不同品种苹果果胶含量及结构差异分析

doi:10.3864/j.issn.0578-1752.2019.13.011

摘要/Abstract

摘要：

【目的】比较分析不同品种苹果原料果胶结构的差异性,为品种识别提供帮助,为苹果相关产品的加工以及苹果副产物的利用提供理论数据基础。【方法】以来自全国7个产区的14个品种20份苹果样品为研究对象,由每份苹果的细胞壁物质（alcohol-insoluble residue,AIR）提取3种类型果胶：水溶性果胶（water-soluble pectin,WSP）、螯合性果胶（CDTA-soluble pectin,CSP）及碱溶性果胶(Na₂CO₃-soluble pectin,NSP),研究分析果胶的半乳糖醛酸（galacturonic acid,GalA）含量、酯化度、重均分子量(weight-average molar mass,Mw)、中性糖含量以及结构官能团,并进行主成分分析以及热图分析。【结果】不同品种苹果样本间果胶特性存在一定差异性。3种类型果胶含量以NSP半乳糖醛酸含量最多,WSP次之,CSP含量最少,最富含果胶含量的苹果品种是‘澳洲青苹’（215.75 mg GalA·g^-1 AIR）,产自不同地区的‘富士’（栖霞、新疆、青岛‘烟6’、河北‘三优’）苹果的各果胶半乳糖醛酸含量有着较大的差异;‘秋锦’的WSP甲酯化度最高,CSP的甲酯化度偏高,且大多数为高酯化度果胶;WSP的乙酰化度均在3.5%以下;WSP的Mw在各品种苹果间差异性最为显著,辽宁‘华月’WSP的Mw最高;‘红将军’WSP的Mw/Mn高于其他品种,但其CSP的Mw/Mn低于其他品种;Mw/Mn在3种类型果胶间差异性较小;中性糖含量组成均以鼠李糖、阿拉伯糖、半乳糖3种单糖居多,岩藻糖、木糖、甘露糖呈微量状态,葡萄糖存在居多的原因可能是在果胶的提取过程中,有可溶性淀粉、糊精或低聚糖混杂;各果胶以同型聚半乳糖醛酸和鼠李聚半乳糖醛酸II型结构为主,且果胶侧链较多;主成分分析得出苹果样本间的主要差异性指标为WSP的半乳糖含量、阿拉伯糖含量、岩藻糖含量以及CSP的半乳糖含量、鼠李糖含量、中性糖比率（鼠李糖与半乳糖醛酸含量的比值）。【结论】不同品种苹果原料中3种类型果胶的含量及其结构存在一定的差异性,具有父本、母本等基因杂交关系的苹果品种的果胶结构特点间存在关联性,研究可为苹果育种与种植结构调整提供理论支持。

关键词: 苹果品种, 果胶, 结构, 差异性

Abstract:

【Objective】 The differences in pectin structure of different apple raw materials were compared and analyzed to give assistance for variety identification, so as to provide theoretical data basis for the processing of apple-related products and the utilization of apple by-products. 【Method】 Twenty apple samples of fourteen cultivars from seven producing areas in China were researched. Three types of pectin were extracted from the alcohol-insoluble residue (AIR) of each apple, including water-soluble pectin (WSP), CDTA-soluble pectin (CSP) and Na₂CO₃-soluble pectin (NSP). The galacturonic acid (GalA) content, esterification degree, weight-average molar mass (Mw), neutral sugar content, and structural functional groups of pectin were analyzed, then the principal component analysis (PCA) and heat map analysis were performed. 【Result】 The results showed that the content and structure of pectin were different in varying degrees. Among the three types of pectin, the content of NSP was the highest (determined with GalA as standard), followed by WSP and CSP. The most pectin-rich apple variety was the Granny Smith (215.75 mg GalA·g ^-1 AIR). Fuji (Qixia, Xinjiang, Yan6-Qingdao and Hebei) from different regions had great differences in the contents of galacturonic acid. The DM of Qiujin was the highest among the WSP of various varieties of apples. CSP had relatively higher DM and the most of them were high DM pectin. The degree of acetylation of WSPs were all below 3.5%. The Mw of WSP was the most significant one among all apple varieties. The Mw of Huayue’s WSP showed the highest value. The Mw/Mn of Hongjiangjun’s WSP was the highest, but the Mw/Mn of Hongjiangjun’s CSP was the lowest one. Mw/Mn had a small difference between the three types of pectin. Through the heatmap analysis, Rhamnose (Rha), arabinose (Ara) and galactose (Gal) were three main neutral sugars, and fucose (Fuc), xylose (Xyl) and mannose (Man) were in trace amount. The reason for plenty of glucose might be due to the presence of soluble starch, dextrin or oligosaccharides during the extraction of pectin. The pectin structure mainly consisted of homogalacturonan and rhamnogalacturonan-II. The PCA showed that the main differential indexes of different apple cultivars were WSP-Gal, WSP-Ara, CSP-Gal, CSP-Rha, WSP-Fuc and CSP-Rha/GalA. 【Conclusion】 There were certain differences among the content and structure of three types of pectin from various apple cultivars. Which were related to the pectin structural characteristics of apple varieties with parental and maternal crosses. The study could provide a theoretical support for the structural adjustment of apple breeding and planting.

