水溶性磷酸盐柱[5]芳烃与吖啶橙的络合行为

doi:10.11938/cjmr20202802

摘要/Abstract

摘要： 本文首先构建了水溶性磷酸盐柱[5]芳烃（PP5A）与阳离子荧光染料吖啶橙（AO）主-客体络合物.然后通过紫外光谱（UV）、红外吸收光谱（IR）、分子荧光光谱（MFS）、一维和二维核磁共振（NMR）波谱技术（包括¹H NMR和NOESY）研究了PP5A与AO的络合行为.此外，还研究了pH及两种表面活性剂——十二烷基硫酸钠（SDS）和十六烷基三甲基溴化铵（CTAB）对AO/PP5A络合体系的荧光强度的影响.最后，采用分子对接计算了PP5A与AO和CTAB的络合模式及络合能.研究表明，AO与PP5A形成1：1的主-客体络合物；在pH=3~11范围内，PP5A均能使AO的荧光强度发生减弱或淬灭；SDS和CTAB的加入并不会对AO/PP5A络合体系的荧光强度产生显著影响.AO与PP5A络合时产生的荧光强度变化可为荧光传感器的设计提供理论基础.

关键词: 络合, 分子对接, 水溶性磷酸盐柱[5]芳烃, 吖啶橙

Abstract: The host-guest complex of water-soluble phosphate salt pillar[5]arene (PP5A) and cationic fluorescent dye acridine orange (AO) was constructed, and studied with ultraviolet spectrum (UV), infrared absorption spectrum (IR), molecular fluorescence spectroscopy (MFS), and nuclear magnetic resonance (NMR) spectra (¹H NMR and NOESY). And then, the effect of pH and two surfactants, including sodium dodecyl sulfate (SDS) and cetyltrimethylammonium bromide (CTAB) on the fluorescence intensity of AO/PP5A complex system were investigated. Finally, the complexation mode and energy of PP5A with AO and CTAB were calculated by molecular docking. The results showed that AO and PP5A formed a 1:1 host-guest complex. PP5A reduced or quenched the fluorescence intensity of AO in the pH range of 3~11. The addition of SDS and CTAB did not affect the fluorescence intensity of AO/PP5A complex significantly. The fluorescence changes generated by AO and PP5A complexation can provide a theoretical basis for the design of fluorescence sensors.

Key words: complexation, molecular docking, water-soluble phosphate salt pillar[5]arene, acridine orange

中图分类号:

O482.53

保秋连, 杨云汉, 魏可可, 罗建萍, 古捷, 鲁佳佳, 杨丽娟. 水溶性磷酸盐柱[5]芳烃与吖啶橙的络合行为[J]. 波谱学杂志, 2020, 37(4): 469-483.

BAO Qiu-lian, YANG Yun-han, WEI Ke-ke, LUO Jian-ping, GU Jie, LU Jia-jia, YANG Li-juan. Complexation Analysis of Water-Soluble Phosphate Salt Pillar[5]arene with Acridine Orange[J]. Chinese Journal of Magnetic Resonance, 2020, 37(4): 469-483.

