Open Access Article
Tingwei Zhu†
a,
Yali Zhao†a,
Minhua Zonga,
Bing Liab,
Xia Zhangab and
Hong Wu
*ab
aSchool of Food Science and Engineering, South China University of Technology, Guangzhou 510640, China. E-mail: bbhwu@scut.edu.cn; Tel: +86-20-22236669
bGuangdong Province Key Laboratory for Green Processing of Natural Products and Product Safety, Guangzhou 510640, China
First published on 7th July 2017
In order to obtain good quality special fats for fast frozen food, blends of palm stearin (PS) and soybean oil (SO) (5
:
5, 6
:
4 and 7
:
3, PS
:
SO) were subjected to enzymatic interesterification in a fluidized bed reactor. The slip melting point of the interesterified blends thus obtained was 45 °C when the flow rates were 2.24, 1.57 and 0.40 mL min−1, respectively. After interesterification, the contents of SSS- and UUU-type TAGs decreased, whereas the contents of SUU-type TAGs increased. In addition, the β form crystal reduced and β′ form crystal increased due to the change in the type of TAGs. The solid fat content of the interesterified blends was 5–40% at 10–45 °C. The results of sensory evaluation indicated that the special fats prepared from the interesterified blends had better quality when they were applied in the preparation of fast frozen dumplings. Hence, enzymatic interesterification is promising in preparing high-quality special fat for fast frozen food.
Interesterification is one of the most important oil and fat modification technologies, which has received increasing attention in the production of trans-free plastic fats by rearranging the distribution of fatty acids on the glycerol backbone without changing their composition. Compared with chemical interesterification, enzymatic interesterification has numerous advantages such as milder reaction condition, fewer by-products and lesser pollution to the environment.9 The properties of the interesterified blends such as slip melting point, plastic range and crystals would alter after enzymatic reaction, and they can provide desirable properties and smoother mouth feel for food products.10,11 However, little has been known about the relationship between the physicochemical property of special fats and the quality of fast frozen food prepared using these special fats. Ma et al. found that the fast frozen food had quite a good quality and mouth feel when it was prepared using the special fats with a slip melting point of 45 °C; however, they did not further investigate the physicochemical properties and the polymorphs of these special fats.2,12
Palm stearin (PS), a palm oil fraction, cannot be used directly for edible purposes due to its high slip melting point. However, it can be appropriately interesterified with vegetable oils in order to modify its physicochemical characteristics.13 Soybean oil (SO) is a type of widely used edible liquid oil with advantages of low price, high productivity as well as abundant nutrition. Therefore, in this study, the base oil of the special fats for fast frozen food was produced by lipozyme TL IM-catalyzed interesterification of palm stearin (PS) and soybean oil (SO) with different mass ratios (5
:
5, 6
:
4 and 7
:
3, PS
:
SO) in a fluidized bed reactor. The slip melting point of approximately 45 °C was considered as the evaluation index for the interesterified blends. In order to reveal the relationship between the microscopic structure and the macroscopic physical properties of the blends before and after interesterification, the triacylglycerol (TAG) distribution, solid fat content profiles, thermal properties, crystal polymorphisms and crystal microstructure were analyzed. In addition, the interesterified blends were used as base oil to prepare the special fats for fast frozen food. In order to evaluate their qualities, the resulting special fats were applied in the preparation of fast frozen dumplings, the sensory properties of which were further investigated. The interesterified blends with improved physical properties are favorable for the preparation of high-quality special fats for fast frozen food industry.
:
5, 6
:
4, and 7
:
3, PS
:
SO) and control the flow rate. The reaction temperature was set at 60 °C.
The TAGs of the blend were analyzed by reversed-phase high-performance liquid chromatography (HPLC) equipped with an evaporative light scattering detector (ELSD) and a Symmetry C18 column (5 μm, 4.6 × 150 mm). The blend (30 mg) was dissolved in 30 mL chloroform and then filtered using a 0.45 μm membrane filter before determination. The mobile phase was a binary solvent system of acetonitrile (solvent A) and 2-propanol/hexane (5
:
4, by volume) (solvent B) and the flow rate was 1.0 mL min−1. The detector temperature was 70 °C and the injection volume was 3 μL. The individual TAG content was calculated as the percentage of the peak area of individual TAGs relative to the total peak area of the total TAGs in the blend. The identification of TAG species eluted by HPLC is carried out mainly according to its equivalent carbon number (ECN) and the fatty acid composition.
