CN115304749B - 一种含邻苯二酚侧基的荧光共轭高分子及其制备方法 - Google Patents
一种含邻苯二酚侧基的荧光共轭高分子及其制备方法 Download PDFInfo
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- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 title claims abstract description 81
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Abstract
本发明公开了一种含邻苯二酚侧基的荧光共轭高分子及其制备方法。将二乙炔基单体、含邻苯二酚基团和含苯基的二溴芳烃单体通过Sonogashira偶联反应合成邻苯二酚侧基被保护的共轭高分子前驱体,再经四丁基氟化铵脱除保护基团,得到一种含邻苯二酚侧基的荧光共轭高分子。本发明将含有已保护邻苯二酚基团的多巴胺和含苯基的苯乙胺通过胺基与羧基之间形成酰胺键的形式引入到共轭聚合物的侧基,可通过调整两种二溴芳烃单体的投料比以及利用苯基的相对化学惰性,实现对邻苯二酚基团含量的精确调控,从而改变其粘附性能,在化学、生物成像、痕迹检验等领域具有应用潜力。
Description
技术领域
本发明涉及一种荧光共轭高分子材料及制备,特别涉及一种含邻苯二酚侧基的荧光共轭高分子及其制备方法。
背景技术
共轭聚合物具有饱和键和非饱和键形成的共轭体系,其中的共轭π电子受光激发从基态跃迁到激发态,再通过辐射跃迁产生荧光发射,或非辐射跃迁释放热能回到基态(参见文献:Chemical Society Reviews, 2020, 49, 8179-8234)。共轭聚合物作为荧光材料与其他小分子荧光团相比具有许多优点,如合成简便、化学结构和发射颜色可调、成本相对较低、毒性低、抗光漂白性强、机械稳定性好等(参见文献:Chemical Reviews, 2000, 100,1605-1644),因此被广泛地应用于生物成像、传感检测、防伪技术和法医学领域中。
多巴胺和苯乙胺是人体中重要的神经递质,且都被广泛地应用在药物中,多用于治疗精神疾病。多巴胺也存在于动物体内,如贻贝的足丝蛋白中被发现含有多巴胺结构,其结构中的邻苯二酚基团为贻贝在海洋环境中锚定在复杂潮湿的表面提供粘附力。受此启发,一些文献报道了将邻苯二酚基团用于工程材料,如胶粘剂(参见文献:Journal ofmaterials Science, 2016, 51, 4320-4327)。目前,关于将邻苯二酚基团引入到聚合物的侧基的报道不多。只有极个别研究将邻苯二酚基团引入到聚合物的侧基,通过交联反应提高聚合物和基材的粘附性能,同时保留聚合物的性能并应用于生物医学领域(参见文献:Chemical Engineering Journal, 2022, 427, 130910)。也有文献报道了用邻苯二酚基团修饰的噻吩单体通过Suzuki偶联反应合成共聚物,应用于生物成像和传感检测(参见文献:Advanced Functional Materials, 2013, 23, 764-769; Reactive and FunctionalPolymers, 2020, 153, 104616)。文献还报道了一种含邻苯二酚侧基的聚苯撑乙炔撑噻吩撑乙炔撑荧光共轭高分子(参见文献:ACS Applied Polymer Materials, 2021, 3, 4543-4553),其中有两种侧基是用不同方式保护的邻苯二酚基团,希望能够通过调整这两种侧基的比例并通过选择性脱保护的方式,实现侧基中邻苯二酚基团的含量的控制;但由于两种保护基化学性质相对不稳定,当环境中的pH值改变时不同的保护基都有可能会被脱去,因此在实际应用中邻苯二酚基团的含量比较难以实现真正的精准调控。综上,该荧光共轭高分子在化学、生物成像、痕迹检验方面的应用具有局限性。
