Chemical Composition Differences of Different Apricot Fruits in Xinjiang Based on Nuclear Magnetic Resonance Analysis

WANG Sidan; HE Weizhong; PAN Juxiu; MA Lei; TAO Yongxia; SHEN Qi

doi:10.13718/j.cnki.xdzk.2025.10.004

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To characterise the quality diversity and potential differences in nutrient composition of apricot fruits of the main cultivars in Xinjiang production areas (small white apricot of Aksu production area, large white apricot of Bayin'guoleng Mongol Autonomous Prefecture, Mukyu apricot of Hotan production area, Saimaiti apricot of Kashgar production area, Tasi apricot of Turfan production area, and on-tree dried apricot of Ili Kazakh Autonomous Prefecture production area). In this study, Nuclear Magnetic Resonance (NMR) technology was employed for Nuclear Magnetic Resonance Hydrogen Spectroscopy (¹H-NMR) analysis and identification of pulp of Xinjiang main apricot varieties. Main chemical components in attributive spectra was clarified, and the nutritional quality of pulp of Xinjiang main apricot varieties was comprehensively evaluated with principal component analysis and least square discriminant analysis. The multivariate statistical analysis showed that the nutritional quality of apricot fruit of Xinjiang's main planted varieties had a better overall separation. ¹H-NMR showed that compared with other production areas, the chemical component signals of Tashi apricot in Turfan production area were obviously more. Seven chemical components with large contributions to the differences were screened out, namely histidine, lysine, arginine, serine, glutamine, sucrose and D-fructose. In small white apricots of Aksu, the contents of serine and lysine in the chemical composition were higher. In large white apricots from Bayin'guoleng Autonomous Prefecture, the contents of lysine, glutamine, D-fructose and histidine in the chemical composition were higher. In Mukyu apricots of Hotan and Saimaiti apricots of Kashgar, the contents of histidine and sucrose in the chemical composition were higher, and in Tasi apricots from Turfan, the contents of arginine, serine, lysine and glutamine in the chemical composition were higher. Histidine, sucrose and D-fructose were found to be more abundant in the chemical composition of on-tree dried apricots from Ili Kazakh Autonomous Prefecture.

Corresponding author: SHEN Qi

Received Date: 13/09/2024

Available Online: 20/10/2025

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杏子(Prunus armeniaca L.)属于蔷薇科杏属落叶乔木，果实一般呈圆形或卵圆形，口味酸甜，营养丰富，含有大量的糖、有机酸、胡萝卜素和糖苷^[1-3]。目前，对新疆不同产区杏子的研究主要集中于总有机酸和总糖含量的差异化、品种特性差异^[4]、采后的保鲜贮藏^[5-7]以及产品加工^[8-9]等方面。我国杏种植资源相对丰富，主要种植在华北及西北地区，而新疆作为杏子栽培种植的主产区之一，种质资源丰富^[10]，所产杏子果实风味浓郁、营养品质较好。

近年来，核磁共振(Nuclear Magnetic Resonance，NMR)技术在研究待测物的系统性和完整性方面有一定的优势，可以通过获得样本间化学成分的结构信息，比较不同样本之间的差异，现已成为食品研究领域中颇受青睐的技术之一^[11-14]。NMR技术可以系统完整地分析果实品质的差异，也可以分析不同品种或不同产地作物间的品质差异。安莉等^[15]基于NMR技术从不同品种草莓的氮谱(¹H-NMR)图中识别出20种化学成分，分析了不同品种草莓间的化学成分差异，并结合多元统计分析筛选出了丙氨酸、柠檬酸、苹果酸等7种潜在的差异代谢物; 魏亮等^[16]的研究表明NMR技术可以比较不同产地铁棍山药间的化学成分，通过谱图信息指认共识别出30种主要的化学成分，并利用葡萄糖、果糖的含量鉴别铁棍山药是否为道地怀山药。此外，NMR技术还用于分析灵芝^[17]、甜瓜^[18]、芍药^[19]等作物的品质差异。

