Research & Reviews: Journal of Food and Dairy Technology
MenuISSN: 2321-6204
ISSN: 2321-6204
+1-845-458-68821Cátedra de Química General, Facultad de Bioquímica, Química y Farmacia, Universidad Nacional de Tucumán, Ayacucho 471, 4000, San Miguel de Tucumán. Tucumán, Argentina
2Cátedra de Fisicoquímica I, Instituto de Química Física, Facultad de Bioquímica, Química y Farmacia, Universidad Nacional de Tucumán, San Lorenzo 456, T4000CAN, S. M. de Tucumán, Argentina
Received date: 28/08/2015 Accepted date: 08/09/2015 Published date: 15/09/2015
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In this work, the physicochemical properties and the infrared spectra of three different natural orange juices derived from the sour orange (Citrus aurantium), the common orange (Citrus bigardia Riss) and the sweet orange (Citrus sinensis) varieties, named A, C, and D respectively were studied at room temperature with the storage days during the 92 days. The physicochemical properties studied were the pH, refractive index, density, conductivity and the quantity of total soluble solids expressed as degree Brix. The natural A and C juices show a great quantity of bands attributed principally to the ascorbic and citric acid while the natural D juice evidence a higher content of bands associated with sucrose. The assignments of the bands observed in the infrared spectra of the natural A, C and D varieties in the 4000-400 cm-1 region was proposed. From the three natural studied juices, the D juice is the most instable with the time, as evidenced by the Infrared (IR) spectra and the physicochemical properties.
Natural orange juices, Density, Refractive index, Soluble solids, Infrared spectrum
The orange juices are of great importance in nutrition because they are sources of nutrients, such as vitamins C, B6, B9, proteins and minerals calcium, potassium and Mg, among other [1-3]. For this reason, the quality of these beverages should be permanently controlled and directed toward the safety and human health protection since the adulteration represents a serious problem actual [4,5]. From recent times, the Fourier Transform Infrared (FT-IR) spectroscopy is a rapid technique used to control falsifications in the final products [6-11] and, also as an alternative for the classification of orange varieties, as reported by Suphamitmongkol [12]. In this work, we have considered only the references of some recent papers taking into account the great diversity of related studies [1-12]. Industrially, the acid content in a natural juice is one of the important quality attributes in the orange fruit, being the ascorbic and citric acids the main organic acid components [2,13,14]. On the other hand, from the four varieties of oranges known, the bitter (sour) orange (Citrus aurantium), the sweet orange (Citrus sinensis), and the common orange (Citrus bigardia Riss), the most important for juice production is the sweet orange in its four varieties, namely the common orange, the acidless orange, the pigmented orange, and the navel orange [2]. Industrially, there is a significant difference between the commercial and natural orange juices because the pasteurization process in the commercial juices is very important for food safety and quality requirement previous to packaging and distribution while a fresh juice is highly susceptible to contamination and, for this reason, it should be consumed quickly [3]. The recent spectroscopic studies [15-20] reported for the ascorbic and citric acids and sucrose have permitted their vibrational assignments and their quick identifications by using Fourier Transform Infrared (FT-IR) and Raman spectroscopies. Consequently, the constituents of major proportion in an orange juice can be easily identified by using IR spectroscopy. Thus, recent studies on model orange juices combining the Fourier Transform Infrared (FT-IR) spectra with physicochemical properties at room temperature with the storage time were reported by Bichara [21]. Hence, these authors have performed the assignments of the bands observed in the spectra of aqueous solutions of sucrose containing ascorbic (AA) and citric acids (CA) in different concentrations together with the study of their physicochemical properties [21]. These results are very important taking into account that the mixtures simulate diluted model orange juices. So far, for a fresh orange juice there are no experimental Infrared (IR) studies related to their main components in the 4000-400 cm-1 region combined with studies on their physicochemical properties during a storage time of 92 days. The changes performed in the Infrared (IR) spectra and in the physicochemical properties of the three natural juices with the storage days are of importance for known the stability of the different natural juices in relation to the diverse orange varieties and to the identification of its main components taking into account that they are the fruit juices of high consumption in many countries. Moreover, to know the profile of the infrared spectra of natural juices during the storage time is of importance to detect adulteration in these juices. For these reasons, the goal of this work is the characterization of three natural orange juices derived from the sour orange (Citrus aurantium), the common orange (Citrus bigardia Riss) and the sweet orange (Citrus sinensis) varieties by using Fourier Transform Infrared (FTIR) spectroscopy and some physicochemical properties simultaneously at room temperature in order to observe the modifications performed by the storage time during the 92 days. Then, the results for the three natural juices are compared with results obtained for model juices of different concentrations [21]. Here, the pH, refractive index, density, conductivity and the quantity of total soluble solids expressed as degree Brix are the physicochemical properties evaluated at room temperature.