近年来,苯乙胺作为间隔阳离子的配体被掺杂进钙钛矿材料中,一方面可以减少钙钛矿层间距离,达到增强电荷传输的效果;另一方面通过空间位阻和电子效应可以一定程度上避免水对钙钛矿材料性能的影响(参见文献:Adv. Funct. Mater. 2022, 32,2110392;Adv. Funct. Mater. 2019, 29, 1900221),这是利用了其结构中苯环的化学惰性和疏水性。然而将苯乙胺基团通过形成共价键的方式引入到共轭聚合物的侧基还未见报道。因此,将含有已保护邻苯二酚基团的多巴胺和苯乙胺基团通过胺基与羧基之间形成酰胺键的形式引入到共轭聚合物的侧基,并利用苯基的相对化学惰性实现对邻苯二酚基团含量的精确调控,以适应不同的场景具有重要的应用价值和实际意义。
发明内容
本发明针对现有技术存在的不足,提供一种侧基化学性质稳定、分子结构可调、合成简便且荧光明亮的含邻苯二酚侧基的荧光共轭高分子及其制备方法。
实现本发明的技术方案是提供一种含邻苯二酚侧基的荧光共轭高分子,它的结构式为:
,
其中,x为邻苯二酚侧基含量,x=0.1~0.3;(1-x)为苯基侧基含量,n为聚合度,n=8~21。
本发明技术方案还包括一种含邻苯二酚侧基的荧光共轭高分子的制备方法,步骤如下:
(1)按物质的量份数计,将1份记作化合物C1的羧酸化合物,1.5~2.8份1-(3-二甲氨基丙基)-3-乙基碳二亚胺盐酸盐,0.5~0.8份4-二甲氨基吡啶和880~900份二氯甲烷混合,在冰水浴中搅拌0.5~1 h,加入1.5~1.8份苯乙胺继续搅拌1.5~2 h,再加热回流12~24 h;反应结束后,置于室温下,经萃取、旋蒸、柱层析分离提纯和干燥,得到一种含苯基的二溴芳烃单体,记作M3;
所述化合物C1的结构式为:
;
所述单体M3的结构式为:
;
(2)按物质的量份数计,将记作M1的二乙炔基单体1份,记作M2的含邻苯二酚基团的二溴芳烃单体x份,x=0.1~0.3,步骤(1)制备的单体M3 (1-x)份, 0.15份的(PPh3)4Pd,0.03份的CuI和640份的甲苯混合,在温度为45~50℃的条件下搅拌至单体全部溶解,再加入1600份二异丙胺,加热回流24~48小时;反应结束后,冷却至室温,经过滤、重结晶、离心、干燥,得到一种共轭高分子前驱体,记作pre-P-catx;
所述单体M1的结构式为:
;
所述单体M2的结构式为:
;
所述前驱体pre-P-catx的结构式为:
,
其中,x为M2单体单元的含量,x=0.1~0.3;(1-x)为M3单体单元的含量;n为聚合度,n=8~21;
(3)按物质的量份数计,将1份步骤(2)制备的共轭高分子前驱体pre-P-catx和3500~3600份四氢呋喃混合,在冰水浴中缓慢滴加1.25~1.5份四丁基氟化铵与1100~1300份四氢呋喃的混合溶液,在常温条件下反应;反应结束后,经过滤、重结晶、离心、干燥,得到一种含邻苯二酚侧基的荧光共轭高分子。
本发明提供的含邻苯二酚侧基的荧光共轭高分子溶液,其邻苯二酚侧基与客体存在多种非共价相互作用。通过改变单体的投料比能精准地调控邻苯二酚侧基的含量,从而改变高分子的粘附性能,因此在化学、生物成像、痕迹检验等领域有极大的应用潜力。
与现有技术相比,本发明的有益效果在于:
1. 本发明制备的含邻苯二酚侧基的荧光共轭高分子的邻苯二酚侧基与客体存在多种非共价相互作用,如氢键、π-π电子效应、阳离子-π相互作用以及与金属阳离子存在配位作用。
2. 本发明制备的含邻苯二酚侧基的荧光共轭高分子将苯基通过苯乙胺与羧基形成共价键的方式引入到共轭聚合物的侧基,且苯基化学性质相对稳定,在酸性或碱性环境中都不易发生化学反应,在共轭聚合物的结构中对邻苯二酚基团的含量起到稀释作用。