:
5, 6
:
4 and 7
:
3, PS
:
SO) were used as the base oil to prepare special fats for fast frozen food. The specific steps of making special fats are as follows. The oil phase (84%, wt%), the water phase (15%, wt%) and the emulsifier (Span-60
:
trimethylene glycol ester
:
soybean lecithin: 1
:
1
:
8, 1%, wt%) were fully mixed at 60 °C and 2000 rpm for 20 min. The resulting mixtures were kept at 40 °C for 10 min. After that, they were put into a bath (−10 °C) and mixed at 300 rpm for 2 min, and then kept at 25 °C for 48 h.
The special fats prepared from the interesterified blends (5
:
5, 6
:
4 and 7
:
3, PS
:
SO) and the commercial fat were used in the production of fast frozen dumplings. The specific steps of making fast frozen dumplings are as follows. First, the dumpling pellicles were prepared. To obtain soft dough, 450 g flour, 7 g salt, 14 g special fat and 250 g water were placed into a bowl and kneaded until the dough became smooth and slightly elastic. The dough without fat was used as the control. Then, the dough was rolled into a long roll, which was cut into equal pieces. Following this, each piece was pressed to be a circular pellicle (diameter 60 mm, thickness 2 mm). Second, the filling was prepared by mixing 300 g fatty ground pork, 600 g chive and 30 g salt in a bowl and stirring sufficiently. Finally, the dumplings were obtained by placing the same mass weight filling on the central part of the circular pellicle and sealing the edge of the circular pellicle thoroughly to enclose the filling completely. The prepared dumplings were frozen at −30 °C.
The sensory analysis was performed by 20 non-trained panelists who were recruited from the students and staff members of the department. At the same time, the panelists were seated in individual testing areas and given a brief orientation on the testing method. The important sensory attributes selected as appropriate indexes for evaluating the quality of fast frozen dumplings were cracking rate, appearance, boil-resisting ability and mouth feel. The results were recorded using a 5-point scale (1 point indicates very poor (weak), whereas 5 point denotes very well (strong)) for each attribute and the overall acceptability.
All the experiments were carried out in triplicate and the results were presented as the average values with standard deviations.
:
5, 6
:
4 and 7
:
3, PS
:
SO) were catalyzed by lipozyme TL IM in a fluidized bed reactor. When the flow rate was 2.24 mL min−1, the SMP of the interesterified blend of PS
:
SO (5
:
5) was 45 °C. The flow rates were 1.57 and 0.40 mL min−1, to obtain interesterified blends of 6
:
4 and 7
:
3 PS
:
SO, respectively, at 45 °C. The physicochemical properties of the resulting interesterified blends were analyzed, and their application in the preparation of fast frozen food was investigated.
:
5, 6
:
4 and 7
:
3, PS
:
SO) before and after interesterification are given in Table 2. According to the number of unsaturated fatty acids, TAGs were divided into four types, namely SSS, SUS, SUU and UUU (S-saturated fatty acid, U-unsaturated fatty acid). The interesterified blends were mostly composed of TAG species with ECN 44 (LLO and PLL), ECN 46 (LOO, PLO, PPL and PPM), ECN 48 (OOO, SLO, POO, POP/PPO and PPP) and ECN 50 (SOO, POS/PSO and PPS). The content of TAGs with ECN 44 (LLO, PLL) increased with the reduction in PS in the blends. The interesterification caused a decrease in the contents of SSS- and UUU-type TAGs and an increase in the contents of SUU- and SUS-type TAGs. The contents of SSS-type TAGs in the blends (5
:
5, 6
:
4 and 7
:
3, PS
:
SO) declined from 21.7%, 25.1% and 29.7% before interesterification to 15.7%, 16.3% and 17.5% after interesterification, respectively. Similarly, the contents of UUU-type TAGs decreased from 28.4%, 22.8% and 14.5% to 22.0%, 16.2% and 11.9%, respectively. However, SUU-type TAGs increased from 22.0%, 20.6% and 19.8% to 36.0%, 39.6% and 39.6%, respectively. There was a clear reduction in the content of SSS-type TAGs and an increase in the content of SUU-type TAGs in the blends after interesterification, which was consistent with the previous report.17 It was found that the crystal transformation has a relationship with the main TAGs composition. The reduction of SSS-type TAGs would be favorable for the generation of small crystals,18,19 and the increase in intermediate melting point of TAGs and SUU-type TAGs tends to generate strong β′ polymorphs.20,21 The TAG profiles of interesterified blends indicate that they are more suitable for the preparation of high-quality special fats for fast frozen food than physical blends.