Natural Orange Juices
Three natural orange juices were prepared from fresh oranges obtained from different cultivars of San Miguel de Tucumán (Argentine) and of the sour orange (Citrus aurantium), the common orange (Citrus bigardia Riss) and the sweet orange (C. sinensis) varieties, named A, C, and D respectively. The compositions of these varieties of juices expressed as total solids, total sugars, acidity, and pectin contents of oranges were taken [3] and they can be seen in Table S1 while in Table 1 are presented the composition for a sweet orange juice according to Sandhu [3]. Here, these juices were used after of their manual extraction and, then their Fourier Transform Infrared (FTIR) spectra and physicochemical properties at room temperature were studied with the storage time during the 92 days. In all this study the juices were maintained free of the light and the heat.
| Valor nutricional por cada 100 g (citrus sinensis) | |||
|---|---|---|---|
| Energía 50 Kcal. 200 kJ | |||
| Carbohidratos | 11.57 g | Vitamina B6 | 0.060 mg (5%) |
| Azúcares | 9.35 g | Ácido fólico (Vit. B9) | 30 µg (8%) |
| Fibra alimentaria | 2.4 g | Vitamina B12 | 0 µg (0%) |
| Grasas | 0.12 g | Vitamina C | 53.2 mg (89%) |
| saturadas | 0.015 g | Vitamina D | 0 µg (0%) |
| monoinsaturadas | 0.023 g | Vitamina E | 0.18 mg (1%) |
| poliinsaturadas | 0.025 g | Vitamina K | 0 µg (0%) |
| Proteínas | 0.94 g | Calcio | 40 mg (4%) |
| Agua | 86.75 g | Hierro | 0.10 mg (1%) |
| Vitamina A | 11 µg (1%) | Magnesio | 10 mg (3%) |
| β-caroteno | 71 µg (1%) | Manganeso | 0.025 mg (1%) |
| Tiamina (Vit. B1) | 0.087 mg (7%) | Fósforo | 14 mg (2%) |
| Riboflavina (Vit. B2) | 0.040 mg (3%) | Potasio | 181 mg (4%) |
| Niacina (Vit. B3) | 0.282 mg (2%) | Sodio | 0 mg (0%) |
| Ácido pantoténico (B5) | 0.250 mg (5%) | Zinc | 0.67 mg (7%) |
Table 1. Composition of a sweet orange juice (Citrus sinensis) [3].
| Natural orange juices | ||||
|---|---|---|---|---|
| Variety | Total Solids, % | Total Sugars, % | Acidityc | Pectin, %d |
| C Orange (bitter) | ||||
| Edible portion | 13.59 | 5.49 | 3.30 | 0.86 |
| Peel and pith | 27.27 | 5.86 | 0.46 | 0.89 |
| Juice | 10.72 | 5.74 | 3.77 | |
| D Orange (sweet) | ||||
| Edible portion | 12.98 | 7.88 | 0.79 | 0.59 |
| Peel and pith | 25.52 | 6.81 | 0.27 | |
| Juice | 11.09 | 8.47 | 1.17 | 0.13 |
a: [3]
bMoney and Christian.
cAcidity No. cc 0.1N Per 100 g
dPectin, % as Calcium Pectate
Table S1. Total Solids, Total Sugars, Acidity, and Pectin Contents of Orangesa,b.
Physicochemical Properties
The equipments used in the determinations of pH, refractive index, density, conductivity and the quantity of total soluble solids expressed as degree Brix for the three natural orange juices at 25 ºC were reported in an above paper [21].
Infrared Spectra
The infrared (IR) spectra of the natural orange juices were recorded between Silver Chloride (AgCl) windows from 4000 to 400 cm-1. FTIR GX1 Perkin Elmer spectrometer, equipped with Raman accessory and a Deuterated Triglycerine Sulfate (DTGS) detector cooled at liquid nitrogen temperature was used for all measurements. All spectra were recorded with a resolution of 1 cm-1 and 60 scans.
Physicochemical Properties
Densities (d): Table 2 summarizes the studied physicochemical properties for the three natural orange juices at 25 ºC with the storage time while Figure 1 show the density variations with the time for the three juices. The comparisons with commercial orange juices and with model orange juices are shown in Figure S1 (Supporting information). Note that the graphics for the A, C and D juices show clearly different behaviors on the densities in function of the time. Thus, it is important to observe for D a similar variation with the time than the commercial juices, it is a decrease quick in the density values from the first up to the 7 days. Later, an increase immediate in the density up to a maximum value in the 15 days continued with a decrease up to the 92 days is observed. On the contrary, the densities of the A and C juices increase slightly up to the 7 days, being higher the variation of C than A while the values decrease fast for C up to the 15 days but in lower proportion than A. When these variations are compared with those graphics studied for the commercial and model juices by Bichara [21], as observed in Figure S1a, we observed that: (i) the density of the D juice have a similar behaviour with the time than the commercial C2 juice up to the 30 days changing drastically the values up to the 92 days in similar form than B1, (ii) the density values for the A juice present a behavior similar to the model juices being more quick the variation from the 30 days than the other ones and, (iii) the sweet oranges C and D evidence different behaviour of the density with the storage time. The commercial C2 juice is constituted by higher quantity of orange juices, has a higher proportion of ascorbic acid and, besides no present conserving agent while, the natural D juice has an acidity lower but a higher content of total sugars. Probably, the difference between the natural D and the commercial C2 juice from the 30 days is justified in part by the presence of other components, such as proteins and vitamins. On the other hand, in the components of the model juices, these are ascorbic acid, citric acid and sucrose, sucrose have (Figure S1b) a higher proportion (2.5% of ascorbic acid, 2.5% of citric acid, 10% of sucrose and 85% of water) where the solution 1 is the more concentrated. A very important observation is that the behaviour of the density in A (sour orange) is similar to the model juice which has the highest proportion of sucrose while the behaviour of D is similar to a commercial juice. Thus, perhaps the similitude for these juices justifies the variations observed in the densities with the storage time because the density is a property depends on the volume.