3. 本发明提供的含邻苯二酚侧基的荧光共轭高分子的邻苯二酚侧基与苯基侧基除了最外端的化学结构不同外、其他结构完全一样,因此共聚相对溶液、对所得聚合物的溶解性和其他性质影响不大。通过调整含邻苯二酚侧基的单体(M2)和苯基侧基单体(M3)的比例,即通过控制反应投料比可以精确调控聚合物的分子结构;从而改变其粘附性能,尤其在痕迹检验领域有极大的应用前景。
4. 本发明提供的含邻苯二酚侧基的荧光共轭高分子在良溶剂中有明亮的黄绿色荧光,荧光量子效率均达到35%以上,在化学、生物成像、痕迹检验等领域有极大的应用潜力。
附图说明
图1是本发明实施例1提供的含苯基的二溴芳烃单体M3的合成路线图;
图2、3分别是本发明实施例1制备的含苯基的二溴芳烃单体M3的核磁谱图和红外谱图;
图4是本发明实施例2提供的含邻苯二酚侧基的荧光共轭高分子PPETE-catx的合成路线图;
图5、6分别是本发明实施例2制备的共轭高分子前驱体pre-P-catx的核磁谱图和红外谱图;
图7、8分别是本发明实施例2中制备的含邻苯二酚侧基的荧光共轭高分子PPETE-catx的核磁谱图和红外谱图;
图9是本发明实施例2制备的含邻苯二酚侧基的荧光共轭高分子PPETE-catx的光物理性能数据图。
具体实施方式
下面结合附图和实施例对本发明技术方案作进一步的阐述。
实施例1
本实施例提供含苯基基团的二溴芳烃单体及其制备方法。
在本实施例中,记作化合物C1的羧酸化合物的合成可参见文献(Journal ofcolloid and interface science, 2018, 528, 200-207)。具体方法是:在氩气气氛下,将己二酸(15 g,0.1 mol)、碳酸钾(10 g,72.35 mmol)和 N,N-二甲基甲酰胺(120 mL)加入250 mL圆底烧瓶中,将1,4-二溴-3-溴甲基噻吩(5.54 g,16.5 mmol)溶于适量N,N-二甲基甲酰胺加入体系中,45℃加热回流12 h。反应结束后抽滤,收集滤液,加入适量去离子水和二氯甲烷萃取分液,去除N,N-二甲基甲酰胺。收集有机相,经无水硫酸钠干燥后旋转蒸发,得到粗产物。粗产物经硅胶柱层析分离提纯,展开剂为石油醚/乙酸乙酯(V石油醚 : V乙酸乙酯 =3 : 1),得到黄色粘液状化合物C1(3.84 g,产率:58.1%)。
化合物C1的结构式为
。
参见附图1,是本实施例提供的记作单体M3的含苯基的二溴芳烃单体的合成路线图;单体M3的制备:在氩气气氛下,向250 mL圆底烧瓶中加入化合物C1(0.7 g,1.75 mmol)和二氯甲烷(100 mL)。然后加入1-(3-二甲氨基丙基)-3-乙基碳二亚胺盐酸盐(0.5 g,2.60mmol)和4-二甲氨基吡啶(0.1 g,0.82 mmol)在冰水浴中搅拌0.5 h。加入苯乙胺(0.33 g,2.70 mmol),继续在冰浴条件下搅拌2 h,然后加热回流24 h。反应结束后,分别用去离子水和饱和氯化钠溶液洗三次,经无水硫酸钠干燥后旋转蒸发去除溶剂得到粗产物。粗产物经硅胶柱层析分离提纯,展开剂为石油醚/乙酸乙酯(V石油醚 : V乙酸乙酯 = 5 : 1),得到白色粉末M3(0.67 g,产率:76%)。1H NMR (400 MHz, CDCl3): δ 7.32-7.18 (m, 5H), 6.96 (s,1H), 5.47 (s, 1H), 4.98 (s, 2H), 3.52 (m, 2H), 2.82 (t, 2H), 2.35 (m, 2H),2.14(m, 2H), 1.64 (m, 4H). Elemental Anal. Calcd for C19H21N1O3S1Br2(%): C,45.35; H, 4.21; N, 2.78; Found: C, 45.40; H, 4.32; N, 2.92. Elemental Anal.Calcd for C19H21N1O3S1Br2(%): C, 45.35; H, 4.21; N, 2.78; Found: C, 45.40; H,4.32; N, 2.92.