杏果中化学成分组成多样，仅靠感官评价或某一类化学成分含量都不能全面反映其果实的品质。传统的研究方法往往忽略了杏果中化学成分的整体特征，无法实现对杏果中所含化学成分信息的高通量捕获和不同杏果间化学成分的差异性鉴别。NMR技术则可以系统全面地分析待测物的化学成分，是一种可以应用于生物的代谢组学分析方法^[20]。杏果中的糖类、氨基酸类和有机酸类物质与杏果的口味和营养品质密切相关，故本研究利用NMR技术结合多元统计分析方法探讨新疆6产区主栽品种杏果的营养品质差异，旨在为新疆不同产区主栽品种杏果特色挖掘提供一定的理论依据。

1. 材料与方法

1.1. 试剂与仪器

N，N二甲基甲酰胺(DMF)、二甲基亚砜(DMSO)，化学纯，国药集团化学试剂有限公司。

核磁共振波谱仪(ADVANCE 400型)，瑞士Brucker公司; 电子天平(FA2004型)，上海舜宇恒平科学仪器有限公司; 磁力加热搅拌器(IKA RCT basic型)，德国IKA公司; 真空泵(IKA VACSTAR digital)，德国IKA公司; 真空冷冻干燥机(LGJ-25C型)，北京四环科学仪器厂有限公司。

1.2. 试验方法

1.2.1. 样品采集

根据杏果成熟及上市时间，于2023年7-8月，采集新疆阿克苏产区小白杏、巴音郭楞蒙古自治州产区大白杏、和田产区穆克尤杏、喀什产区赛麦提杏、吐鲁番产区塔西杏、伊犁哈萨克自治州产区树上干杏，分别对应A、B、C、D、E、F产区。根据采样产区主栽杏果种植面积的大小，在产区内各乡镇采集杏果样品，A产区10份、B产区16份、C产区15份、D产区27份、E产区27份、F产区10份，共采集杏果样品105份，样品采集详细信息见表 1。

每份杏果样品质量为(3±0.5) kg，样品采集后直接运回实验室。由于核磁共振谱图采集成本较高，无法采集所有样品谱图，故将同产区内采集的样品以该产区乡镇为单位混匀后表征该产区杏果的整体营养品质特征，去核取果肉后打浆制成混样。根据各产区作物种植面积大小确定混样个数，混样共24份，其中A产区4份、B产区3份、C产区3份、D产区6份、E产区4份、F产区4份，置于-80 ℃冰箱预冻后，经真空冷冻干燥机冻干为粉末状待测。

1.2.2. 检测及分析方法

称取20 mg的冻干杏果样品粉末，加入0.4 mL的磷酸缓冲液(0.05 mol/L Na₂HPO₄和NaH₂PO₄的重水溶液)以及1 mL氘代DMSO，超声促进溶解，用一次性注射器吸取样液，微量过滤器过滤，使滤液装入核磁管待测。核磁共振氢谱(¹H-NMR)检测于室温(25 ℃)测定，5 mm OneNMR探头，脉冲序列为PRESAT以压制样品中的水峰，扫描64次，谱宽4 800 Hz，采样点数16 K，弛豫时间2 s，采集时间3.408 s。

1.2.3. 核磁共振谱图数据预处理

使用MestReNova软件(V 9.0.1，Mestrelab Research，Santiago de Compostela，Galicia，Spain)对谱图进行傅立叶变换，相位调整，基线校正等处理，所有谱图在进行傅立叶变换时均乘以增宽因子为0.3 Hz的指数窗函数以提高信噪比。核磁共振谱图以内标物(TSP)在δ 0 ppm处的单峰定标，对比6产区杏果样品的¹H-NMR分段谱图，对谱图进行分段积分。积分区间为δ 0.2~10 ppm，积分间距为0.04 ppm，全谱积分并将数据导出后归一化。为了消除基线波动和溶剂峰、水峰对数据分析带来的影响，在进行统计分析时去除δ 2.52~3.32 ppm和δ 4.72~5.12 ppm之间的信号。