| A | |||||
|---|---|---|---|---|---|
| T (days) | d (g/cm3) | pH | k(mS/cm) | n 25°C | ºBrix |
| 0 | 1.03640 | 3.97 | 2.410 | 1.3462 | 9.0 |
| 7 | 1.03670 | 4.15 | 2.410 | 1.3464 | 9.1 |
| 14 | 1.04690 | 4.11 | 2.650 | 1.3462 | 9.0 |
| 31 | 1.03020 | 4.06 | 3.230 | 1.3450 | 8.2 |
| 92 | 0.99870 | 4.12 | 3.150 | 1.3430 | 6.8 |
| B1 | |||||
| 0 | 1.04270 | 3.24 | 1.832 | 1.3480 | 10.0 |
| 7 | 1.04455 | 3.45 | 1.910 | 1.3480 | 10.2 |
| 14 | 1.05330 | 3.49 | 2.000 | 1.3484 | 10.3 |
| 31 | 1.02360 | 3.55 | 2.140 | 1.3432 | 7.0 |
| 92 | 1.00050 | 3.67 | 1.950 | 1.3386 | 3.8 |
| B2 | |||||
| 0 | 1.02050 | 3.21 | 1.976 | 1.3460 | 5.1 |
| 7 | 1.02249 | 3.14 | 1.990 | 1.3406 | 5.3 |
| 14 | 1.03450 | 3.45 | 2.200 | 1.3406 | 5.3 |
| 31 | 1.01670 | 3.49 | 2.240 | 1.3384 | 3.7 |
| 92 | 1.00980 | 3.86 | 2.060 | 1.3364 | 2.4 |
| C1 | |||||
| 0 | 1.05320 | 3.61 | 2.240 | 1.3520 | 12.6 |
| 7 | 1.05455 | 3.79 | 2.410 | 1.3522 | 12.8 |
| 14 | 1.06960 | 3.81 | 2.650 | 1.3518 | 12.5 |
| 31 | 1.04100 | 3.86 | 2.520 | 1.3494 | 11.0 |
| 92 | 1.00310 | 4.14 | 2.700 | 1.3412 | 5.6 |
| C2 | |||||
| 0 | 1.04580 | 3.32 | 2.60 | 1.3486 | 10.5 |
| 7 | 1.04205 | 3.59 | 2.74 | 1.3492 | 10.8 |
| 14 | 1.06690 | 3.61 | 2.31 | 1.3486 | 10.5 |
| 31 | 1.02820 | 3.67 | 3.02 | 1.3450 | 8.2 |
| 92 | 1.02672 | 3.84 | 2.81 | 1.3450 | 8.2 |
Table 2. Physicochemical properties of commercial orange juices with the storage time.
Figure 1: Variation of density against time, for the natural A, C and D juices at 25 °C.
Figure S1. Variation of density against time, for (a) the commercial A, B1, B2, C1 and C2 juices and, (b) model 1, 2, 3 and 4 juices at 25 °C [21,22].
Conductivities (k): Figure 2 shows the conductivity values for the three studied natural juices at 25ºC against at the storage time during the 92 days. There are differences notable in the values during the studied time, thus, in the first 15 days the conductivity values increase for D while for A and C decrease in the first 7 days and later increase up to the 15 days. For A and D, after the 15 days and up to the 92 days the conductivities of both juices decrease with the time while only for C an increase in the values is observed between 15 and 92 days, as showed in Figure 2. When these natural juices are compared with the conductivity values corresponding to the commercial and model juices, studied [21] and presented in Figures S2a and S2b, the behaviors show similitude and differences among them. Hence, in the first 15 days the variations for A and C are similar to the commercial B2 juice; it is the values decrease to the 7 days and then increase up to the 15 days. For D, the behaviour of the conductivity is similar to the remains commercial juices up to the 30 days and, then, the values decrease for A and D up to the 92 days. The increase in the conductivity values could be related in part to the presence of H+, OH-, ascorbate and citrate ions in the medium and to the A2- species derived from the ascorbic acid decomposition, in similar form to the more diluted model juice, because in aqueous medium the decomposition process is accelerated. Whereas, the decrease in the conductivity could be justified by the presence of the A and A2 species derived from the decomposition of the ascorbic acid and, also to the di-hydrate and penta-hydrate sucrose formation, as reported by Max and Chapados [22]. Here, the similitude between A, C and the commercial B2 juice are attributed to a higher quantity of ascorbic acid while the D juice has a higher quantity of soluble solid, as indicated in Tables 1 and 2. This way, the formation of H bonds and sugar in aqueous solution justifies the presence of higher neutral species that diminishing the conductivity.
Figure 2. Variation of conductivity against time, for the natural A, C and D juices at 25 °C.
Figure S2. Variation of conductivity against concentration, for (a) the commercial A, B1, B2, C1 and C2 juices and, (b) model 1, 2, 3 and 4 juices at 25 °C [21,22].