| Fatty acid/% | Before interesterification | After interesterification | ||||
|---|---|---|---|---|---|---|
5 : 5 |
6 : 4 |
7 : 3 |
5 : 5 |
6 : 4 |
7 : 3 |
|
| a Notes: ∑UFA, total unsaturated fatty acids; ∑SFA, total saturated fatty acids. | ||||||
Myristic (14 : 0) |
0.36 | 0.41 | 0.57 | 0.37 | 0.39 | 0.52 |
Palmitic (16 : 0) |
46.31 | 45.79 | 44.93 | 46.28 | 45.32 | 44.37 |
Stearic (18 : 0) |
3.07 | 3.25 | 3.57 | 3.03 | 3.71 | 3.53 |
Oleic (18 : 1) |
26.03 | 26.79 | 25.98 | 26.04 | 27.12 | 26.57 |
Linoleic (18 : 2) |
22.09 | 21.73 | 21.94 | 22.11 | 22.4 | 21.97 |
Linolenic (18 : 3) |
2.14 | 2.03 | 3.01 | 2.17 | 1.06 | 3.04 |
| ∑SFA | 49.74 | 49.45 | 49.07 | 49.68 | 49.42 | 48.42 |
| ∑USFA | 50.26 | 50.55 | 50.93 | 50.32 | 50.58 | 51.58 |
| ECN | TAG | Before interesterification | After interesterification | ||||
|---|---|---|---|---|---|---|---|
5 : 5 |
6 : 4 |
7 : 3 |
5 : 5 |
6 : 4 |
7 : 3 |
||
| a Notes: P, palmitic; M, myristic; S, stearic; O, oleic; L, linoleic; Ln, linolenic. Equivalent carbon number (ECN) = CN-2DB, where CN is the carbon number of TAG and DB is the total number of double bonds in TAG; SSS, trisaturated triacylglycerols; SSU, disaturated–monounsaturated triacylglycerols; SUU, monosaturated–diunsaturated triacylglycerols; UUU, tri-unsaturated triacylglycerols. | |||||||
| 40 | LLLn | 1.8 | 1.5 | 1.3 | 0.4 | 0.2 | 0.2 |
| 42 | LLL | 9.8 | 7.9 | 4.0 | 6.2 | 4.1 | 2.6 |
| 42 | LLnP | 0.9 | 0.6 | 0.4 | 1.5 | 1.7 | 1.9 |
| 44 | LLO | 9.8 | 7.1 | 4.3 | 7.1 | 4.8 | 3.1 |
| 44 | PLL | 7.6 | 6.5 | 4.8 | 11.9 | 12.6 | 9.2 |
| 46 | LOO | 5.5 | 4.9 | 3.4 | 5.6 | 4.6 | 4.0 |
| 46 | PLO | 3.4 | 3.6 | 3.4 | 12.0 | 12.6 | 14.0 |
| 46 | PPL | 7.1 | 6.7 | 6.5 | 9.6 | 11.0 | 12.2 |
| 46 | PPM | — | — | — | 0.7 | 0.8 | 0.8 |
| 48 | OOO | 1.5 | 1.5 | 1.5 | 2.7 | 2.5 | 2.1 |
| 48 | SLO | — | — | — | 0.9 | 0.8 | 0.8 |
| 48 | POO | 7.8 | 8.0 | 9.5 | 9.2 | 11.1 | 12.5 |
| 48 | PPP | 19.1 | 22.4 | 26.5 | 13.0 | 13.5 | 14.1 |
| 48 | POP/PPO | 19.0 | 22.9 | 26.8 | 14.0 | 15.9 | 15.5 |
| 50 | SOO | 2.3 | 1.9 | 1.8 | 0.2 | 0.5 | 0.8 |
| 50 | POS/PSO | 1.1 | 1.3 | 2.5 | 2.4 | 2.9 | 3.0 |
| 50 | PPS | 2.6 | 2.8 | 2.9 | 1.9 | 2.0 | 2.6 |
| UUU | 28.4 | 22.8 | 14.5 | 22.0 | 16.2 | 11.9 | |
| SUU | 22.0 | 20.6 | 19.8 | 36.0 | 39.6 | 39.6 | |
| SSU | 27.1 | 30.9 | 35.7 | 26.1 | 29.8 | 30.7 | |
| SSS | 21.7 | 25.1 | 29.7 | 15.7 | 16.3 | 17.5 | |
:
5, 6
:
4 and 7
:
3, PS
:
SO) before and after interesterification are shown in Fig. 1. The interesterified blends had lower SFC values between 10 and 45 °C than the physical blends. At 45 °C, the SFC of physical blends varied from 10% to 15%. However, the SFC of all the interesterified blends was reduced to approximately 5%. Generally, the SFC between 10 °C and 40 °C gives a measure of fat plasticity and it also influences fat sensory characteristics. It was reported that shortening had a wide plastic range when its SFCs were 10–45% between 10 °C and 40 °C.22 Apparently, the interesterified blends with decreased SFC had a wider plastic range compared with the physical blends. It is well known that the SFC at 10 °C determines the spread of fat.23 The SFCs of physical blends varied from 57.5% to 42.5% at 10 °C with a reduction in the PS
:
SO ratio, but the corresponding values for the interesterified blends were in the range of 37–41%, indicating that the interesterified blends had better plastic range than the physical blends. The changes in the SFCs of blends are usually related to their TAG profiles.23,24 The reduction in the SFC was attributed to the decrease in the content of SSS-type TAGs, and the increase in the content of SUS- and SUU-type TAGs could improve the plastic range of fat and its sensory properties.13,20
