Effects of temperature,solid content and pH on the stability of black carrot anthocyanins

Anthocyanin stability of black carrots was studied at various solid contents (11, 30, 45 and 64° Brix) and pHs (4.3 and 6.0) during both heating, at 70–90 °C, and storage at 4–37 °C. Monomeric anthocyanin degradation fitted a first-order reaction model. Degradation of monomeric anthocyanins increased with increasing solid content during heating, while it decreased during storage. For example, at pH 4.3, half-life periods for anthocyanins at 30, 45 and 64° Brix were, respectively, 8.4, 6.9 and 5.2 h during heating at 80 °C and 18.7, 30.8 and 35.9 weeks during storage at 20 °C. At 30–64° Brix, increasing pH from 4.3 to 6.0 enhanced the degradation of anthocyanins during heating. The effect of pH on thermal stability of anthocyanins was also studied at six different pHs (2.5–7.0) in citrate-phosphate buffer solutions and significant decrease in anthocyanin stability was observed at pHs above 5.0. Higher activation energies (E_a) were obtained during heating than during storage with increasing solid contents. At 30–64° Brix, E_a values ranged from 68.8 to 95.1 kJ mol⁻¹ during heating and from 62.1 to 86.2 kJ mol⁻¹ during storage. Q₁₀ values at 20–37 °C were as high as 3.1 at 45° Brix and 3.6 at 64° Brix.     

Effect of water activity on the thermal stability of Thermomyces lanuginosus xylanases for process time–temperature integration

Three strains of the thermophilic fungus Thermomyces lanuginosus were used to produce β-xylanases. The thermal stability of these xylanases at low levels of water activity was studied. Isothermal inactivation experiments were performed in the temperature range of 100–130 °C. Reduction of water activity to 0.63 and as low as 0.13 had a drastic effect on the observed D and z-values. At water activity of 0.13 the D_120 °C and z-values of the three xylanases ranged from 20.4 to 37.6 min and from 23.3 to 28.9 °C, respectively. The applicability of the developed kinetic models was tested under time–temperature profiles representative of typical thermal processes. The developed systems can be applied as time–temperature integrators (TTI) at this high thermal processing range. Calculations demonstrated that the use of a triple xylanase TTI system could provide acceptable F-values prediction for z-values lower than the achieved range.     

Solid-state fermentation of apple pomace using Phanerocheate chrysosporium – Liberation and extraction of phenolic antioxidants

Apple pomace is a by-product from the apple processing industry and can be used for the production of value-added phenolic compounds. A study was carried out to understand the changes and liberation of phenolic compounds and improvement in antioxidant activity during solid-state fermentation of apple pomace using Phanerocheate chrysosporium. The solid-state fermentation of apple pomace using P. chrysosporium mobilised the polyphenolic compounds and improved the nutraceutical properties. The polyphenol content in acetone extract increased and the results were statistically significant (P < 0.05) from 4.6 to 16.12 mg GAE/g dry weight during solid-state fermentation. The effect of various solvents, temperature, time and detergents were also investigated for the extraction of polyphenolics by ultrasonication and microwave-assisted extraction methods. The polyphenol content of the extracts was found to be in the range of 5.78–16.12 mg GAE/g DW of samples, depending on the solvent, extraction time and temperature. Antioxidant activities of polyphenol extracts were tested using the 2,2-diphenyl-1-picryhydrazyl (DPPH) radical methods, where the IC₅₀ ranged from 12.24 to 23.42 μg DW sample, depending on the extraction conditions and the antioxidant activities correlated well with the polyphenol concentrations.     

Green and gold kiwifruit peel ethanol extracts potentiate pentobarbital-induced sleep in mice via a GABAergic mechanism

Kiwifruit is one of the most popular fruits worldwide, and it has various biological properties, including antioxidant, anti-allergic, and cardiovascular protective effects. The peel of kiwifruit, which is a by-product of processing, is a good source of flavonoids; however, its bioactivity has not been widely investigated. In this study, we evaluated the hypnotic effects of green (GRPE, Actinidia deliciosa) and gold (GOPE, Actinidia chinensis) kiwifruit peel ethanol extracts and their solvent fractions, and the possible underlying mechanisms. Oral GRPE and GOPE administration (125–1000 mg/kg) produced a dose-dependent decrease in sleep latency and an increase in sleep duration in pentobarbital-treated mice. Among three different solvent fractions of GRPE and GOPE, ethyl acetate (EA) fractions had the greatest effect on sleep duration at 250 mg/kg. The total flavonoid contents of solvent fractions were proportional to sleep duration. Like diazepam (a GABA_A–benzodiazepine (BZD) receptor agonist), the hypnotic effects of GRPE, GOPE, and their EA fractions were fully inhibited by flumazenil (a GABA_A–BZD receptor antagonist). These results suggest that potentiation effects of GRPE and GOPE on pentobarbital-induced sleep in mice may be modulated by a GABAergic mechanism.     