参见附图2和3,分别是本实施例提供的含苯基的二溴芳烃单体M3的核磁谱图和红外谱图,由图2和3可以看出,含苯基的二溴芳烃单体M3的结构与合成路线图1中所示结构是一致的。
实施例2
本实施例提供含邻苯二酚侧基的荧光共轭高分子及其制备方法。
在本实施例中,记作单体M1的二乙炔基单体合成可参见文献(ACS AppliedMaterials & Interfaces, 2014, 6, 5041-5049)。具体方法是:以对苯二酚为原料,在冰水浴中与液溴反应生成2,5-二溴对苯二酚;通过亲核取代反应、酯化反应引入长烷烃侧基;再通过偶联反应生成二乙炔基单体M1。
单体M1的结构式为:
。
在本实施例中,记作单体M2的原料合成可参见文献(ACS Applied PolymerMaterials, 2021, 3, 4543-4553)。具体方法是:在氩气气氛下,向250 mL圆底烧瓶中加入实施例1中提供的化合物C1(0.7 g,1.75 mmol)和二氯甲烷(100 mL)。然后加入1-(3-二甲氨基丙基)-3-乙基碳二亚胺盐酸盐(0.5 g,2.60 mmol)和4-二甲氨基吡啶(0.1 g,0.82mmol)在冰水浴中搅拌0.5 h。加入酚羟基被保护的盐酸多巴胺(1.03 g,2.7 mmol),继续在冰浴条件下搅拌2 h,再加热回流24 h。反应结束后,冷却至室温,然后分别用去离子水和饱和氯化钠溶液洗三次,经无水硫酸钠干燥后旋转蒸发去除溶剂得到粗产物。粗产物经硅胶柱层析分离提纯,展开剂为石油醚/乙酸乙酯(V石油醚 : V乙酸乙酯= 2 : 1),得到单体M2:黄色粘液(1.06 g,产率:82.6%)。
单体M2的结构式为:
。
参见附图4,为本实施例制备含邻苯二酚侧基的荧光共轭高分子的核磁路线图。
步骤1,前驱体聚合物记作pre-P-catx的制备:
以x = 0.2为例,x为M2单体单元的含量;在氩气气氛下,将单体M1(0.15 g,0.25mmol)、单体M2(0.039 g,0.05 mmol)、单体M3(0.10 g,0.20 mmol)、四(三苯基膦)钯(0.005g,0.0043 mmol)、碘化亚铜(0.0015 g,0.0079 mmol)和重蒸的甲苯(17 mL)加入到50 mL圆底烧瓶中,50℃搅拌至单体全部溶解。加入重蒸的二异丙胺(6 mL),升温至75℃回流48 h。反应结束后,冷却至室温,然后用孔径为0.22 μm的针头式滤器过滤混合液,旋转蒸发除去有机溶剂。用少量二氯甲烷溶解,然后滴入冷甲醇中(预先放置于冰箱中冷藏)使聚合物再沉淀。离心并倒去上层清液,收集固体沉淀并放入真空干燥箱充分干燥,得到红色固体pre-P-cat0.2(0.213 g,产率:84.8%)。1H NMR (400 MHz, CDCl3): δ 7.18-7.16 (m, 2H), 6.93(m, 1.5H), 6.73-6.64 (m, 1.5H), 5.62 (1H), 5.23-5.02 (m, 2H), 4.70 (m, 4H),4.22 (m, 4H), 3.50 (m, 2H), 2.77 (m, 2H), 2.37 (m, 2H), 2.12 (m, 2H), 1.64(m, 8H), 1.24 (m, 36H), 0.98 (s, 9H), 0.87 (t, 6H), 0.18 (s, 6H). ElementalAnal. Calcd for C59.4H82.6N1O9.4S1Si0.4(%):C, 71.01; H, 8.22; N, 1.39; Found: C,67.41; H, 8.67; N, 1.25. GPC: = 7,88 kDa; /> = 12.78 Da; PDI = 1.66, n=16。