![]() | ||
| Fig. 1 SFC of the palm stearin (PS) and soybean oil (SO) blends before and after interesterification. | ||
:
5, 6
:
4, 7
:
3, PS
:
SO) before and after interesterification are presented. The physical blends had higher crystallization onset temperature (Tco) and melting completion temperature (Tmc) than the corresponding interesterified blends. As shown in Fig. 2A–C, for blends of 5
:
5, 6
:
4 and 7
:
3 PS
:
SO, Tmc decreased from 47.6, 48.8 and 49.5 before interesterification to 44.8, 45.8, and 45.2, respectively, after interesterification. This behavior was highly correlated with the decrease in the content of SSS-type TAGs and the increase in the content of SUS- and SUU-type TAGs after interesterification, which was consistent with the previous report.25 It was worth noting that the peak areas of the highest SMP changed to be smaller and close to 45 °C for all the interesterified blends. The differences in thermal behavior between physical blends and their interesterified blends were attributed to the changes in TAG species. The presence of high-melting TAGs, such as OOO and PPP or SSS species with similar structures in the physical blends, may impart its poor mouth feel.26 Fig. 2D–F depicts the crystallization profiles of the blends. After interesterification, the Tco for the blends of 5
:
5, 6
:
4 and 7
:
3 PS
:
SO decreased from 1.2, −0.2 and −6.2 to −2.6, −6.7 and −7.3, respectively. It was reported that the rearrangement of FAs in TAGs after enzymatic interesterification led to the production of new TAG species, which in turn changed the thermal behaviors.27
![]() | ||
| Fig. 2 DSC melting (A–C) and cooling (D–F) curves of the palm stearin (PS) and soybean oil (SO) blends before and after interesterification. | ||
:
5, 6
:
4 and 7
:
3, PS
:
SO) before and after interesterification were detected by XRD (Fig. 3). The three representative polymorphic forms of fat crystal are named as α, β′, and β, and the polymorph could be determined by the short spacing of the crystal. The short spacing of α form (hexagonal) is the least stable and it appears near 4.15 Å.11 The β form (triclinic) is the most stable and has a strong short spacing at 4.6 Å.19 The β′ form (orthorhombic) displayed a metastable form and has two strong short spacings at about 3.8 and 4.2 Å.28 The β′ form with small crystals is desirable for providing good texture and properties in most margarines and shortenings.29 Before interesterification, the physical blends (5
:
5, 6
:
4 and 7
:
3, PS
:
SO) showed four short spacings at 4.62, 4.2, 4.31 and 3.83 Å, respectively, indicating the coexistence of β′ and β form. After interesterification, the intensity of the peak at 4.6 Å significantly decreased, particularly the blend of 6
:
4 PS
:
SO had the weakest peak intensity at 4.6 Å, which indicated that β form reduced and β′ form increased. Therefore, in the interesterified blends, their polymorphism showed predominant β′ form crystal. The transformation of polymorphism is dependent on the degree of homogeneity of TAGs.21 The PPP mainly tends to form β crystal and PLO, POO, and PPS tend to be β′ crystal.17 The results given in Table 1 showed that after interesterification, the content of POP and PPP decreased, whereas the content of PLO and POO increased for all the blends. Thus, the interesterified blends canform β′ crystal more easily than the physical blends.
