), thermal and mechanical properties of PLLA/starch blends with antioxidants were assessed. PLLA/starch blend films with α-TOC and resveratrol showed a yellowish color influenced by the combined effect of white starch and the brown color of the antioxidants. The glass transition and melting temperatures were significantly reduced with the addition of antioxidants while enhanced thermal stability was observed, which could be a benefit and important for processing and production. The enhanced mechanical properties could be attributed to not only a compatibilization effect based on the chemical linkage between PLLA and starch chains, but also restriction of the chain mobility by antioxidants. The release of resveratrol from PLLA and PLLA/starch blend films into ethanol followed Fickian behavior. The D values of α-TOC were in the range of 0.47–3.95 × 10⁻¹¹ cm² s⁻¹ for PLLA films and 0.70–6.83 × 10⁻¹¹ cm² s⁻¹ for PLLA/starch blend films at 13 °C, 5.67–13.0 × 10⁻¹¹ cm² s⁻¹ for PLLA films and 4.10–24.2 × 10⁻¹¹ cm² s⁻¹ for PLLA/starch blend films at 23 °C, and 89.0–118.0 × 10⁻¹¹ cm² s⁻¹ for PLLA films and 123–282 × 10⁻¹¹ cm² s⁻¹ for PLLA/starch blend films at 43 °C. The D values of resveratrol were in the range of 0.073–0.54 × 10⁻¹⁰ cm² s⁻¹ for PLLA films and 1.42–6.93 × 10⁻¹⁰ cm² s⁻¹ for PLLA/starch blend films at 13 °C, 0.90–3.44 × 10⁻¹⁰ cm² s⁻¹ for PLLA films and 4.16–22.3 × 10⁻¹⁰ cm² s⁻¹ for PLLA/starch blend films at 23 °C, and 24.8–74.1 × 10⁻¹⁰ cm² s⁻¹ for PLLA films and 40.1–309 × 10⁻¹⁰ cm² s⁻¹ for PLLA/starch blend films at 43 °C.     

Adsorption of dark compounds with bentonites in apple juice

The adsorption equilibrium of dark-coloured compounds from apple juice has been investigated as a function of several variables including activation conditions of bentonite (heat and acid treatments), clay concentrations (2×10⁻³-8×10⁻³ kg clay/dm³ apple juice) and temperature (range of 296-336 K). The adsorption efficiency with acid-activated bentonite was greater than that with heat-activated and native bentonite, depending on surface properties; specific surface areas were 95.31, 71.95 and 71.76 m²/g, respectively.Absorbance data at 420 nm were fitted reasonably well with the Langmuir and Freundlich isotherms. The parameters K, Q₀, K_fr and n were determined for different temperatures. Thermodynamic parameters such as Gibbs free energy (ΔG), enthalpy (ΔH) and entropy (ΔS) change of adsorption were determined as about −3.125, 9.43 and 0.039 kJ mol⁻¹ K⁻¹, respectively, for acid-activated bentonite. These parameters were also determined for native and heat-activated bentonites. It was shown that the adsorption process was endothermic, spontaneous and controlled by physical mechanism. The adsorption and desorption rate constants (k_a and k_d) were obtained separately by applying a geometric approach to the first-order Langmuir model. k_a varied from 5.717×10⁻⁴ to 20.667×10⁻³ s⁻¹ and k_d from 1.425×10⁻⁴ to 7.473×10⁻³ s⁻¹. The results showed that acid-activated bentonite is more suitable for the adsorption of dark compounds from apple juice.     