Phytochemical composition and thermal stability of two commercial açai species, Euterpe oleracea and Euterpe precatoria

Açai fruit are native to the Amazon region of South America and two predominant species are commercially exported as fruit pulps for use in food and beverage applications. Detailed characterisation of the polyphenolic compounds present in the de-seeded fruits of Euterpe oleracea and Euterpe precatoria species were conducted by HPLC–ESI–MSⁿ analyses and their thermal stability and overall influence on antioxidant capacity were determined. Anthocyanins were the predominant polyphenolics in both E. oleracea (2247 ± 23 mg/kg) and E. precatoria (3,458 ± 16 mg/kg) species, and accounted for nearly 90% of the trolox equivalent antioxidant capacity in both E. oleracea (87.4 ± 4.4 μmol TE/g) and E. precatoria (114 ± 6.9 μmol TE/g) fruits. Various flavones, including homoorientin, orientin, taxifolin deoxyhexose and isovitexin; various flavanol derivatives, including (+)-catechin, (−)-epicatechin, procyanidin dimers and trimers, and phenolic acids, including protocatechuic, p-hydroxybenzoic, vanillic, syringic and ferulic acids, were also present in both species. Thermal stability of these compounds was evaluated, following a thermal holding cycle (80 °C for up to 60 min) in the presence and absence of oxygen. Both species experienced only minor changes (<5%) in non-anthocyanin polyphenolic contents during all thermal processes whereas 34 ± 2.3% of anthocyanins in E. oleracea and 10.3 ± 1.1% of anthocyanins in E. precatoria were lost under these conditions, regardless of the presence of oxygen. Proportional decreases (10–25%) in antioxidant capacity accompanied the anthocyanin changes. Results suggest that both açai species are characterised by similar polyphenolic profiles, comparable antioxidant capacities, yet only moderate phytochemical stability during heating.     

Immobilization of pepsin on chitosan beads

In this study, chitosan beads were prepared by using a cross-linking agent and the resulting beads were employed in immobilization process. Studies on free and immobilized pepsin systems for determination of optimum temperature, optimum pH, thermal stability, pH stability, operational stability, storage stability and kinetic parameters were carried out. The optimum temperature interval for free pepsin and immobilized pepsin were 30–40 and 40–50 °C, respectively. Free and immobilized pepsin showed higher activity at pH 2.0–4.0. Apparent K_m = 12.0 g L⁻¹ haemoglobin (1.56 mM tyrosine) and V_max = 5220 μmol (mg protein min)⁻¹ values were obtained for free pepsin, while apparent K_m = 20.0 g L⁻¹ haemoglobin (2.16 mM tyrosine) and V_max = 2780 μmol (mg protein min)⁻¹ values were obtained for immobilized pepsin. Thermal stability and storage stability of immobilized pepsin were higher than that of free pepsin. Milk clotting activity was used for evaluation of the applicability of pepsin immobilization to industrial process. Optimum milk clotting temperature was found as 40 °C for free pepsin and 50 °C for immobilized pepsin.     

A convective multi-flash drying process for producing dehydrated crispy fruits

The aim of this work was to evaluate the application of a convective multi-flash drying process (CMFD) to producing dehydrated and crisp fruits. To accomplish this process, samples of banana (Musa sapientum L.) or mango (Mangifera indica L.) were heated to 60 °C by hot air, and a vacuum pulse was applied, which resulted in dehydration by a combination of convective drying and flash evaporation. Banana processed by CMFD had a moisture content of 0.293 g/g (dry basis) and a_w = 0.272 after 3 h of processing. Mango had a moisture content of 0.09 g/g and a_w = 0.359 after 4 h of processing. Puncture tests on fruits dehydrated by CMFD and on commercial freeze-dried fruits showed strain-force curves with many peaks (jagged curves). For CMFD much smaller global shrinkage was observed. These results indicate that the CMFD process can be applied for producing crispy fruits and is an alternative to the freeze-drying process.     