参考文献

[1] OGOSHI T, KANAI S, FUJINAMI S, et al. Para-bridged symmetrical pillar
[5] arenes:their synthesis and host-guest property[J]. J Am Chem Soc, 2008, 130(15):5022-5023.
[2] CHI X D, JI X F, HUANG F H, et al. A dual-responsive supra-amphiphilic polypseudorotaxane constructed from a water-soluble pillar
[7] arene and an azobenzene-containing random copolymer[J]. J Am Chem Soc, 2015, 137(4):1440-1443.
[3] YU G, ZHAO R, WU D, et al. Pillar
[5] arene-based amphiphilic supramolecular brush copolymer:fabrication, controllable self-assembly and application in self-imaging targeted drug delivery[J]. Polym Chem, 2016, 7(40):6178-6188.
[4] WEI T B, CHENG X B, Li H, et al. Novel functionalized pillar
[5] arene:synthesis, assembly and application in sequential fluorescent sensing for Fe³⁺ and F^- in aqueous media[J]. Rsc Adv, 2016, 6(25):20987-20993.
[5] CHEN J F, CHENG X B, LI H, et al. A copillar
[5] arene-based fluorescence "on-off-on" sensor is applied in sequential recognition of an iron cation and a fluoride anion[J]. New J Chem, 2017, 41(5):2148-2153.
[6] NOUJEIM N, ZHU K, VUKOTIC V N, et al.
[2] Pseudorotaxanes from t-shaped benzimidazolium axles and crown-8wheels[J]. Org Lett, 2012, 14(10):2484-2487.
[7] CHEN L, TIAN Y K, DING Y, et al. Multistimuli responsive supramolecular cross-linked networks on the basis of thebenzo-21-Crown-7/secondary ammonium salt recognition motif[J]. Macromolecules, 2012, 45(20):8412-8419.
[8] LI S J, HUANG J Y, COOK T R, et al. Formation of
[3] catenanes from 10 precursors via multicomponent coordination-driven self-assembly of metallarectangles[J]. J Am Chem Soc, 2013, 135(6):2084-2087.
[9] HAN Y, MENG Z, MA Y X, et al. Iptycene-derived crown ether hosts for molecular recognition and self-assembly[J]. Accounts Chem Res, 2014, 47(7):2026-2040.
[10] YANG Y H, DU Y, YING F X, et al. Inclusion behavior of naringenin/-cyclodextrin supramolecular complex[J]. Chinese J Magn Reson, 2019, 36(3):319-330. 杨云汉, 杜瑶, 应飞祥, 等. 柚皮素/β-环糊精超分子体系的包合行为[J]. 波谱学杂志, 2019, 36(3):319-330.
[11] DU Y, ZHOU S Y, YANG Y H, et al. Study on molecular recognition of pinocembrin with methylated-β-cyclodextrin[J]. Chinese J Anal Chem, 2019, 47(3):371-379. 杜瑶, 周树娅, 杨云汉, 等. 松属素与甲基化-β-环糊精的分子识别研究[J]. 分析化学, 2019, 47(03):371-379.
[12] DENG Y H, SU L N, PANG Y H, et al. Preparation, characterization and water solubility of Inclusion complexes of daidzein with amino-modified β-cyclodextrins[J]. Chinese J Anal Chem, 2017, 45(5):648-653. 邓颖慧, 苏丽娜, 庞艳华, 等. 大豆苷元与氨基修饰β-环糊精包合物的制备、表征及水溶性[J]. 分析化学, 2017, 45(5):648-653.
[13] LIU X B, LIN J L, WANG H, et al. Water-solubilization of acyclic cucurbiturils for arenes and aromatic aldehydes and the promotion for the generation of two hydrazine-based macrocycles[J]. Chinese J Org Chem, 2020, 40:663-668. 刘旭波, 林佳乐, 王辉, 等. 开环葫芦脲在水中对芳烃和芳醛的增溶和对腙大环形成的促进作用[J]. 有机化学, 2020, 40:663-668.
[14] MA J, ZHANG X Z, LIU S M. Characteristics of cucurbit
[8] uril host-guest Inclusion complexes and determination of thebinding constants of metal ions with cucurbit