Values pH: Figure 3 shows the pH variations for the natural juices at 25ºC versus the storage time during 92 days while the values obtained for the three juices can be observed in Table 2. Initially, the natural A and C juices present similar behaviors with the time up to the 30 days and, later, the values for A increase with the time but remain practically constant for C. As it is expected and as observed in Table 1, the C juice product of an orange bitter has lower pH values and, for this, it has the higher acidity than A and D in spite the value of the acidity expressed as 0.1N per 100 g is 3.77 different from D whose values is 1.17, as observed in Table S1. On the contrary, the variation of the pH with the storage time for D is different from A and C up to the 15 days and, then the values increase from the 15 to 92 days showing a medium acidity between A and C. When these natural juices are compared with the commercial juices we observed in the A and C juices behaviours similar to the commercial A, B1, C1 and C2 juices up to the 30 days and, later, the values increase strongly for A but remain practically constant for C (Figure S3a). While the behaviour of the pH values of D in the first 15 days is similar to the commercial B2 juice. On the other hand, when the natural juices are compared with the model juices the variation of the pH with the storage time for D are similar to the more concentrated solutions 1, 2 and 3 (Figure S3b). Possibly, this decrease in the pH values during the first 15 days are associated with a higher acid concentration, as in the model juices cases. The presence of other components in the natural juices could be justifying the low acidity of these juices than the model ones. Figure S3a show clearly the decrease in the pH values with the storage time for B2. Probably, the presence of the ascorbic acid, citric acid and sucrose support the variations in the pH values for B2 and the juices model. These results justify the increase in the conductivity in the aqueous medium and the decreasing in the pH values due to the acid species. These results agree with those obtained by means of conductivity values.
Figure 3. Variation of pH against time, for the natural A, C and D juices at 25 °C.
Figure S3. Variation of pH against concentration, for (a) the commercial A, B1, B2, C1 and C2 juices and, (b) model 1, 2, 3 and 4 juices at 25 °C [ 21,22].
Refractive index (n): The graphics of the refractive index for the natural A, C and D juices against to the storage time during 92 days at 25ºC are presented in Figure 4 while the comparisons with commercial and model juices can be observed in Figure S4. First, the behaviour of n versus the time are different in the three juices, presenting the more important modifications the C juice. Thus, for this juice n decreases significantly with the time from the first up to the 15 days and then the values increase until the 30 days and, from here diminish newly the values up to the 92 days. The A and D juices, both products of sweet oranges, present minima to the 7 days while both present maxima in different times, A has a maximum approximately at the 20 days while D to the 15 days. The results show clear differences in the compositions of both juices. This way, when the three juices are compared with the commercial and model juices, presented in Figure S4, A and D show behaviours similar to the commercial juices while for C, the variation of n with the time is similar to the commercial B2 and to the most diluted solution of the model juices. Probably the low quantity of soluble solids in the commercial B2 justifies such variations because the solution 4, which is the most diluted solution of the model juices, shows drastically lower proportion of ascorbic acid, citric acid and sucrose during the storage time than solution 1, 2 and 3. Thus, C is the natural juice with lower values of n while A show strong decreasing of n with the time.
Figure 4. Variation of refractive indexes against time, for the natural A, C and D juices at 25 °C.
Figure S4. Variation of refractive index against concentration, for (a) the commercial A, B1, B2, C1 and C2 juices and, (b) model 1, 2, 3 and 4 juices at 25 °C [21,22].
Quantity of soluble solid (ºBrix): In this work, the quantity of total soluble solids for the three natural juices was expressed as degree Brix and studied at 25ºC against at storage time during 92 days, as can be seen in Figure 5. On the other hand, the graphics for the natural juices were compared with those corresponding to different commercial and model oranges juices (Figure S5). Note that the behaviours of the soluble solids for the three juices are similar to the variations of n by the time, given in Figure 4, a result different from those obtained for the commercial juices (Figure S5a). A very important result for the D juice is observed in the ºBrix values due to that it has a higher quantity of soluble solid than A and C, as decrypted in Table S1. Probably, the low quantity of soluble solids in C can be justified in part by the ascorbic acid decomposition because it juice has low pH values and, for this, lower acidity than A and D. Moreover, these latter juices have behaviours similar than the commercial juices showing A and D decrease quick of the soluble solid with the time, being it more notable in A. Thus, the three juices after about 30 days show different slopes, as observed in Figure 5.
Figure 5. Variation of the soluble solids (°Brix) against time, for the natural A, C and D juices at 25 °C [21,22].
Figure S5. Variation of soluble solids (°Brix) against concentration, for (a) the commercial A, B1, B2, C1 and C2 juices and, (b) model 1, 2, 3 and 4 juices at 25 °C [21,22].
Infrared Spectra: Figure 6 shows the variations of the IR spectra of the natural A, C and D juices recorded on the first day compared with the corresponding to the mixture of ascorbic and citric acids and sucrose (model juice) in solid phase while from Figures 7-9 show the variations of each spectrum with the storage time. The observed wavenumbers and the assignments for the natural orange juices studied compared with the bands observed in the more concentrated juice model can be seen in Table 3. Figure S6 shows clearly the differences among the spectra for the A, C and D natural juices, in the form, positions and intensities of the bands observed while in the Figures S7-S9 it is possible to observe the comparisons with the Infrared (IR) spectra for ascorbic acid, citric acid and sucrose. Note that Figure S7 shows for the A juice a higher proportion of the ascorbic and citric acids than C and D while a high content of sucrose is expected in the D juice, as can be seen in Figure S9, and as expected because it juice is of sweet orange.