Key words: apple cultivar, pectin, structure, difference

曹风,刘璇,毕金峰,吴昕烨,张彪,刘嘉宁. 不同品种苹果果胶含量及结构差异分析[J]. 中国农业科学, 2019, 52(13): 2328-2340.

CAO Feng,LIU Xuan,BI JinFeng,WU XinYe,ZHANG Biao,LIU JiaNing. Difference Analysis of Pectin Content and Structure from Various Apple Cultivars[J]. Scientia Agricultura Sinica, 2019, 52(13): 2328-2340.

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https://www.chinaagrisci.com/CN/Y2019/V52/I13/2328

图/表 9

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表4

不同品种苹果原料WSP、CSP及NSP的中性糖比率"

序号 No.	水溶性果胶Water-soluble pectin			螯合性果胶 CDTA-soluble pectin			碱溶性果胶Na₂CO³-soluble pectin
序号 No.	I	II	III	I	II	III	I	II	III
1	5.47±0.44fghi	0.02±0.00bc	8.39±0.76bcde	—	—	—	—	0.02±0.00de	5.07±0.15def
2	9.84±0.80cd	0.01±0.00d	7.00±0.36def	—	0.00±0.00e	8.24±0.00cde	—	0.03±0.00cde	5.36±0.87def
3	9.13±0.78cde	0.01±0.00d	10.89±2.97ab	—	0.00±0.00e	11.78±0.59bcd	—	0.02±0.00de	6.17±0.18bcdef
4	10.2±0.86c	0.01±0.00d	6.16±0.85def	—	0.00±0.00e	8.36±1.35cde	—	0.07±0.01a	5.76±1.53cdef
5	—	0.01±0.00d	8.64±1.22bcde	—	0.00±0.00e	10.97±1.00cd	13.27±1.23a	0.01±0.00e	5.34±0.64def
6	10.5±0.42c	0.01±0.00d	7.00±0.26def	—	0.03±0.00a	8.05±0.70cde	—	0.03±0.00cde	7.54±0.06abc
7	2.51±0.20i	0.04±0.00a	9.09±1.19bcd	—	0.02±0.00b	8.23±1.04cde	—	0.03±0.00de	8.60±1.35a
8	7.22±0.45cdefgh	0.02±0.00bc	4.63±0.85f	—	0.01±0.00c	6.11±1.02cde	—	—	—
9	6.63±0.09defgh	0.01±0.00cd	8.20±1.05bcde	—	0.00±0.00e	9.91±1.36cde	—	0.02±0.00de	5.38±0.86def
10	5.91±0.42efgh	0.01±0.00d	13.39±2.79a	7.18±0.22	0.00±0.00e	29.28±3.24a	—	0.02±0.00e	4.70±0.86f
11	5.38±0.05ghi	0.02±0.00b	5.98±0.67ef	—	0.01±0.00c	8.36±0.24cde	—	0.05±0.00bc	4.92±0.35def
12	14.95±1.65b	0.01±0.00d	10.06±0.76bc	—	—	—	—	0.01±0.00e	5.93±0.77cdef
13	9.09±0.68cde	0.01±0.00d	10.85±0.57ab	—	0.01±0.00c	18.33±3.20b	—	0.03±0.00cde	7.92±1.51ab
14	6.41±0.01defgh	0.01±0.00d	10.49±1.22b	—	—	—	—	0.03±0.00cde	4.90±0.08ef
15	8.90±0.41cdef	0.01±0.00d	7.31±0.84cdef	—	0.00±0.00e	7.41±0.63cde	—	0.04±0.00bcd	5.42±0.24def
16	6.12±0.79efgh	0.02±0.00bc	6.15±0.62def	—	0.00±0.00e	9.85±0.57cde	—	0.05±0.01ab	6.44±0.37bcdef
17	8.70±0.13cdefg	0.01±0.00d	6.53±0.73def	—	0.00±0.00e	12.66±2.60bc	—	0.02±0.00de	7.98±0.45ab
18	6.69±0.54defgh	0.02±0.00bc	5.16±0.20f	—	0.01±0.00c	10.73±0.02cd	—	0.02±0.00e	6.89±0.18abcde
19	4.59±0.16hi	0.02±0.00bc	8.24±1.43bcde	—	0.02±0.00b	11.77±1.21bcd	—	0.02±0.00de	8.39±0.72a
20	20.13±2.04a	0.01±0.00d	8.3±1.01bcde	—	—	—	6.18±0.70ab	0.02±0.00de	6.91±0.04abcd