[8] uril[J]. J Anal Sci, 2019, 35(1):41-46. 马军, 张雄志, 刘思敏. 葫芦
[8] 脲主客体包合物特性及对金属离子键合常数测定[J]. 分析科学学报, 2019, 35(1):41-46.
[15] GUO D S, LIU Y. Calixarene-based supramolecular polymerization in solution[J]. Chem Soc Rev, 2012, 41(18):5907.
[16] MA X Q, WANG Y, WEI T B, et al. A novel AIE chemosensor based on quinoline functionalized pillar
[5] arene for highly selective and sensitive sequential detection of toxic Hg²⁺ and CN^-[J]. Dyes Pigments. 2019, 164:279-286.
[17] YU G C, MA Y J, HAN C Y, et al. A sugar-functionalized amphiphilic pillar
[5] arene:synthesis, self-assembly in water, and application in bacterial cell agglutination[J]. J Am Chem Soc, 2013, 135(28):10310-10313.
[18] SI W, CHEN L, HU X B, et al. Selective artificial transmembrane channels for protons by formation of water wires[J]. Angew Chem Int Edit, 2011, 123(52):12772-12776.
[19] HU X B, CHEN Z, TANG G, et al. Single-molecular artificial transmembrane water channels[J]. J Am Chem Soc, 2012, 134(20):8384-8387.
[20] ZHANG F, MA J K, SUN Y, et al. Construction of a switchable nanochannel for protein transport via a pillar
[5] arene-based host-guest system[J]. Anal Chem, 2018, 90(13):8270-8275.
[21] DUAN Q P, CAO Y, LI Y, et al. pH-responsive supramolecular vesicles based on water-soluble pillar
[6] arene and ferrocene derivative for drug delivery[J]. J Am Chem Soc, 2013, 135(28):10542.
[22] CAO Y, HU X Y, LI Y, et al. Multistimuli-responsive supramolecular vesicles based on water-soluble pillar
[6] arene and saint complexation for controllable drug release[J]. J Am Chem Soc, 2014, 136(30):10762-10769.
[23] YU C, YAN L, HU X Y, et al. Supramolecular nanoparticles constructed by dox-based prodrug with water-soluble pillar
[6] arene for self-catalyzed rapid drug release[J]. Chem Mater, 2016, 27(3):1110-1119.
[24] XU Z Y, ZHANG Y C, LIN J L, et al. Supramolecular self-assembly applied for the design of drug delivery[J]. Systems Prog Chem, 2019, 11:1-10. 徐子悦, 张运昌, 林佳乐, 等. 药物输送体系构筑中的超分子组装策略[J]. 化学进展, 2019, 11:1-10.
[25] YU G C, YU W, SHAO L, et al. Fabrication of a targeted drug delivery system from a pillar
[5] arene-based supramolecular diblock copolymeric amphiphile for effective cancer therapy[J]. Adv Funct Mater, 2016, 26(48):1-9.
[26] YANG Y H, YANG J L, LU J J, et al. Preparation of cationic water-pillar
[5] arene modified zeolite and its adsorption to bromocresol purple[J]. Chinese J Anal Chem, 2019, 47(12):1922-1930. 杨云汉, 杨俊丽, 鲁佳佳, 等. 阳离子化柱
[5] 芳烃改性沸石对溴甲酚紫的吸附研究[J]. 分析化学, 2019, 47(12):1922-1930.
[27] LI P, ZHANG D W, JIA Q. Research advances in supramolecular macrocyclic compounds for dye adsorption[J]. Chinese J Chro, 2020, 38(3):297-306.李萍, 张大伟, 贾琼. 超分子大环化合物用于染料吸附的研究进展[J]. 色谱, 2020, 38(3):297-306.
[28] WAGNER B D, STOJANOVIC N, DAY A I, et al. Hostproperties of cucurbit
[7] uril:fluorescence enhancement of anilinon aphthalene ulfonates[J]. J Phys Chem B, 2003, 107:10741-10746.
[29] MOHANTY J, BHASIKUTTAN A C, NAU W M, et al. Host-guest complexation of neutral red with macrocyclic host molecules:contrasting pKa shifts and binding affinities for cucurbit