调整两种二溴芳烃单体的投料比,以x = 0.1为例,分别采用M2(0.020 g,0.025mmol)、M3(0.11 g,0.22 mmol),按上述步骤1的方法,制备前驱体聚合物记作pre-P-cat0.1,得到pre-P-cat0.1(0.188 g,产率:78.2%)。1H NMR (400 MHz, CDCl3): δ 7.18-7.16 (m,2H), 6.93 (m, 1.5H), 6.73-6.64 (m, 1.5H), 5.63 (1H), 5.23-5.02 (m, 2H), 4.70(m, 4H), 4.22 (m, 4H), 3.50 (m, 2H), 2.79 (m, 2H), 2.36 (m, 2H), 2.11 (m,2H), 1.63 (m, 8H), 1.24 (m, 36H), 0.97 (s, 9H), 0.87 (t, 6H), 0.18 (s, 6H).Elemental Anal. Calcd for C59.4H82.6N1O9.4S1Si0.4(%):C, 71.44; H, 8.16; N, 1.43;Found: C, 67.01; H, 8.58; N, 1.25. GPC: = 7.63 kDa; /> = 11.50 Da; PDI= 1.51, n=16. 。
再以x = 0.3为例,分别采用M2(0.057 g,0.075 mmol)、M3(0.087 g,0.17 mmol),按上述步骤1的方法制备前驱体聚合物记作pre-P-cat0.3,得到pre-P-cat0.3(0.235 g,产率:92.8%)。1H NMR (400 MHz, CDCl3): δ 7.18-7.16 (m, 2H), 6.94 (m, 1.5H), 6.73-6.64 (m, 1.5H), 5.64 (1H), 5.23-5.02 (m, 2H), 4.70 (m, 4H), 4.20 (m, 4H),3.48 (m, 2H), 2.79 (m, 2H), 2.36 (m, 2H), 2.12 (m, 2H), 1.64 (m, 8H), 1.24(m, 36H), 0.97 (s, 9H), 0.87 (t, 6H), 0.18 (s, 6H). Elemental Anal. Calcd forC59.4H82.6N1O9.4S1Si0.4(%):C, 70.62; H, 8.29; N, 1.36; Found: C, 68.19; H, 8.66;N, 1.31. GPC: = 10.12 kDa; /> = 17.61 Da; PDI = 1.74, n=20. 。
步骤2,含邻苯二酚侧基的聚苯撑乙炔撑噻吩撑乙炔撑荧光共轭高分子聚合物记作PPETE-catx的制备:
以x = 0.2为例,在氩气气氛下,将前驱体聚合物pre-P-cat0.2(0.052 g,0.052mmol)和重蒸的四氢呋喃(15 mL)加入到50 mL圆底烧瓶中。将浓度为1 M的四丁基氟化铵的四氢呋喃溶液(0.065 mL)和重蒸的四氢呋喃(5 mL)加入恒压滴液漏斗中,在冰水浴下缓慢滴加,室温下反应0.5 h。反应结束后,加入稀盐酸至体系变黄,加入去离子水和二氯甲烷萃取分液,经无水硫酸钠干燥后,旋转蒸发去除溶剂。用少量二氯甲烷溶解,然后滴入冷甲醇中(预先放置于冰箱中冷藏)使聚合物再沉淀。离心并倒去上层清液,收集固体沉淀并放入真空干燥箱充分干燥,得到红色固体记作PPETE-cat0.2(0.044 g,产率:88.6%)。1H NMR(400 MHz, CDCl3): δ 7.18-7.16 (m, 2H), 6.92-6.66 (m, 3H), 5.62 (1H), 5.23-5.02 (m, 2H), 4.70 (m, 4H), 4.21 (m, 4H), 3.48 (m, 2H), 2.79 (m, 2H), 2.53-2.36 (m, 2H), 2.11 (m, 2H), 1.64 (m, 8H), 1.24 (m, 36H), 0.87 (t, 6H).Elemental Anal. Calcd for C57H77N1O9.4S1(%): C, 71.41; H, 8.03; N, 1.46; Found:C, 65.39; H, 7.88; N, 1.27. Φf=38% in THF. 。