| A (sour orange) | |||||
|---|---|---|---|---|---|
| T (days) | d (g/cm3) | pH | n 25°C | ºBrix | k (mS/cm) |
| 0 | 1.0374 | 3.84 | 1.3462 | 9.60 | 4.42 |
| 7 | 1.0391 | 4.24 | 1.3448 | 8.00 | 4.25 |
| 14 | 1.0365 | 4.38 | 1.3448 | 8.00 | 5.35 |
| 31 | 1.0326 | 4.34 | 1.3444 | 7.80 | 5.13 |
| 92 | 1.0090 | 5.64 | 1.3380 | 3.50 | 4.91 |
| C (common orange) | |||||
| 0 | 1.0383 | 2.92 | 1.3458 | 8.50 | 5.1 |
| 7 | 1.0405 | 3.20 | 1.3452 | 8.30 | 4.91 |
| 14 | 1.0179 | 3.32 | 1.3400 | 4.58 | 5.47 |
| 31 | 1.0153 | 3.40 | 1.3408 | 5.30 | 5.55 |
| 92 | 1.0085 | 3.46 | 1.3390 | 4.00 | 6.1 |
| D (sweet orange) | |||||
| 0 | 1.0421 | 6.13 | 1.3492 | 11.00 | 4.75 |
| 7 | 1.0289 | 4.38 | 1.3484 | 10.50 | 5.06 |
| 14 | 1.0516 | 4.23 | 1.3482 | 10.30 | 5.64 |
| 31 | 1.0186 | 4.23 | 1.3462 | 8.90 | 5.55 |
| 92 | 1.0008 | 4.86 | 1.3418 | 6.00 | 5.14 |
Table 3. Physicochemical properties of natural orange juices with the storage time.
Figure 6. Comparisons of the Infrared spectra of the model juice in solid phase with those corresponding to the natural A, C and D juices at 25 °C.
Figure S6. Infrared spectra of the natural A juice 1 at the first day (upper), for C (medium), and for D (bottom).
Figure 7. Comparisons of the Infrared spectra of the natural A with the storage time at 25 °C.
Figure S7. Infrared spectrum for the natural A compared with the corresponding to ascorbic acid, citric acid and sucrose.
Figure 8. Comparisons of the Infrared spectra of the natural C with the storage time at 25 °C.
Figure S8. Infrared spectrum for the natural C compared with the corresponding to ascorbic acid, citric acid and sucrose.
Figure 9. Comparisons of the Infrared spectra of the natural D with the storage time at 25 °C.
Figure S9. Infrared spectrum for the natural D compared with the corresponding to ascorbic acid, citric acid and sucrose.
Natural Orange A Juices: The Infrared (IR) spectra for this juice recorded each week from the first day can be seen in Figure 7. It is important to note the different variations that experiment this juice with the storage days especially during the 7 and 31 days, as observed in the physicochemical studies. The numbers of bands increase notably in this two week as a consequence of the decomposition products of ascorbic and citric acids and for this reason, increase the density and the pH in both times while decrease the conductivity. The broad Infrared (IR) bands at 3402 and 1654 cm-1 are strongly related with the presence of those two acids, as shown in Figure S7. The first band is assigned to the expected OH stretching modes of both acids while the band at 1654 cm-1 is assigned simultaneously to the C=O stretching mode of the ascorbic acid and to the OH deformation modes corresponding to the water molecules [17,18,20].
Natural Orange C Juice: Table 4 shows that the positions of the bands associated with the OH stretching and deformation modes for this juice are located at 3416 and 1650 cm-1, respectively. In Figure S8 can be seen the higher presence of acids in C and, for this juice, as for A, the more important variations are also observed at the 7 and 31 days, as shown in the different spectra of Figure 8. The probable formed species are those derived from of ascorbic acid which are the un-oxidized H2A, the HA- and A2- anions, the oxidized A and dimeric A2 forms, in accordance with reported data [17,18,20]. The increasing of the density and in the pH values and the decreasing in the conductivity, n and ºBrix values the 7 days justified the modifications in the bands observed in the IR spectrum fro this juice.
| Ascorbic acid (H2A)a | Citric acidb | Sucrosec | Mixtured | Natural orange juicese | ||||||
|---|---|---|---|---|---|---|---|---|---|---|
| IR,Raman | Assignment | IR,Raman | Assignment | IR,Raman | Assignmentc | IR Solid | IR Solut | A | C | D |
| 3523s | nO-H (H2A), HA-, A2-, A) | 3535 | n O-H | 3564 m | n(O-H)w | 3565 | 3538 vs,br | 3642 | ||