[7] uril and b-cyclodextrin[J]. J Phys Chem, 2006, 110:5132-5238.
[30] ZHOU Y Y, YU H P, ZHANG L, et al. Host properties of cucurbit
[7] uril:fluorescence enhancement of acridine orange[J]. J Incl Phenom Macro, 2008, 61(3,4):259-260.
[31] YANG M, LIU Q, TANG Q, et al. Water-soluble supramolecular fluorescent probe for sensing carbendazim and its application in living cell imaging[J]. Chem Res Chinese U, 2018, 39(12):2665-2672. 杨梅, 刘青, 唐青, 等. 水溶性超分子荧光探针对多菌灵的识别及细胞成像[J]. 高等学校化学学报, 2018, 39(12):2665-2672.
[32] LIU Q, YANG H R, WANG A J. Sensitive fluorescence method for the determination of levofloxacin in pharmaceuticals using bromate-bromide, methylene blue and β-cyclodextrin as reagents[J]. Anal Lab, 2012, 31(5):6-9. 刘奇, 杨红瑞, 王爱军. β-环糊精增敏亚甲基蓝荧光法测定左氧氟沙星[J]. 分析试验室, 2012, 31(5):6-9.
[33] LIN L B, GUO H Y, YANG F F, et al. Novel biscalix
[4] arene with large conjugated aromatic bridges:synthesis and complexation properties for dyes[J]. Chinese J Org Chem, 2016, 36(8):1863-1868. 林梁斌, 郭红玉, 杨发福, 等. 大共轭芳香基桥联双杯
[4] 芳烃的合成与染料配合性能[J]. 有机化学, 2016, 36(8):1863-1868.
[34] YAN Z X, GUO H Y, YANG F F, et al. Syntheses and dyes complexation properties of multiple-azo calix
[4] arene derivatives containing thiourea groups[J]. Chinese J Org Chem, 2016, 36(5):1088-1093. 严祯曦, 郭红玉, 杨发福, 等. 含硫脲基的多重氮杂杯
[4] 芳烃衍生物的合成与有机染料配合性能[J]. 有机化学, 2016, 36(5):1088-1093.
[35] QIAN X C, ZHOU X J, YANG L, et al. One-step and green strategy for exfoliation and stabilization of graphene by phosphate pillar
[6] arene and its application for fluorescence sensing of paraquat[J]. Microchem J, 2019, 150:104203.
[36] HUA B, SHAO L, ZHANG Z H, et al. Pillar
[6] arene/acridine orange host-guest complexes as colorimetric and fluorescence sensors for choline compounds and further application in monitoring enzymatic reactions[J]. Sensor Actuat B-Chem, 2018, 255:1430-1435.
[37] HU X Y, LIU X, ZHANG W, et al. Controllable construction of biocompatible supramolecular micelles and vesicles by water-soluble phosphate pillar[5,6] arenes for selective anti-cancer drug delivery[J]. Chem Mater, 2016, 28:3778.
[38] MORRIS G M, HUEY R, LINDSTROM W, et al. Autodock4 and autodocktools4:automated docking with selective receptor flexibility[J]. Comput Chem, 2009, 30:2785.
[39] VENKATESAN M, SATHIYANARAYANAN K I. Highly selective chemosensor for the detection of Ru³⁺ ion by fluorescentturn-on response and its bioimaging recognition in living cellsSens[J]. Sensor Actuat B-Chem, 2018, 18:267-373.
[40] XIAO X D, SHI L, GUO L H, et al. Determination of dopamine hydrochloride by host-guest interaction based on water-soluble pillar
[5] arene[J]. Spectrochim Acta A, 2017, 173:6.
[41] ZHOU Z G, YUAN Y Y, LIU H B, et al. An NMR study on prucalopride[J]. Chinese J Magn Reson, 2018, 35(1):119-127. 周中高, 元洋洋, 刘红波, 等. 普卡必利的NMR研究[J]. 波谱学杂志, 2018, 35(1):119-127.
[42] FAN H Y. Spectral analyses of a novel ibuprofen-phillygenin ester[J]. Chinese J Magn Reson, 2018, 35(1):98-108. 樊宏宇. 新型连翘脂素-布洛芬酯合物的波谱学数据解析[J]. 波谱学杂志, 2018, 35(1):98-108.