1.2.4. 核磁共振数据分析

使用SIMCA-P14.0软件对归一化后的核磁数据进行主成分分析(Principle Component Analysis，PCA)和最小二乘法判别分析(Partial Least Squares Discriminant Analysis，PLS-DA)，对于PLS-DA模型，利用随机置换排列对模型的可靠性进行验证。

3. 讨论与结论

3.1. 讨论

基于NMR技术以及PLS-DA模型分析发现，6产区样品整体分离度较好，其中巴音郭楞蒙古自治州大白杏(B)与阿克苏产区小白杏(A)样品大致重叠，原因可能是两个产区的主栽品种都是白杏，差异并不显著; 喀什产区赛麦提杏(D)与和田产区穆克尤杏(C)有1个样品重叠，可能是由于两个产区地理位置较接近，气候差异较小、种植方式相近等。有研究报道显示，在不同产区的作物会由于地理位置较近等因素导致化学成分较为相似，差异不明显^[6]。

新疆6产区主栽杏果品种中潜在的差异化学成分为氨基酸和糖类，各产区杏果中差异代谢物含量与杏果品质之间均有着密切的联系，这些差异可能使不同产区杏果呈现出不同的特征优势。氨基酸是蛋白质、酶和核酸的前体物质，作为信号分子在果实的合成代谢和渗透调节中发挥作用，蔗糖、D-果糖是果实中主要的可溶性糖，是杏果口感与风味的重要影响因子^[24]。果实中部分氨基酸与可溶性糖的转化具有相关性，特别是呈味氨基酸，如甘氨酸本身作为一种甜味氨基酸，能够通过促进气孔开放和光合电子转移速率提高净光合速率，增加光合产物，提高果实中可溶性糖的含量，利于果实着色^[25]; 谷氨酰胺是果实中氮同化过程中产生的第一种氨基酸，除了为果实带来鲜味外，还可以降解柠檬酸，降低杏果的酸度，从而提高适口性。

研究表明，氨基酸种类及含量与果实品质和抗病性密切相关，Yan等^[26]发现以丝氨酸为前体合成的丝氨酸蛋白酶处理果实后可以通过抑制菌类生长、提高果实抗病性等相关基因的相对表达量来增强果实对病原真菌的抗性。诸多学者^[27-29]的报道表明，赖氨酸处理可以抑制相关病原真菌的活性，提高果实的抗病性，减少果实腐烂，从而保持果实的采后品质。阿克苏产区小白杏(A)和吐鲁番产区塔西杏(E)果实中丝氨酸、赖氨酸含量较高，这为新疆杏果的病害防治与采后贮藏提供了新的思路。还有研究发现^[30-31]，精氨酸处理可以通过调控果实中多胺、脯氨酸和一氧化氮等物质的合成、增强抗氧化酶活性并提高植物的抗冷性，减轻果实贮藏期的冷害。吐鲁番产区塔西杏(E)果实中精氨酸含量较高，在冷藏期冷害率较低，可能更适合长途冷链运输。通过研究解析新疆不同产区主栽品种杏果差异化学成分的相对含量，有利于明确不同产区主栽品种杏果的营养品质特征及差异性，对打造和增强新疆不同产区杏果品牌特色具有积极的意义。

3.2. 结论

对6个产区的主栽品种杏果进行化学成分指认和差异分析，并找出潜在的差异化学成分，共鉴别出组氨酸、赖氨酸、精氨酸、丝氨酸、谷氨酰胺、蔗糖、D-果糖等7种差异化学成分。研究表明，NMR技术能够用于不同产区杏果化学成分及其含量的差异分析，并且可以结合多元统计分析筛选各产区之间影响杏果品质的差异化学成分，可为新疆不同产区杏果营养品质差异分析及杏果资源深度开发利用提供理论依据。

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Chemical Composition Differences of Different Apricot Fruits in Xinjiang Based on Nuclear Magnetic Resonance Analysis

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Chemical Composition Differences of Different Apricot Fruits in Xinjiang Based on Nuclear Magnetic Resonance Analysis

Corresponding author: SHEN Qi