| 3498 | n O-H | 3469 sh | n O-H | 3525 | ||||||
| 3409 vs | nO-H (H2A), HA-, A) | 3394 s | n O-H | 3412 | 3402 | 3416 | 3392 | |||
| 3316 s | nO-H (H2A), HA-) | 3350 | n O-H | 3337 s | n O-H | 3389 | 3302 vs.br | |||
| 3247 | n O-H | 3257 sh | n O-H | 3322 | ||||||
| 3217 m | nO-H (H2A)) | 3132 m | naCH2 | 3226 | 3087 vs,br | 3249 | 3266 | |||
| 3030 s | nO-H (H2A)) | 3035 | naCH2 op | 3052 sh | nC-H | 3034 | 3044 | |||
| 3002 m | naCH2 (H2A)), nC-H (A) | 2994 | naCH2 op | 2993 w | naCH2 | 2997 | ||||
| 2978 m | na CH2 (H2A)) | 2975 | naCH2 ip | 2970 w | naCH2 | 2971 | ||||
| 2960 w | na CH2 (A2-, A) | 2961 w | nsCH2 op | 2958 sh | nC-H | 2958 | ||||
| 2944 m | nC-H (H2A)), na CH2 (HA-) | 2933 w | nO-H | 2943 m | nsCH2 | 2944 | 2945 sh | 2940 | ||
| 2916 m | nC-H (H2A), HA-), ns CH2 (H2A)) | 2916 m | nC-H | 2915 | ||||||
| 2903 vs | nC-H (H2A), HA-), ns CH2 (H2A), A2-, A) | 2902 m | nsCH2 | 2984 sh | 2894 | |||||
| 2854 w | nO-H(H2A)),nsCH2(HA-)nC-H(H2A),HA-,A2-,A) | 2849 sh | 2859 | |||||||
| 2737 w | nC-H (A2-) | 2763 sh | ||||||||
| 2641 sh | nO-H (A2-) | 2650 sh | ||||||||
| 1753 m | n C=O (H2A), HA-, A2-, A) | 1756 vs | nsC=O1 | 1733 w | dH2O | 1757 | ||||
| 1708 vs | naC=O3 | 1714 w | dH2O | 1709 | ||||||
| 1672 s | n C=C (H2A)), dCOH (A2-), | 1662 vw | dH2O | 1674 | 1677 vs | |||||
| 1667 vs | n C=C (HA-),n C=O (A), d CH2 dim(H2A)) | 1698 sh | nsC=O3 | 1648 s | dH2O | 1654 | 1645 | 1650 | ||
| 1538 vw | n(C-C) | 1546 | 1573 | |||||||
| 1525 vw | dCH2 | |||||||||
| 1517 vw | dCH2 | |||||||||
| 1495b m | nC-Cdim (H2A)),wagCH2 (HA-), d CH2(H2A), A) | 1493 vs | dsCOH | 1496 vw | wagCH2 | 1502 | 1503 | |||
| 1459 m | wagCH2 (H2A)), dCH2 (H2A), HA-, A2-) | 1469 w | naC-C2 | 1463 w | rC-H | 1465 | 1455 sh | 1459 | 1460 | 1459 |
| 1438 sh | dCOH(HA-),wagCH2(A),dHOC(H2A)),nC-C(H2A)) | 1430 m | nC-C, dCH2 ip | 1432 w | wagCH2 | 1432 | 1431 | |||
| 1426 w | t(O---H),twH2O(2) | 1428 s | 1422 | 1421 | ||||||
| 1413 sh | t(O---H),twH2O(2) | 1419 | ||||||||
| 1399 sh | rC-H | 1392 | ||||||||
| 1387 w | wag CH2 (H2A)) | 1389 m | daCOH, wagCH2op | 1388 w | d(O-H),r’(C-H) | 1380 | ||||
| 1363 sh | dCOH (HA-), wagCH2 (A2-), dOCH (A) | 1365 w | wag CH2 ip | 1365 m | t(O---H),twH2O(2) | 1366 | 1365 | 1363 | 1368 | |
| 1353 m | dCOH (H2A), HA-, A2-, A), d CCO (H2A)) | 1358 w | rCH2 ip | 1354 sh | rC-H | 1347 w | ||||
| 1344 vw | dCCH(H2A),HA-,A2-),dOCH (A) dCOH(H2A),HA-) | 1340 sh | ds COH | 1348 m | rC-H | 1343 | ||||
| 1321 m | dCOH (H2A)), dCCH (HA-) | 1325 vw | ds COH | 1325 m | rCH2 d(O- H) | 1323 | 1323 sh | |||
| 1302 sh | rCH2 (H2A), HA-), d OCH (A2-)n C-O (H2A)), | 1308 w | wagCH2 ip,daCOH | 1302 w | r’(C-H) | 1306 | 1318 | 1320 | 1315 | |
| tw CC2 (H2A)) | ||||||||||
| 1292 w | rCH2 ip, wagCH2 ip | 1293 w | rC-H | 1292 | ||||||
| 1274 s | dOCH (HA-,A2-,A),rCH2 (A), wagCH2 (HA-), | 1271 w | dO-H | 1276 | 1265 sh | 1275 | 1280 | |||
| dCOH(H2A)),dCCH(H2A)) | ||||||||||
| 1246 m | dCOH (H2A)), rCH2 dim (H2A)), dOCH (HA-), | 1242 m | nsC-O | 1241 m | dO-H | 1246 | 1253 | 1257 | ||
| rCH2 (A2-, HA-) | ||||||||||
| 1233 m | 1240 | 1242 | 1245 | |||||||
| 1221 w | twCC2 (H2A)), d OCH (A2-),dCOH(A) | 1214 m | rCH2 ip | 1212 w | dO-H | 1227 | ||||
| 1197 w | dCOH (H2A), HA-), n C-C (HA-, A2-), | 1191 vw | dO-H | 1200 | 1192 | 1192 | ||||
| tw CC2 (H2A), A) | ||||||||||
| 1174 s | n C-O | 1172 m | dO-H | 1177 | ||||||
| 1163 m | nC-O | 1152 m | 1162 | |||||||
| 1139 m | twCC2 (HA-, A2-), n C-O (H2A), A), n C-C (H2A)) | 1140 s | nC-O | 1141 m | nC-O | 1140 | 1140 | 1138 | 1139 | |
| 1130 s | nC-O | |||||||||
| 1120 | nC-O (H2A)), d COH (H2A)) | 1126 m | nC-O | 1120 | ||||||
| 1112 s | nC-C (HA-, A),n C-C (A2-) | 1115 m | nC-O | 1112 | 1110 | 1110 | ||||
| 1105 s | nC-O | 1107 w | ||||||||
| 1074b m | nC-O (H2A), HA-, A2-, A) | 1081 w | daCOH | 1074 m | nC-O | 1071 | 1079 sh | 1080 | 1084 | 1078 |