![]() | ||
| Fig. 3 XRD spectra of the palm stearin (PS) and soybean oil (SO) blends before and after interesterification. | ||
:
5, 6
:
4 and 7
:
3, PS
:
SO) before and after interesterification were analyzed by polarized light microscopy (PLM) and the result is illustrated in Fig. 4. The crystal morphologies of the blends were explicitly different. The interesterified blends (5
:
5, 6
:
4 and 7
:
3, PS
:
SO) consisted of crystal aggregates with tightly packed, uniform, needle-shaped crystals, particularly the interesterified blend of 7
:
3 PS
:
SO. The physical blends exhibited coarse, large symmetrical spherulite-shaped crystals with diameters exceeding 50 μm. In addition, the crystals tended to aggregate to form clusters with the increase in PS content. The crystal with small size and needle-like structure was β′ crystal and the crystal that aggregated to form spherulites with large size corresponded to β crystal.21 Ribeiro et al. found that the microstructure alteration of the blend of canola oil and fully hydrogenated cottonseed oil after interesterification was attributed to the decrease in symmetrical high-melting-point TAGs (SSS).19 Hence, the resulting interesterified blends with the ideal crystal form are much suitable for the preparation of high-quality special fats for fast frozen food.
![]() | ||
| Fig. 4 PLM image of the palm stearin (PS) and soybean oil (SO) blends before (A, C, E) and after (B, D, F) interesterification. | ||
:
5, 6
:
4 and 7
:
3, PS
:
SO) in improving the quality of special fat for fast frozen food, they were used as base oil to prepare special fats, which were further applied in the production of fast frozen dumplings. The fast frozen dumpling prepared using commercial fat was used as a comparison and that without fat was used as the control. The sensorial properties of these five groups of fast frozen dumplings were investigated by detecting their cracking rate, appearance, boil-resisting ability and mouth feel. As shown in Fig. 5, the fast frozen dumplings prepared using the interesterified blends exhibited low cracking rates, and the cracking rates of these five groups of fast frozen dumplings followed the order: PS
:
SO 7
:
3 ≈ PS
:
SO 6
:
4 < PS
:
SO 5
:
5 ≈ commercial fat < control. The fast frozen dumplings prepared using the interesterified blends 6
:
4 and 7
:
3 had smoother appearance before and after cooking and better boil-resisting ability than other groups, and the orders were PS
:
SO 7
:
3 ≈ PS
:
SO 6
:
4 > PS
:
SO 5
:
5 ≈ commercial fat > control, indicating that addition of fats into fast frozen dumplings decreased their stickiness and improved their tolerance to overcooking. The mouth feel of the fast frozen dumplings prepared using the interesterified fats and the commercial fat were similar and better than that of the control, which was due to the change in the texture of fast frozen dumplings after the addition of fat. The overall acceptability of these five groups of fast frozen dumplings followed the order PS
:
SO 7
:
3 > PS
:
SO 6
:
4 > PS
:
SO 5
:
5 ≈ commercial fat > control, indicating that the special fats prepared from the interesterified blends had better quality in preparation of fast frozen dumplings, particularly for the blends of PS
:
SO 6
:
4 and 7
:
3. These sensory evaluation results were consistent with the results of previous studies,12,30 in which special oils based on interesterified blend were used for preparing dumpling balls. During the freezing process of fast frozen flour product, the movement of water molecules separating from the surface of dough caused the dissipation of the dough. The plastic fat may limit the movement of water and thereby improve the ability of dough to maintain its structure during freezing and storage.31 Furthermore, lipids are believed to contribute a desirable mouth feel and influence flavor perception.32
Furthermore, the crystal in the plastic fats could impact their application in food products. The β′ form with very small crystals, which enable it to incorporate relatively large amounts of liquid oil in the crystal network, leads to the production of smooth, continuous and homogeneous plastic fats in the application.33 Therefore, according to this study, the enzymatic interesterified blend-based special fat with more β′ form crystal has better quality than physical blend-based special fat and commercial fat (data not shown). These results suggest that enzymatic interesterification is an efficient strategy to prepare high-quality special fat for fast frozen food.
:
5, 6
:
4 and 7
:
3, PS
:
SO) were improved by enzymatic interesterification. The interesterified blends with specific SMP can be obtained by regulating the flow rate of reactants in the fluidized bed reactor. The SSS- and UUU-type TAGs decreased and the SUU-type TAGs increased after interesterification. The interesterified blends had better plastic range than the physical blends and the SFCs of the interesterified blends were 5–40% between 10 and 45 °C. The interesterified blends were easier to form β′ crystal than the physical blends due to the change in the type of TAGs. The fast frozen dumplings prepared using special fats, which were produced with interesterified blends as base oil, had better sensory characteristics, indicating that enzymatic interesterification is promising in the preparation of high-quality special fat for fast frozen food.
Footnote |
| † This authors have the same contribution and are co-first authors. |
| This journal is © The Royal Society of Chemistry 2017 |