Molecular characteristics of partially hydrolyzed fucoidans from sporophyll of Undaria Pinnatifida and their in vitro anticancer activity

The effects of molecular characteristics on the anticancer activity of fucoidans were investigated after hydrolysis by copper acetate and then fractionation with 30 and 5 kDa membranes, which produced three fucoidan fractions: F_>30 K, F_5–30 K and F_<5 K. The F_>30 K and F_5–30 K consisted of mostly carbohydrate (58.2–61.3%) and sulphate (31.7–35.5%) with small amounts of proteins (1.2–6.4%). However, the major constituents of F_<5 K were sulphate (31.8%) and ash (37.5%) with smaller amounts of carbohydrate (15.5%) and protein (1.2%). The molecular weights (M_w) of F_>30 K, F_5–30 K and F_<5 K, obtained by a light scattering technique, were 262, 5.6 and 1.6 kDa, respectively. The observed anticancer activities were 18.0–28.5% for F_>30 K, 19.2–57.5% for F_5–30 K and 26.5–36.5% for F_<5 K, respectively, in the concentration range of 0.2–0.8 mg/mL. The results suggest that the anticancer activity of fucoidans could be considerably improved by lowering their M_w and by improving the binding properties of sulphate groups possibly through changing the molecular conformation.     

Physico-mechanical properties of chitosan films with carvacrol and grape seed extract

The physico-mechanical properties of 3 films composed by carvacrol, grape seed extract (GSE) and chitosan in different proportions were studied. The films, prepared by solvent casting technique with the following compositions of the casting solutions in carvacrol, GSE and chitosan: film-1: 9.6 ppm–684 ppm–1.25% w/v, film-2: 60 ppm–400 ppm–1.2% w/v and film-3: 90 ppm–160 ppm–1.24% w/v and were compared to a control (1.25% w/v chitosan) film. Mechanical, structural, barrier and colour properties of the films were evaluated. Film-3 presented the lowest water vapour and carbon dioxide permeabilities (WVP and CO₂P) and tensile strength (TS) values and the highest oxygen permeability (O₂P), whereas film-1 presented the highest water content and the lowest crystallinity, CO₂P, TS and luminosity. These results suggest that in the range studied, carvacrol and GSE affect the film structure and its mechanical properties due to hydrophilic (GSE) and hydrophobic (carvacrol) compounds. This work will help the development of edible films, based on physico-mechanical properties, contributing to food preservation and shelf-life extension.     

Development and characterization of a prototype of a lactic acid–based time–temperature indicator for monitoring food product quality

Temperature is a crucial factor affecting the quality and safety of food products during both distribution and storage. The difficulty in controlling and monitoring the temperature history of food products makes it difficult to precisely predict shelf life. Time–temperature indicators (TTIs) provide a visual summary of a product’s accumulated chill-chain history, recording the effects of both time and temperature. Attempts have been made to develop a prototype of a time–temperature indicator based on the diffusion of lactic acid, which is temperature-dependent. Four lactic acid-based TTIs were made in different substrate concentrations. Color changes associated with the diffusion of lactic acid were monitored. In the vapor diffusion of lactic acid, an irreversible color change of a chemical chromatic indicator (from green to red) clearly and progressively occurred due to the pH reduction. The temperature dependence of these TTIs kinetics was characterized isothermally in the range of 4–45 °C, yielding activation energy (E_a) of, approximately, 50 kJ mol⁻¹. The mathematical models of each TTI were established according to the relationships between color changes and time and temperature. The differences between the E_a values of the TTIs and the E_a associated with food quality losses – including enzymatic loss, hydrolysis, lipid oxidation, nutrient loss and microbial growth – were less than 40 kJ mol⁻¹, and therefore these TTIs could be considered as good candidates to monitor food quality losses. Although these TTIs do not cover the whole range of food quality losses, they could be applied to show the time–temperature history of some foods, especially fruits and vegetables, and to indicate food quality associated with time–temperature exposure.     

