维生素C和熊果酸(ursolic acid,UA)是刺梨主要代表性活性组分,研究表明二者功能活性存在协同增效关联,然而其分子之间存在的互作关系及机制尚不明晰。为此,该研究通过紫外-可见光谱(ultraviolet-visible spectroscopy, UV-Vis)、傅里叶变换红外光谱(Fourier transform infrared spectroscopy, FTIR)、循环伏安法(cyclic voltammetry,CV)及分子模拟技术,分析维生素C与UA分子的互作影响及作用特性。结果显示,维生素C可显著提高UA的贮藏稳定性,在35 ℃贮藏30 d后,UA损失率较空白组降低27.2%(P<0.05);维生素C损失率较空白组无显著差异(P>0.05);UV-Vis显示维生素C-UA体系在290.4 nm处出现红移,二者形成电荷转移复合物;FTIR结果表明维生素C的烯二醇羟基与UA羧基通过氢键结合(3 434 cm-1处O—H伸缩振动峰蓝移);CV法显示维生素C-UA复合物的氧化峰电位左移(第一峰ΔE1=0.012 V,第二峰ΔE2=0.066 V),二者形成有电活性复合物;分子模拟表明维生素C与UA的结合能为-23.46 kcal/mol,主要作用位点为UA的C-28羧基与维生素C的C-2羟基和维生素C羟甲基上的羟基。维生素C-UA互作呈现单向保护效应,归因于氢键选择性稳定UA羧基活性位点,而维生素C烯二醇结构的易氧化双键未被覆盖,致UA稳定性增强但维生素C稳定性未显著改善。该研究丰富完善了刺梨原料活性分子相互关系基础研究,并为后续刺梨活性成分的科学利用及功能性食品高效开发提供理论依据和技术指导。
Vitamin C and ursolic acid (UA) are key bioactive components in Rosa roxburghii, exhibiting synergistic functional effects, yet their molecular interaction mechanisms remain unclear.This study investigated the interaction characteristics between vitamin C and UA using Ultraviolet-visible spectroscopy (UV-Vis), Fourier transform infrared spectroscopy (FTIR), cyclic voltammetry (CV), and molecular simulations.Results showed that vitamin C significantly enhanced UA’s storage stability, reducing UA loss by 27.2% (P<0.05) compared to the control after 30 days at 35 ℃, while vitamin C stability remained unchanged (P>0.05).UV-Vis analysis revealed a redshift at 290.4 nm, indicating charge transfer complex (CTC) formation.FTIR confirmed hydrogen bonding between vitamin C’s enediol hydroxyl groups and UA’s carboxyl groups, evidenced by a blueshift in the O—H stretching vibration peak (3 434 cm-1).CV analysis demonstrated that the vitamin C-UA complex exhibited leftward shifts in oxidation peak potentials (ΔE1=0.012 V for the first peak, ΔE2=0.066 V for the second peak), suggesting enhanced electrochemical activity of UA due to hydrogen bond-mediated adsorption.Molecular simulations revealed a binding energy of -23.46 kcal/mol, with primary interaction sites at UA’s C-28 carboxyl group and vitamin C’s C-2 hydroxyl/hydroxymethyl groups.The vitamin C-UA interaction exhibited a unidirectional protective effect, hydrogen bonds selectively stabilized UA’s carboxyl groups but failed to protect vitamin C’s oxidation-prone enediol structure, leading to improved UA stability without affecting vitamin C degradation resistance.These findings advance the understanding of bioactive component interactions in Rosa roxburghii and provide theoretical insights for developing functional foods utilizing its active constituents.
[1] 范晓燕, 孙彬焰, 郝东升, 等.刺梨的生物活性成分及加工利用研究进展[J].保鲜与加工, 2025, 25(1):139-147.
FAN X Y, SUN B Y, HAO D S, et al.Research progress on bioactive components and processing and utilization of Rosa roxburghii[J].Storage and Process, 2025, 25(1):139-147.
[2] 杜涛. 贵州刺梨产业全链条发展[N].中国食品报, 2024-12-24(002).
DU T.Comprehensive development of Guizhou Rosa roxburghii industry chain[N].China Food News, 2024-12-24(002).
[3] WANG J M, WANG G P, WANG X T, et al.Chemical constituents and bioactivities of Rosa roxburghii:A systematic review[J].Food Science and Technology, 2022, 42:e72722.
[4] FU M, LIU J, LI Q, et al.Synthesis of lipophilic vitamin C and evaluation of its antioxidant performance in sunflower seed oil frying[J].Food Chemistry, 2024, 460:140727.