| 1065b m | nC-O (H2A)), n C-C (H2A)), tw CH2 (A2-) | 1069 vs | nC-O | 1070 | ||||||
| 1053 m | nC-C | 1055 s | nC-O | 1054 | 1061 | 1065 | 1060 | |||
| 1046 sh | nC-O (H2A), HA-, A2-, A) | 1042 sh | twH2O(2),t(O---H) | |||||||
| 1036 sh | wagCH2 op,twCH2 op | 1039 s | 1033 | 1034 | 1040 | |||||
| 1026 vs | nC-C (HA-), n C-O (H2A), A) | 1022 w | nC-C | 1028 | ||||||
| 1015 m | twH2O(2),t(O---H) | 1015 | 1013 | 1015 | ||||||
| 1004 m | nC-O | |||||||||
| 990 m | nC-O (HA-, A2-),n C-C (H2A), HA-, A)bC=O (A) | 994 s | nC-O | 991 | 998 sh | 995 | 996 | 999 | ||
| 966 vw | ns C-C2 | 966 sh | nC-O | 945 | 963 | 966 | ||||
| 945 w | ns C-C1 | 946 w | tR1(A6) | 922 | 925 w | 920 | 920 | 928 | ||
| 924 vw | twCH2 (H2A), A) t (OH) (A2-),n C-C (HA-) | 914 sh | twCH2 op | 912 | 908 | |||||
| 904 w | twCH2 op, nC-O | 899 sh | tR1(A5) | 872 | 892 | |||||
| 870 | nC-O (A) | 881 w | twCH2 ip | 885 sh | n(C-O) | 852 | 867 | |||
| 820b m | nC-C (H2A)), twCH2 (HA-, A2-, A), n C-O (HA-) | 842 vw | na C-C1 | 836 s | d(OCC),twCH2,nC1-C5) | 825 | 821 | 829 | ||
| 795 sh | gCOO2 | 799 vs | 806 | |||||||
| 783 vw | gC-C (H2A), HA-) | 785 vw | wagH2O(1) | 774 | 776 | |||||
| 756b s | t(OH)ip dim (H2A)), bC-O (A2-) | 755 sh | bR1(A6) | 759 | ||||||
| 722 m | gC=O dim (H2A)), gC-C (A) | 729 sh | dCOO5 | 722 w | bR2(A6) | 736 | ||||
| 711b vw | gC=O (H2A)), bC-O (HA-) | 714 sh | bR3 (A6) | 713 sh | 714 | |||||
| 697 s | tw CH2 dim(H2A)), bC=O (H2A)), bR1 (A2-), | 700 w | dCOO4 | 701 vw | rH2O | |||||
| n C-C (A), gC=O (HÁ-) | ||||||||||
| 686 w | bC=O (H2A)), n C-C (H2A)) | 686 w | gCOO5 | 686 w | dC-C-C | 686 | 684 | 676 | ||
| 675b m | n C-O (H2A), HA-), t (OH) (HA-) | 666 vw | gCOO3 | 666 sh | dO-C-O | |||||
| 649 | t(OH)op dim(H2A)), gC=O (A2-) | 640 w | t(O-H) | 644 w | rH2O | 643 | 653 | |||
| 628 m | bR1 dim(H2A)), bC=O (A), bR1 (HA-) | 627 vw | t(O-H),dCOO3 | 636 m | rH2O | 632 | ||||
| 591 w | gC-O (HA-), n C-C (A2-)bR1 (H2A), A), | 599 s | t(O-H),dCOO5, | 594 m | bR1(A5) | 600 | 605 | 603 | ||
| bR2(HA-) | dCCC,rCOO5 | |||||||||
| 581 vs | 573 | |||||||||
| 565b m | dOCH(H2A)), gC-O (H2A), A2-),bR2 (H2A), A2-, A), | 571 w | gCOO4 | 570 w | dO-C-O | 573 | 565 | |||
| wagCC2 (A) | ||||||||||
| 541 w | dCOO1 | 548 s | rH2O(1) | 553 | ||||||
| 520 sh | gCOO6 | 537 w | tO-Hw | 520 | ||||||
| 496 w | dCCO(H2A)), wagCC2 (A2-) | 504 w | gCOO1 | 504 m | twH2O | 498 | 498 | |||
| 482 w | tO-H | |||||||||
| 473 w | gC=O (A) | 477 sh | gCOO6 | 474 m | dO-C-C | 474 | 477 w | 473 | ||
| 467 w | wagH2O | |||||||||
| 449 w | rCC2 (H2A)), Wag CC2(H2A), HA-)t(OH) (A) | 438 vvw | rCOO4 | 451 w | twH2O | 434 | 432 | |||
| 412 s | tO-H | 424 | 404 sh | 420 | 418 | 420 | ||||
| 396 w | t(OH) (H2A)), bC-O (HA-, A2-) | 397 w | dCCC | 393 s | tO-H | 406 | 403 | |||
| 378 s | tO-H | |||||||||
| 363 m | t(OH) (H2A)), gC-O (A2-)r CC2 (A2-), bC=O (A) | 367 w | rCOO3, rCOO1 | 368 vs | dC-C-O | |||||
| 357 sh | dC-C-O | |||||||||
| 340b w | gC-O (H2A), HA-), gC=O (A) t (OH) (H2A)), | 348 w | rCOO6 | 342 sh | tO-H | |||||
| bC-O (A2-), d CCO (A) | ||||||||||
| 323 vw | dCCC | 329 w | tO-H | |||||||
| 320 sh | dO-C-C | |||||||||
| 292b w | βC-O(H2A)), dCCO (A2-), bC=O (A), gC-O (HA-) | 306 w | dCCC | 309 vw | tw (O-C) | |||||
| 254 sh | dCCC | 252 sh | d(OCC),r’(C-C) | |||||||
| 238b m | t(OH) dim(H2A)),d CCC (A2-), | 247 vw | dCCC | 241 sh | dO-C-C | |||||
| t (OH) (H2A), HA-, A), β C-O(HA-) | ||||||||||
| 223 m | t(OH) (H2A), HA-), β C-O(H2A)), | 237 vw | dCCC | 235 m | dO-C-C | |||||
| tCC (A2-), d CCC (A) | ||||||||||
| 212 w | dCCC op | 212 vs | dO-C-C | |||||||
| 208 m | dCCC (H2A)), t (O-H) (A2-) | 204 sh | nOH---Ow | |||||||
| 180 w | gC-C dim(H2A)) | 180 vvw | tw2O(2),t(O---H) | |||||||
| 172 vw | nOH---Ow | |||||||||
| 166 vvw | tR1(A5) | |||||||||
| 163 m | tCCCO dim(H2A)) | 160 vw | tO-Hw | |||||||
| 148 m | gC-O(H2A),) d OCH (H2A)), | 140b | ns (O-H--O)# | 153 vvw | tO-Hw | |||||
| 138 m | tR1 (H2A), HA-,A) | 138 vvw | tR3(A6) | |||||||
