Enzymatic synthesis of structured lipids from liquid and fully hydrogenated high oleic sunflower oil

Figures & data

Table 1. Fatty acid compositions (%) of the raw materials, high oleic sunflower (SO), fully hydrogenated high oleic sunflower oil (FHSO), and the binary blends (SO:FHSO).

	Raw materials (%w/w) SO:FHSO (% w/w)
Fatty acid (%)	SO	FHSO	60:40	50:50	40:60	30:70
C16:0 (P—palmitic)	3.7 ± 0.2	3.7 ± 0.0	3.7 ± 0.0	3.7 ± 0.0	3.7 ± 0.2	3.8 ± 0.0
C18:0 (S—stearic)	3.2 ± 0.2	96.3 ± 0.1	40.4 ± 0.3	49.7 ± 0.0	58.7 ± 0.2	68.2 ± 0.2
C18:1 (O—oleic)	87.4 ± 0.2	-	52.4 ± 0.1	43.7 ± 0.0	35.3 ± 0.1	26.2 ± 0.1
C18:2 (L—linoleic)	5.8 ± 0.2	-	3.5 ± 0.0	2.9 ± 0.0	2.3 ± 0.0	1.8 ± 0.0
ΣSaturated	6.9	100.0	44.1	53.4	62.4	72.0
ΣUnsaturated	93.1	-	55.9	46.6	37.6	28.0

Table 2. TAG composition (%) of high oleic sunflower (SO) and fully hydrogenated high oleic sunflower oil (FHSO), blend (BE), and after chemical (CI) and enzymatic interesterification (EI).

				SO:FHSO (%w/w)
Raw materials				60:40			50:50			40:60			30:70
NC	TAG	SO	FHSO	BE	CI	EI	BE	CI	EI	BE	CI	EI	BE	CI	EI
50	PPO/POP	0.5 ± 0.0	ND	0.2 ± 0.0	ND	ND	0.3 ± 0.0	ND	ND	0.2 ± 0.0	ND	ND	0.1 ± 0.0	ND	ND
52	PSS/SPS	ND	11.9 ± 0.0	4.8 ± 0.0	1.8 ± 0.0	2.0 ± 0.0	6.1 ± 0.0	2.7 ± 0.0	2,9 ± 0.0	7.2 ± 0.0	4.2 ± 0.0	4.2 ± 0.0	8.1 ± 0.0	5.6 ± 0.0	5.7 ± 0.0
	PSO/POS	ND	ND	ND	5,3 ± 0.0	5.3 ± 0.0	ND	5.1 ± 0.0	5.2 ± 0.0	ND	5.2 ± 0.0	5.1 ± 0.0	ND	4.5 ± 0.0	4.7 ± 0.0
	POO/OPO	11.2 ± 0.0	ND	6.8 ± 0.0	3.7 ± 0.0	3.2 ± 0.0	5.0 ± 0.0	2.0 ± 0.0	2.6 ± 0.0	4.5 ± 0.0	1.6 ± 0.0	1.6 ± 0.0	3.4 ± 0.0	ND	ND
54	SSS	ND	88.1 ± 0.0	35.9 ± 0.0	17.0 ± 0.0	7.3 ± 0.0	44.4 ± 0.0	11.6 ± 0.0	14.9 ± 0.0	52.9 ± 0.0	20.5 ± 0.0	21.2 ± 0.0	61.8 ± 0.0	33.5 ± 0.0	35.4 ± 0.0
	SSO/SOS	ND	ND	ND	20.0 ± 0.0	30.2 ± 0.0	ND	32.2 ± 0.0	31.6 ± 0.0	ND	38.0 ± 0.0	36.4 ± 0.0	ND	36.3 ± 0.0	34.5 ± 0.0
	SOO/OSO	ND	ND	ND	30.0 ± 0.0	30.5 ± 0.0	ND	29.8 ± 0.0	26.6 ± 0.0	ND	21.4 ± 0.0	22.0 ± 0.0	ND	14.4 ± 0.0	14.0 ± 0.0
	OOO	80.4 ± 0.1	ND	48.7 ± 0.0	15.7 ± 0.0	15.1 ± 0.0	40.5 ± 0.0	11.2 ± 0.0	10.9 ± 0.0	32.1 ± 0.0	6.6 ± 0.0	7.0 ± 0.0	24.2 ± 0.0	4.2 ± 0.0	4.3 ± 0.0
	OOL/OLO	5.8 ± 0.0	ND	2.4 ± 0.0	4.2 ± 0.0	4.1 ± 0.0	2.8 ± 0.0	3.8 ± 0.0	3.6 ± 0.0	2.3 ± 0.0	2.5 ± 0.0	2.5 ± 0.0	1.8 ± 0.0	1.5 ± 0.0	1.4 ± 0.0
	OLL	2.1 ± 0.0	ND	1.2 ± 0.0	2.3 ± 0.0	2.3 ± 0.0	0.9 ± 0.0	1.6 ± 0.0	1.7 ± 0.0	0.8 ± 0.0	ND	ND	0.6 ± 0.0	ND	ND

CN: Carbon number; ND: no detected; fatty acids: P: palmitic; S: stearic; O: oleic; L: linoleic.

Table 3. Acylglycerides composition (%), triacylglycerol (TAG), diacylglycerol (DAG), and monoacylglycerol (MAG) of the blends (BE) and the after chemical (CI) and enzymatic interesterification (EI).