[5] LUAN M Z, WANG H Y, WANG J Z, et al.Advances in anti-inflammatory activity, mechanism and therapeutic application of ursolic acid[J].Mini Reviews in Medicinal Chemistry, 2022, 22(3):422-436.
[6] KRASTEVA D, IVANOV Y, CHENGOLOVA Z, et al.Antimicrobial potential, antioxidant activity, and phenolic content of grape seed extracts from four grape varieties[J].Microorganisms, 2023, 11(2):395.
[7] TOFFALINI A, VIGOLO N, ROLLI N, et al.Association of low vitamin C concentrations and low consumption of fresh fruit and vegetables with cardiovascular disease in type 2 diabetes[J].BMC Nutrition, 2025, 11(1):68.
[8] 王晓霞, 马力通, 孙吉盛, 等.多光谱法和分子对接模拟法研究茶碱和胃蛋白酶的相互作用[J].光谱学与光谱分析, 2024, 44(3):714-721.
WANG X X, MA L T, SUN J S, et al.Study on the interaction between theophylline and pepsin by multispectral and molecular docking simulation[J].Spectroscopy and Spectral Analysis, 2024, 44(3):714-721.
[9] 尚永辉, 李子媛, 刘鑫雨, 等.抗坏血酸在多壁碳纳米管修饰玻碳电极上的电化学行为及其与DNA的相互作用[J].咸阳师范学院学报, 2021, 36(6):37-40;71.
SHANG Y H, LI Z Y, LIU X Y, et al.Electrochemical behavior of ascorbic acid on multi-walled nanotubes modified glassy carbon electrode and the intercation asarbic acid with DNA[J].Journal of Xianyang Normal University, 2021, 36(6):37-40;71.
[10] LU T, CHEN F W.Multiwfn:A multifunctional wavefunction analyzer[J].Journal of Computational Chemistry, 2012, 33(5):580-592.
[11] BRANDENBURG J G, BANNWARTH C, HANSEN A, et al.B97-3c:A revised low-cost variant of the B97-D density functional method[J].Journal of Chemical Physics, 2018, 148(6):064104.
[12] LEFEBVRE C, RUBEZ G, KHARTABIL H, et al.Accurately extracting the signature of intermolecular interactions present in the NCI plot of the reduced density gradient versus electron density[J].Physical Chemistry Chemical Physics, 2017, 19(27):17928-17936.
[13] LU T, CHEN Q X.Independent gradient model based on hirshfeld partition:A new method for visual study of interactions in chemical systems[J].Journal of Computational Chemistry, 2022, 43(8):539-555.
[14] 董志, 舒启江, 田爽, 等.黄芩苷与苦参碱分子间相互作用的量子化学计算与验证 [J].原子与分子物理学报, 2025(4):14-20.
DONG Z, SHU Q J, TIAN S, et al.Quantum chemical calculation and verification of the intermolecular interaction between baicalin and matrine [J].Journal of Atomic and Molecular Physics, 2025(4):14-20.
[15] EMAMIAN S, LU T, KRUSE H, et al.Exploring nature and predicting strength of hydrogen bonds:A correlation analysis between atoms-in-molecules descriptors, binding energies, and energy components of symmetry-adapted perturbation theory[J].Journal of Computational Chemistry, 2019, 40(32):2868-2881.
[16] 高莉, 任燕玲, 刘琳琳, 等.黑色素-纳米硒的制备及其性质[J].食品科学, 2023, 44(6):97-106.
GAO L, REN Y L, LIU L L, et al.Preparation and properties of melanin-nanoselenium complex[J].Food Science, 2023, 44(6):97-106.
[17] ALI H H, GHAREEB M M, AL-REMAWI M, et al.New insight into single phase formation of capric acid/menthol eutectic mixtures by Fourier-transform infrared spectroscopy and differential scanning calorimetry[J].Tropical Journal of Pharmaceutical Research, 2020, 19(2):361-369.
[18] MOTSHAKERI M, TRAVAS-SEJDIC J, PHILLIPS A R J, et al.Rapid electroanalysis of uric acid and ascorbic acid using a poly(3, 4-ethylenedioxythiophene)-modified sensor with application to milk[J].Electrochimica Acta, 2018, 265:184-193.
[19] TANG H, HU G Z, JIANG S X, et al.Selective determination of uric acid in the presence of ascorbic acid at poly(p-aminobenzene sulfonic acid)-modified glassy carbon electrode[J].Journal of Applied Electrochemistry, 2009, 39(12):2323-2328.
[20] CAI Z C, ZHU C, CHEN G Q, et al.Study on intermolecular hydrogen bond of uric acid water-clusters[J].Chemical Physics Letters, 2023, 818:140424.