Multiresidue method for determination of 88 pesticides in berry fruits using solid-phase extraction and gas chromatography–mass spectrometry: Determination of 88 pesticides in berries using SPE and GC–MS

A method using solid phase extraction (SPE) cleanup followed by gas chromatography–mass spectrometry (GC–MS) has been established for quantitative determination of 88 pesticide residues in berry fruits including raspberry, strawberry, blueberry and grape. Based on an appraisal of the characteristics of GC–MS, validation experiments were conducted for 88 pesticides. In the method, solid-phase extraction was carried out using Envi-Carb cartridge coupled with NH₂-LC cartridge with acetonitrile–toluene (3:1, v/v) as the eluted solvent. In the linear range of each pesticide, the correlation coefficient was R² ? 0.99. At the low, medium and high three fortification levels of 0.05–0.5 mg kg⁻¹, recoveries fell within 63–137%. The relative standard deviation was between 1% and 19% for all 88 pesticides. Low limits of detection (0.006–0.05 mg kg⁻¹) and quantification (0.02–0.15 mg kg⁻¹) were readily achieved with this method for all tested pesticides.     

Influence of technological processing on apple aroma analysed by high resolution gas chromatography–mass spectrometry and on-line gas chromatography-combustion/pyrolysis-isotope ratio mass spectrometry

Extracts obtained by simultaneous distillation extraction (SDE) from industrial raw materials, namely single strength apple juices, and concentrates and aromas made thereof (each n = 31, from one production line; origin Poland, Germany, Turkey, Romania and China), as well as commercially available juices (n = 27), were analysed by standard controlled capillary gas chromatography–mass spectrometry (HRGC–MS). During the technological processing from juice to the aroma, no qualitative changes in the apple aroma profile were observed. Major constituents of the juices and aromas under study were found to be 1-hexanol (juice, 0.06–5.9 mg/l; aroma, 47–685 mg/l), 1-butanol (juice, 0.1–4.7 mg/l; aroma, 17–370 mg/l); E-2-hexenol (juice, 0.01–3.4 mg/l; aroma, 12–300 mg/l); E-2-hexenal (juice, 0–3.0 mg/l; aroma 0–470 mg/l), and butyl acetate (juice, 0–1.7 mg/l; aroma, 0–165 mg/l). By far the major component of the apple juice concentrates under study was furfural (2.4–56 mg/kg). The observed occurrence of 3-methyl-1-butanol (juice, 0.01–2.1 mg/l; aroma, 1.5–134 mg/l) and, in part, its acetate (juice, 0–0.3 mg/l; aroma, 0–3.3 mg/l), both known not to be genuine apple constituents, was obviously caused by fermentative effects in the course of industrial juice production. In addition, on-line capillary gas chromatography–isotope ratio mass spectrometry was used in the combustion (C) and the pyrolysis (P) modes (HRGC–C/P–IRMS) for the determination of δ¹³C_V-PDB and δ²H_V-SMOW values of selected apple flavour constituents to check potential isotope discrimination during distillative aroma production. As shown by means of the representative examples of E-2-hexenal, 1-hexanol and E-2-hexenol, their δ²H_V-SMOW values were slightly depleted. However, authenticity assessment by stable IRMS will not be influenced by this effect.     

Effect of ozone processing on the colour,rheological properties and phenolic content of apple juice

Apple juice samples were ozonated with processing variables of ozone concentration (1–4.8% w/w) and processing time (0–10 min). Effects of processing variables on colour values (L, a and b), rheological properties and phenolic content were studied. Significant reductions in these parameters were observed during ozonation. Second order polynomial regression modelling was used to investigate the main effects of ozone concentration and processing time on the changes in the selected quality parameters of ozonated apple juice. Predicted models were found to be significant (p < 0.05) with low standard error and high coefficients of determination (R²).     

Effects of light,temperature and water activity on the kinetics of lipoxidation in almond-based products

Lipoxidation in almond-derived products was investigated using the chemiluminescence (CL) and thiobarbituric acid-reactive substances (TBARS) methods to detect the first and later reaction products, respectively. The effects of light during storage at 5 °C, 22 °C and 40 °C were studied, as well as the effects of combined heat/water activity treatments in the 60–120 °C and 0.38–0.72 range. During storage, light was found to enhance the CL and TBARS values, and specific responses were observed in almond paste and the final Calisson product. During the heating of almond paste, as the initial water activity (a_w) increased, the CL rate constants increased during heating to 60 °C and 80 °C, but interestingly, these values decreased during further heating to 120 °C, whereas the maximum TBARS rate constants occurred at a_w 0.57 at all the heating temperatures tested. The activation energies, based on the CL and TBARS values, decreased specifically when the a_w increased from 0.38 to 0.72, giving overall values ranging from110 kJ mol⁻¹ to 60 kJ mol⁻¹. Likewise, in the same water activity range, the temperature-dependent rate constant enhancing factor (Q₁₀) decreased from 3.3 to 1.6.     