SO:FHSO (w/w%)		TAG	DAG	MAG
	BE	99.4 ± 0.1^a	0.0 ± 0.0	0.6 ± 0.0^a
60:40	CI	89.7 ± 0.0^b	7.8 ± 0.1^a	2.4 ± 0.0^b
	EI	89.9 ± 0.0^b	9.7 ± 0.0^b	0.4 ± 0.0^c
	BE	99.3 ± 0.0^a	0.0 ± 0.0	0.7 ± 0.0^a
50:50	CI	89.6 ± 0.0^b	8.0 ± 0.0^a	2.4 ± 0.0^b
	EI	90.7 ± 0.0^c	8.6 ± 0.4^b	0.7 ± 0.3^a
	BE	99.3 ± 0.0^a	0.0 ± 0.0	0.7 ± 0.0^a
40:60	CI	89.7 ± 0.3^b	8.0 ± 0.3^a	2.2 ± 0.0^b
	EI	89.5 ± 0.2^b	9.9 ± 0.2^b	0.6 ± 0.0^c
	BE	99.3 ± 0.0^a	0.0 ± 0.0	0.7 ± 0.0^a
30:70	CI	88.1 ± 0.1^b	9.5 ± 0.0^a	2.4 ± 0.1^a
	EI	89.8 ± 0.4^b	9.4 ± 0.1^a	0.8 ± 0.2^c

Same letters for the same columns indicate that there are no significant differences between the means evaluated by Tukey’s test (p ≤ 0.05); SO: high oleic sunflower oil; FHSO: fully hydrogenated high oleic sunflower oil.

Table 4. Distribution of the fatty acids (%) at the sn-2, sn-1,3 positions on the TAG in the blend (BE), after chemical (CI) and enzymatic interesterification (EI).

		sn-2 Position(%)		sn-1,3 Position(%)
SO:FHSO (%w/w)		UFA	SFA	UFA	SFA
60:40	BE	55.7 ± 0.4^a	44.3 ± 0.8^a	47.0 ± 0.5^a	53.0 ± 0.3^a
	CI	49.2 ± 1.7^b	50.8 ± 0.8^b	46.4 ± 4.3^a	53.6 ± 4.3^a
	EI	53.2 ± 0.1^a	46.8 ± 0.3^c	48.9 ± 0.9^a	51.1 ± 0.8^a
50:50	BE	52.0 ± 0.6^a	48.0 ± 1.5^a	43.6 ± 1.1^ab	56.4 ± 1.1^ab
	CI	42.1 ± 0.3^b	57.9 ± 0.2^b	42.1 ± 0.4^a	57.9 ± 0.6^a
	EI	48.0 ± 1.2^c	52.0 ± 0.9^c	47.5 ± 2.9^b	52.5 ± 3.2^b
40:60	BE	38.5 ± 2.5^a	61.5 ± 2.5^a	32.9 ± 4.5^a	67.1 ± 4.6^a
	CI	33.1 ± 0.7^b	66.9 ± 1.0^b	33.4 ± 1.3^a	66.9 ± 1.0^a
	EI	35.9 ± 1.2^ab	64.1 ± 1.4^ab	32.5 ± 2.8^a	67.5 ± 2.6^a
30:70	BE	32.3 ± 0.5^a	67.7 ± 0.8^a	27.5 ± 0.5^a	72.5 ± 0.3^a
	CI	23.2 ± 0.2^b	76.8 ± 0.3^b	22.3 ± 0.3^b	77.7 ± 0.2^b
	EI	27.0 ± 0.6^c	73.0 ± 0.5^c	25.2 ± 1.5^a	74.8 ± 1.6^a

Same letters for the same columns indicate that there are no significant differences between the means evaluated by Tukey’s test (p ≤ 0.05); SO: high oleic sunflower oil; FHSO: fully hydrogenated high oleic sunflower oil; SFA: saturated fatty acid; UFA: unsaturated fatty acid.

Figure 1. Solid fat content (%) of high oleic sunflower (SO) and fully hydrogenated high oleic sunflower oil (FHSO) blend (BE) (▲), after chemical (CI) (x) and enzymatic interesterification (EI) (■).

Figure 2. The crystallization profiles of high oleic sunflower (SO) and fully hydrogenated high oleic sunflower oil (FHSO) blend (BE), after chemical (CI) and enzymatic interesterification (EI).

Figure 3. Microscopy of high oleic sunflower (SO) and fully hydrogenated high oleic sunflower oil (FHSO) blends (BE), after chemical (CI) and enzymatic interesterification (EI) at 25°C/24h with x40 amplification. Proportions 60:40 (1-3), 50:50 (4 -6), 40:60 (5-7) and 30:70 (8-10).

Figure 4. X-ray diffraction of high oleic sunflower (SO) and fully hydrogenated high oleic sunflower oil (FHSO) (50:50 / 30:70) blend (BE), after chemical (CI) and enzymatic interesterification (EI) at 25°C/24h.

Table 5. Polymorphic forms of the blends before (BE) and the after chemical (CI) and enzymatic interesterification (EI), obtained at 25°C for 24 h.

	Short spacing (Å)
SO:FHSO	4.6	4.2	3.9	3.8	Polymorphic form
50:50—BE	4.60 (s)	4.28 (m)	3.93 (m)		β > β′
30:70—BE	4.59 (m)	4.24 (m)	3.90 (m)		β′ + β
50:50—CI	4.60 (s)	4.27 (m)		3.89 (m)	β > β′
30:70—CI	4.59 (w)	4.28 (s)		3.88 (m)	β′ > β
50:50—EI	4.60 (s)	4.28 (w)	3.92 (m)		β > β′
30:70—EI	4.59 (m)	4.25 (m)	3.90 (m)		β′ + β

> Means more; intensities: w: weak; m: medium; s: strong.

SO: High oleic sunflower oil; FHSO: fully hydrogenated high oleic sunflower oil.