表4

图4

图5

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序号 No.	品种 Cultivar	产地 Geographical origin	序号 No.	品种 Cultivar	产地 Geographical origin
1	富士Fuji	山东栖霞Qixia, Shandong	11	华金Huajin	辽宁葫芦岛Huludao, Liaoning
2	烟富6号Yanfu6	山东青岛Qingdao, Shandong	12	华月Huayue	辽宁葫芦岛Huludao, Liaoning
3	富士Fuji	新疆 Xinjiang	13	秋锦Qiujin	辽宁葫芦岛Huludao, Liaoning
4	三优富士Sanyou Fuji	河北Hebei	14	乔纳金Jonagold	辽宁葫芦岛Huludao, Liaoning
5	半坡秦冠Banpo Qinguan	山西运城Yuncheng, Shanxi	15	红将军Hongjiangjun	山东淄博Zibo, Shandong
6	秦冠Qinguan	甘肃平凉Pingliang, Gansu	16	国光Ralls	山东淄博Zibo, Shandong
7	金冠Golden Delicious	甘肃平凉Pingliang, Gansu	17	花牛Huaniu	甘肃平凉Pingliang, Gansu
8	金冠Golden Delicious	山东泰安Taian, Shandong	18	秦红Qinhong	陕西咸阳Xianyang, Shaanxi
9	新红星Starkrimson	山东泰安Taian, Shandong	19	长蜜欧Changmiou	陕西咸阳Xianyang, Shaanxi
10	新红星Starkrimson	辽宁葫芦岛Huludao, Liaoning	20	澳洲青苹Granny Smith	陕西咸阳Xianyang, Shaanxi

指标 Index		编号 Number	指标 Index		编号 Number	指标 Index		编号 Number
水溶性果胶Water-soluble pectin	半乳糖醛酸含量Galacturonic acid content	W1	螯合性果胶CDTA-soluble pectin	半乳糖醛酸含量 Galacturonic acid content	C1	碱溶性果胶Na₂CO₃- soluble pectin	半乳糖醛酸含量Galacturonic acid content	N1
	甲酯化度 Degree of methoxylation	W2		甲酯化度 Degree of methoxylation	C2
	乙酰化度 Degree of acetylation	W3
	重均分子量 Weight-average molar mass	W4		重均分子量 Weight-average molar mass	C4		重均分子量 Weight-average molar mass	N4
	多分散系数 Polydispersity coefficient	W5		多分散系数 Polydispersity coefficient	C5		多分散系数 Polydispersity coefficient	N5
	岩藻糖Fucose	W6		岩藻糖Fucose	C6		岩藻糖Fucose	N6
	鼠李糖Rhamnose	W7		鼠李糖Rhamnose	C7		鼠李糖Rhamnose	N10
	阿拉伯糖Arabinose	W8		阿拉伯糖Arabinose	C8		阿拉伯糖Arabinose	N11
	半乳糖Galactose	W9		半乳糖Galactose	C9		半乳糖Galactose	N12
	葡萄糖Glucose	W10		葡萄糖glucose	C10		葡萄糖glucose	N13
	木糖Xylose	W11		木糖Xylose	C11		木糖Xylose	N14
	甘露糖Mannose	W12		甘露糖Mannose	C12		甘露糖Mannose	N15
	Ⅰ	W13		Ⅰ	C13		Ⅰ
	Ⅱ	W14		Ⅱ	C14		Ⅱ
	Ⅲ	W15		Ⅲ	C15		Ⅲ

序号 No.	W1 (mg GalA?g^-1 AIR)	C1 (mg GalA?g^-1 AIR)	N1 (mg GalA?g^-1 AIR)	W2 (%)	C2 (%)	W3 (%)	W4 (×10⁵ Da)	C4 (×10⁵ Da)	N4 (×10⁵ Da)	W5	C5	N5
1, 2, 3, 4	54.64	45.38	92.76	56.04	65.31	1.87	4.98	2.56	1.40	2.12	1.52	2.15
5, 6	108.77	43.96	153.05	43.22	81.49	1.63	6.04	4.22	1.60	1.82	1.70	1.91
7, 8	51.39	28.55	94.18	63.50	64.07	2.75	6.81	5.06	1.71	1.98	1.94	2.16
9, 10	77.25	60.87	91.62	46.74	53.25	1.98	5.20	3.70	1.22	1.74	1.87	2.04
11	45.36	32.42	65.25	55.38	61.09	1.06	12.68	2.26	3.58	1.64	1.88	2.53
12	66.68	38.22	139.23	40.61	36.09	0.67	31.63	3.20	1.57	1.36	1.68	2.47
13	48.81	31.50	102.14	80.34	85.06	2.94	3.35	4.12	1.01	2.61	1.68	1.88
14	47.32	36.00	98.62	57.40	82.83	2.35	6.14	6.04	5.34	1.74	1.70	1.96
15	40.81	29.50	91.55	47.58	90.70	1.77	7.49	3.53	1.75	2.67	1.44	2.18
16	38.14	43.65	107.80	62.18	86.30	2.47	11.73	3.60	1.52	2.08	1.62	2.18
17	80.36	43.40	105.55	54.20	85.04	1.81	4.30	3.81	1.40	1.56	1.47	2.14
18	30.73	20.04	77.49	66.81	71.37	2.71	6.37	4.34	2.28	2.24	1.64	2.28
19	55.84	37.60	118.61	55.51	75.94	2.19	13.30	7.18	1.36	2.28	2.21	2.64
20	68.43	53.60	215.75	46.89	81.66	2.04	1.66	3.05	5.00	2.49	1.59	2.50