Characterisation and tissue distribution of polyphenol oxidase of deepwater pink shrimp (Parapenaeus longirostris)

Characterisation and tissue distribution of polyphenol oxidase (PPO) was studied in deepwater pink shrimp (Parapenaeus longirostris) post mortem. PPO activity was the highest in the carapace, followed by that in the abdomen exoskeleton, cephalotorax, pleopods and telson. No PPO activity was found in the abdomen muscle and in the pereopods and maxillipeds using the enzymatic assay. Storage of whole shrimps and of the different organs showed that melanosis (blackening) required the presence of the cephalotorax to be initiated, indicating that its development depends on other factors in addition to the PPO levels. Further characterisation was carried out in extracts partly purified using 40–70% ammonium sulfate fractionation. The enzyme had the highest activity at pH 4.5 and was most stable at pH 4.5 and 9.0. No clear maximum was observed in the 15–60 °C range but the higher stability was achieved at 30–35 °C. Apparent kinetic constants in the partly purified PPO from carapace were K_M = 1.85 mM and V_max = 38.5 U/mg of protein, pointing to a high affinity and reactivity of the enzyme when assayed with DOPA. Electrophoretic mobility was studied in native PAGE and non-reducing SDS–PAGE followed by staining with DOPA. Approximate MW of 500 kDa and 200 kDa were observed, respectively. These two forms could correspond to aggregates of minor PPO subunits that could not be resolved in these electrophoretic systems. The peptide mass fingerprinting obtained by MALDI-TOF analysis showed some peptides whose homology with hemocyanins and different PPO subunit precursors has already been demonstrated in the same species.     

High-pressure destruction kinetics of Clostridium sporogenes ATCC 11437 spores in milk at elevated quasi-isothermal conditions

The high-pressure sterilization establishment requires data on isobaric and isothermal destruction kinetics of baro-resistant pathogenic and spoilage bacterial spores. In this study, Clostridium sporogenes 11437 spores (10⁷ CFU/ml) inoculated in milk were subjected to different pressure, temperature and time (P, T, t) combination treatments (700–900 MPa; 80–100 °C; 0–32 min). An insulated chamber was used to enclose the test samples during the treatment for maintaining isobaric and quasi-isothermal processing conditions. Decimal reduction times (D values) and pressure and temperature sensitivity parameters, Z_T (pressure constant) and Z_P (temperature constant) were evaluated using a 3 × 3 full factorial experimental design. HP treatments generally demonstrated a minor pressure pulse effect (PE) (no holding time) and the pressure hold time effect was well described by the first order model (R² > 0.90). Higher pressures and higher temperatures resulted in a higher destruction rate and a higher microbial count reduction. At 900 MPa, the temperature corrected D values were 9.1, 3.8, 0.73 min at 80, 90, 100 °C, respectively. The thermal treatment at 0.1 MPa resulted in D values 833, 65.8, 26.3, 6.0 min at 80, 90, 95, 100 °C respectively. By comparison, HP processing resulted in a strong enhancement of spore destruction at all temperatures. Temperature corrected Z_T values were 16.5, 16.9, 18.2 °C at 700, 800, 900 MPa, respectively, which were higher than the thermal z value 9.6 °C. Hence, the spores had lower temperature sensitivity at elevated pressures. Similarly, corrected Z_P values were 714, 588, 1250 MPa at 80, 90, 100 °C, respectively, which illustrated lower pressure sensitivity at higher temperatures. By general comparison, it was concluded that within the range operating conditions employed, the spores were relatively more sensitive to temperature than to pressure.     