同样,以x = 0.1为例,将前驱体聚合物pre-P-cat0.1按上述步骤2的方法制备得到PPETE-cat0.1(0.045 g,产率:88.9%)。1H NMR (400 MHz, CDCl3): δ 7.18-7.16 (m, 2H),6.94-6.68 (m, 3H), 5.64 (1H), 5.23-5.02 (m, 2H), 4.70 (m, 4H), 4.22 (m, 4H),3.50 (m, 2H), 2.79 (m, 2H), 2.54-2.37 (m, 2H), 2.12 (m, 2H), 1.65 (m, 8H),1.25 (m, 36H), 0.87 (t, 6H). Elemental Anal. Calcd for C57H77N1O9.4S1(%): C,71.65; H, 8.05; N, 1.47; Found: C, 67.90; H, 8.31; N, 1.30. Φf=35% in THF. 。
再以x = 0.3为例,将前驱体聚合物pre-P-cat0.3按上述步骤2的方法制备得到PPETE-cat0.3(0.050 g,产率:97.5%)。1H NMR (400 MHz, CDCl3): δ 7.18-7.16 (m, 2H),6.94-6.67 (m, 3H), 5.67 (1H), 5.23-5.02 (m, 2H), 4.71 (m, 4H), 4.22 (m, 4H),3.50 (m, 2H), 2.79 (m, 2H), 2.53-2.37 (m, 2H), 2.12 (m, 2H), 1.65 (m, 8H),1.25 (m, 36H), 0.87 (t, 6H). Elemental Anal. Calcd for C57H77N1O9.4S1(%): C,71.17; H, 8.00; N, 1.46; Found: C, 63.55; H, 7.80; N, 1.27. Φf=37% in THF. 。
参见附图5和6,分别是本实施例提供的前驱体聚合物pre-P-catx核磁谱图和红外谱图。
参见附图7和8,分别是本实施例提供的聚合物PPETE-catx的核磁谱图和红外谱图。
由图5~8证明了前驱体聚合物pre-P-catx及聚合物PPETE-catx的结构与合成路线图4中所示结构完全一致。
参见附图9,它是本实施例提供的聚合物PPETE-catx的光物理性能的表征图。由图9可知,聚合物PPETE-catx的最大吸收波长在435 nm左右,最大发射波长在485 nm左右。
Claims (2)
1.一种含邻苯二酚侧基的荧光共轭高分子,其特征在于它的结构式为:
,
其中,x为邻苯二酚侧基含量,x=0.1~0.3;(1-x)为苯基侧基含量,n为聚合度,n=8~21。
2.一种含邻苯二酚侧基的荧光共轭高分子的制备方法,其特征在于包括如下步骤:
(1)按物质的量份数计,将1份记作化合物C1的羧酸化合物,1.5~2.8份1-(3-二甲氨基丙基)-3-乙基碳二亚胺盐酸盐,0.5~0.8份4-二甲氨基吡啶和880~900份二氯甲烷混合,在冰水浴中搅拌0.5~1 h,加入1.5~1.8份苯乙胺继续搅拌1.5~2 h,再加热回流12~24h;反应结束后,冷却至室温,经萃取、旋蒸、柱层析分离提纯和干燥,得到一种含苯基的二溴芳烃单体,记作M3;
所述化合物C1的结构式为:
;
所述单体M3的结构式为:
;
(2)按物质的量份数计,将记作M1的二乙炔基单体1份,记作M2的含邻苯二酚基团的二溴芳烃单体x份,x=0.1~0.3,步骤(1)制备的单体M3 (1-x)份, 0.15份的(PPh3)4Pd,0.03份的CuI和640份的甲苯混合,在温度为45~50℃的条件下搅拌至单体全部溶解,再加入1600份二异丙胺,加热回流24~48小时;反应结束后,冷却至室温,经过滤、重结晶、离心、干燥,得到一种共轭高分子前驱体,记作pre-P-catx;
所述单体M1的结构式为:
;
所述单体M2的结构式为:
;
所述前驱体pre-P-catx的结构式为:
,
其中,x为M2单体单元的含量,x=0.1~0.3;(1-x)为M3单体单元的含量;n为聚合度,n=8~21;
(3)按物质的量份数计,将1份步骤(2)制备的共轭高分子前驱体pre-P-catx和3500~3600份四氢呋喃混合,在冰水浴中缓慢滴加1.25~1.5份四丁基氟化铵与1100~1300份四氢呋喃的混合溶液,在常温条件下反应;反应结束后,经过滤、重结晶、离心、干燥,得到一种含邻苯二酚侧基的荧光共轭高分子。
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