The determination of boron in food and seed by spectrophotometry using a new reagent 3,4-dihydroxyazomethine-H

A new sensitive and selective reagent, 3,4-dihydroxyazomethine-H, was studied for spectrophotometric determination of boron in food and seed. Boron (III) reacts with 3,4-dihydroxyazomethine-H to form a 1:2 yellow complex in an ammonium acetate solution of pH 8.0, which has a maximum absorption peak at 430 nm. Under the optimal conditions, Beer’s law was obeyed over the range 0 ∼ 20 μg of boron (III) in 25 ml of solution. The apparent molar absorptivity is 2.95 × 10⁴ l mol⁻¹ cm⁻¹, in which the sensitivity is higher than 4.2-fold that of azomethine-H. The limit of quantification, limit of detection and relative standard deviations were found to be 5.1, 1.5 ng g⁻¹ and 1.08 %, respectively. The influences of foreign ions on the determination of boron were also investigated in detail, most of the ions studied can be tolerated in considerable amounts. The reaction can be completed within 90 min and the absorbance of the complex remains maximum and almost constant for 24 h under room temperature from 0 to 35 °C, which is advantagous over other derivatives of azomethine-H reported remarkably. The proposed method has been successfully applied to the determination of boron in food and seed.     

Electrochemical determination of Sudan I using montmorillonite calcium modified carbon paste electrode

In the current work, a sensitive, rapid and convenient electrochemical method was developed for the determination of Sudan I utilizing the excellent properties of montmorillonite calcium (MMT-Ca). Compared with the unmodified carbon paste electrode (CPE), MMT-Ca modified CPE not only significantly enhances the oxidation peak current of Sudan I but also lowers the oxidation overpotential, suggesting that the MMT-Ca modified CPE can remarkably improve the determining sensitivity of Sudan I. The experimental conditions such as determining medium, the content of MMT-Ca and accumulation time were optimized for the determination of Sudan I. The oxidation peak current is proportional to the concentration of Sudan I over the range from 0.05 mg L⁻¹ (2.01 × 10⁻⁷ mol L⁻¹) to 1.0 mg L⁻¹ (4.03 × 10⁻⁶ mol L⁻¹), and the limit of detection is 0.02 mg L⁻¹ (8.06 × 10⁻⁸ mol L⁻¹) for 2-min accumulation. Finally this newly-proposed sensing method was successfully employed to detect Sudan I in practical samples and good recovery was achieved.     

Voltammetric determination of the herbicides nitralin and oryzalin in agricultural formulations,vegetables and grape juice samples

A sensitive method for the determination of the herbicides nitralin and oryzalin by adsorptive stripping voltammetry (AdSV) at a hanging mercury drop electrode (HMDE) (pH 6.0) was described. The cyclic voltammograms demonstrate the adsorption of these compounds at the mercury electrode. A symmetric study of the various operational parameters that affect the stripping response was carried out by differential pulse voltammetry. With an accumulation potential of −0.5 V and a 80 s accumulation time, the limit of detection was 2.47 × 10⁻⁸ mol/L and 1.5 × 10⁻⁸ mol/L, the relative standard deviation (n = 10), correlation coefficient values 1.14%, 0.998, 1.48%, 0.999 at concentration levels of 8.3 × 10⁻⁸ mol/L to 1.5 × 10⁻⁶ mol/L and 2 × 10⁻⁸ mol/L to 1.0 × 10⁻⁵ mol/L for both compounds. The degree of interference of some other pesticides on the differential pulse adsorptive stripping signal for nitralin and oryzalin was evaluated. Finally the proposed method was applied for determination of nitralin and oryzalin in agricultural formulations, vegetables and grape juice samples.     

A new rapid spectrophotometric method to determine the rosmarinic acid level in plant extracts

A novel spectrophotometric method to determine the amount of rosmarinic acid in unpurified methanol extracts of the plants was developed. Rosmarinic acid is a naturally occurring bioactive compound in plants as an ester of caffeic acid with 3,4-dihydroxyphenyl lactic acid. The developed method was based on the complexation of rosmarinic acid with Zr⁴⁺ ions, giving a maximum absorbance at 362 nm. The absorptivity coefficient at this wavelength was found to be ε₃₆₂ = 2.66 × 10⁴ L mol⁻¹ cm⁻¹. In fact, this method is also specified giving two more absorption bands in UV region at 299.5 and 263.5 nm besides 362 nm. In addition, the accuracy and sensitivity of the new developed method are compared with the direct UV and rosmarinic acid–Fe²⁺ complex spectrophotometric methods by using methanol extracts of 11 Salvia species. As a conclusion, the present method is faster, cheaper, and more selective than the conventional methods for rosmarinic acid.