Quantitative analysis of phenolic compounds in Chinese hawthorn (Crataegus spp.) fruits by high performance liquid chromatography–electrospray ionisation mass spectrometry

Eleven major phenolic compounds (hyperoside, isoquercitrin, chlorogenic acid, ideain, epicatechin, two procyanidin (PA) dimers, three PA trimers and a PA dimer-hexoside) were quantified in the fruits of 22 cultivars/origins of three species of the Chinese hawthorn (Crataegus spp.) by HPLC–ESI-MS-SIR. Hyperoside (0.1–0.8 mg/g dry mass [DM]), isoquercitrin (0.1–0.3 mg/g DM), chlorogenic acid (0.2–1.6 mg/g DM), epicatechin (0.9–11.7 mg/g DM), PA B2 (0.7–12.4 mg/g DM), PA dimer II (0.1–1.5 mg/g DM), PA trimer I (0.1–2.7 mg/g DM), PA trimer II (0.7–6.9 mg/g DM), PA trimer III (0.01–1.2 mg/g DM) and a PA dimer-hexoside (trace–1.1 mg/g DM) were detected in all the samples. Ideain (0.0–0.7 mg/g DM) was found in all the samples except Crataegus scabrifolia. Significant correlations between the contents of individual PA aglycons were observed (r > 0.9, P < 0.01). A strong correlation between flavonols was also shown (r = 0.71, P < 0.01). Fruits of Crataegus pinnatifida var. major had higher contents of PAs but lower contents of flavonols compared with Crataegus brettschneideri. The fruits of C. scabrifolia contained the highest level of PA dimer-hexoside, which was present in trace amounts in the fruits of C. pinnatifida.     

Kinetics of the formation of radicals in meat during high pressure processing

The kinetics of the formation of radicals in meat by high pressure processing (HPP) has been described for the first time. A threshold for the radicals to form at 400 MPa at 25 °C and at 500 MPa at 5 °C has been found. Above this threshold, an increased formation of radicals was observed with increasing pressure (400–800 MPa), temperature (5–40 °C) and time (0–60 min). The volume of activation (ΔV^#) was found to have the value −17 ml mol⁻¹. The energy of activation (E_a) was calculated to be 25–29 kJ mol⁻¹ within the pressure range (500–800 MPa) indicating high independence on the temperature at high pressures whereas the reaction was strongly dependent at atmospheric pressure (E_a = 181 kJ mol⁻¹). According to the effect of the processing conditions on the reaction rate, three groups of increasing order of radical formation were established: (1) 55 °C at 0.1 MPa, (2) 500 and 600 MPa at 25 °C and 65 °C at 0.1 MPa, and (3) 700 MPa at 25 °C and 75 °C at 0.1 MPa. The implication of the formation of radicals as initiators of lipid oxidation under HPP is discussed.     

Detection of ethanol in food: A new biosensor based on bacteria

A microbial biosensor for determination of ethanol has been developed. The microbial ethanol biosensor comprises a Methylobacterium organophilium-immobilized eggshell membrane and an oxygen (O₂) electrode. The microbial biosensor responds linearly to ethanol in the range 0.050–7.5 mM with a detection limit of 0.025 mM (S/N = 3) and the response time is 100 s. The optimal loading of bacterial cells on the biosensor membrane is 40 mg (wet weight). The optimal working conditions for the microbial biosensor are pH 7.0 phosphate buffer (50 mM) at 20–25 °C. The interference test, operational and storage stability of the biosensor are studied in detail. Finally, the biosensor is applied to determine the ethanol contents in various alcohol samples and the results are comparable to that obtained by a gas chromatographic method. Our work demonstrates that the proposed microbial biosensor is a reliable method to determine the ethanol content in wine samples.     

A spectroscopic and chemometric study of virgin olive oils subjected to thermal stress

The paper describes a study of thermal stress of three different samples of virgin olive oil in terms of oxidative stability. Fatty acid composition, evaluation of oxidative stability under forced conditions (OSI), determination of UV-spectrophotometric oxidation indexes (k₂₃₂ and k₂₇₀) and spectral properties were explored along the thermal treatment. The samples were subjected to heating treatment at 180 °C and evaluated after 0, 30, 60, 90, 120, 150 and 180 min. Middle infrared (MIR) and visible–near infrared (Vis–NIR) spectra were elaborated by partial least squares modelling to individualise regions and bands where critical variations were present. Two bands were found as principal influential ones (1245–1180 cm⁻¹ and 1150–1030 cm⁻¹) on MIR while one primary region was identified on Vis–NIR (2200–1325 cm⁻¹).