| 122 w | tR1 (H2A)), tCCCC (HA-) | 129 vvw | nOH---Ow | |||||||
| 113 w | t CCCO (H2A)), tR2 (A2-), d CCC (A) | 105b | na(O-H--O)#,dCCC ip | 114 vvw | OH---Ow | |||||
| 91 m | t CCCO (H2A)), tCCCC (HA-) | 88b | dCCC ip | 90 | twO-C | |||||
| 81 s | tR2 (H2A)) ,tCCCO (A2-), tCCCC (A) | 82 | twO-C | |||||||
| 73 s | tR2 (H2A), tR1 (A2-), tCCCO (A), tw Ring(HA-) | 68b | twCC ip | 70 | tR2 (A5) | |||||
| 43 vw | tw Ring (H2A)), tCCCC (A2-), tR2 (A), tR1 (HA-) | 44b | twCC op | 41 | t(O---H) | |||||
Table 4. Observed wavenumbers (cm-1) and assignments for all the natural orange juices [17,18,20,22].
Natural Orange D Juice: Figure S8 shows the comparisons of the Infrared (IR) spectra for this juice with those corresponding to the ascorbic and citric acids and sucrose while Figure 8 shows the variations observed in the spectra for this juice with the storage time. In particular for this juice notable variations are observed in the positions of the bands, as shown in both Figures. First, in the higher wavenumbers region the position of the band at 3392 cm-1 attributed to the OH stretching modes of the components are in agreement with the strong band observed in the spectrum of sucrose at 3394 cm-1 and the band at 1650 cm-1 associated with the hydrate-sucrose at 1648 cm-1 support the higher presence of sucrose in this natural juice, as expected because this juice is prepared from the sweet orange. Also, in the 1500-400 cm-1 region for this juice are observing a higher presence of bands associated with those corresponding to sucrose. During the studied time it is possible to observe changes significant in all the spectra presented in Figure 9. The permanent changes in the density values, the increase in the conductivity values and the decreasing in the pH, n and ºBrix values justify all the modifications observed in the Infrared (IR) spectra for this juice during the storage time.
In the present work, three natural orange juices derived from the sour orange (Citrus aurantium), the common orange (Citrus bigardia Riss) and the sweet orange (Citrus sinensis) varieties, named A, C and D, respectively, were characterized by using physicochemical properties and Fourier Transform Infrared (FTIR) spectra with the storage time during 92 days. The natural A and C juices show bands attributed to the ascorbic and citric acid and exhibits notable variations in the physicochemical properties especially at the 7 and 30 days supported by the new Infrared (IR) bands during these times while the infrared spectrum of the natural D juice evidence a higher content of sucrose and during all the studied time the infrared spectra show change in the form, positions and intensities of the observed bands. Thus, the changes in the density values, the increase in the conductivity values and the decreasing in the pH, n and ºBrix values reveal the high instability of this juice with the storage time. The significant decreasing in the n and ºBrix values for all the natural juices confirm that the fresh juices are highly susceptible to decomposition and, for this reason, it should be consumed quickly. In this study, we demonstrated that the Fourier Transform Infrared (FTIR) spectroscopy can be easily used for differentiation of natural juices if its technique is used in combination with the determination of their physicochemical properties. The assignments of the bands observed in the infrared spectra of the sour orange (Citrus aurantium), the common orange (Citrus bigardia Riss) and the sweet orange (Citrus sinensis) varieties in the 4000-400 cm-1 region was proposed. In conclusion, from the three natural studied juices, the D juice is the most instable with the time, as evidenced by the Infrared (IR) spectra and the physicochemical properties.
This work was subsidized with grants from CIUNT (Consejo de Investigaciones, Universidad Nacional de Tucumán).