CN114149369B - 用于甲醛和pH双功能检测的荧光探针FAL1及其制备方法和应用 - Google Patents
用于甲醛和pH双功能检测的荧光探针FAL1及其制备方法和应用 Download PDFInfo
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Abstract
本发明属于化学检测领域,涉及甲醛和pH双功能检测试剂,特别是指基于萘酰亚胺衍生物的甲醛和pH双功能荧光分子及其制备方法和应用。通过荧光光谱仪研究了探针FAL1在DMSO/Tris‑HCl各种常见分析物的识别性能。研究结果表明:探针FAL1对甲醛具有专一的荧光识别性能,并能克服其他常见分析物的干扰,具有较宽泛的pH值适用范围。该探针对甲醛的最低检出限为38 nM,并通过加标回收试验成功的应用于自来水中检测甲醛;该探针对pH值的荧光发射响应在pH值为3‑8范围内,适用于生物体内酸碱度敏感的微环境中的pH标记,在环境检测和生物领域具有较强的实际应用价值。
Description
技术领域
本发明属于化学检测领域,涉及甲醛和pH双功能检测试剂,特别是指基于萘酰亚胺衍生物的甲醛和pH双功能荧光分子及其制备方法和应用。
背景技术
甲醛(FA)是一种无色气体,作为合成材料广泛应用于木材加工、纺织、建筑、地毯、保鲜纸和化工行业。环境中甲醛主要来自工业活动、食品防腐剂和建筑材料。甲醛是室内空气中普遍存在的污染物之一,由于其高反应性和毒性,容易引起DNA损伤、流泪、呕吐、打喷嚏、咳嗽、嗜睡和昏迷、阿尔茨海默病,甚至死亡。根据甲醛损害的明确证据,2004年国际癌症研究机构(IARC)将其归类为一类致癌物。然而,甲醛也自然存在于人类细胞和不同的生物体中。人体血液中内源性甲醛的浓度约为2–3 mg/L;在猴子和大鼠的血液中也发现了类似的结果。甲醛最近被用作代谢中间体和内源性产生的羰基物种,通过蛋白质N-去甲基化、DNA/RNA去甲基化或代谢物去甲基化在许多生物有机体中释放。例如,正常生理大脑中的甲醛浓度为0.2 mmol至0.4 mmol。在这个浓度下,甲醛通过DNA去甲基化循环和认知能力在记忆形成中起着至关重要的作用。鉴于这些对人类健康的重要影响,有必要开发一种快速、简单、低成本、高灵敏度的方法来检测环境、食品和生物***中的甲醛。
酸碱度(pH值)作为一种重要的酸度指标,在化学、生物学、生理学和环境科学中发挥着复杂而重要的作用。酸碱平衡是生物细胞存活的关键参数。例如,癌细胞中较高的细胞内pH值(≥7.4)和较低的细胞外pH值(∼6.7–7.1)与正常细胞(细胞内pH值∼ 7.2;细胞外pH值∼ 7.4)形成“反向”pH梯度,促进细胞增殖、癌细胞侵袭和逃避凋亡。细胞内pH值异常会导致整个细胞内pH值的稳态破坏,导致自由基产生、膜收缩破坏、细胞凋亡和坏死。此外,酸碱失调是癌细胞的一个共同特性,可能影响pH敏感化疗药物的摄取和疗效。因此,追踪酸性细胞器中的pH波动对于研究这些腔室中的正常细胞功能和活动至关重要。
近年来,小分子荧光探针由于其高选择性、高灵敏度和操作的简便化,被认为是检测环境和生物医学中各种离子和生物分子的有力分析工具。同时荧光探针还具有实验测定的多样性、对检测物的损伤小、可以实现无损检测等优点。已被广泛应用于检测环境和生物体系中的金属阳离子、阴离子、生物体内活性小分子等方面。与单一识别荧光探针不同,多功能荧光探针具有一个或多个识别位点, 能够识别多个分析物,或者对特定分析物进行动态成像,识别过程中伴随着荧光变化和识别体系溶液颜色变化。多功能荧光探针由于一个探针可以检测多个目标,有利于提高效率、降低成本而成为荧光探针领域的一个发展方向。因此,构建适合于环境、食品和医药中特定甲醛和pH双功能检测的小分子荧光探针受到了广泛关注。
发明内容
本发明提出基于萘酰亚胺衍生物的甲醛和pH双功能荧光分子及其制备方法和应用,合成的荧光探针能够专一灵敏的从多种常见分析物中高效识别甲醛和pH。
本发明的技术方案是这样实现的:
用于甲醛和pH双功能检测的荧光探针FAL1,其结构式如下:
。
上述的荧光探针FAL1的制备方法,其技术路线如下:
步骤如下:
(1)将4-溴-1,8-萘酐和二甲基二胺溶解于乙醇中,回流条件下搅拌反应,冷却至室温后析出大量固体,经抽滤得淡黄色固体即为中间体Ⅰ;
(2)将步骤(1)的中间体Ⅰ和水合肼水溶液溶解于乙二醇单甲醚溶液中,加热回流条件下反应完全,冷却至室温后,将混合溶液倒入纯净水中析出大量固体,抽滤并用乙二醇单甲醚洗涤所得固体,最终得到橙色固体即为荧光探针FAL1。
所述步骤(1)中4-溴-1,8-萘酐和二甲基二胺的物质的量比为1:(3-10)。
所述步骤(1)中加热回流反应时间为4-10小时,中间体Ⅰ的产率为40-70%。
所述步骤(2)中水合肼水溶液的质量分数为80%wt,中间体Ⅰ和水合肼的物质的量比为1:(4-16)。
所述步骤(2)中加热回流反应的时间为12-24小时。
所述步骤(2)中荧光探针FAL1的产率为30-60%。
上述的荧光探针FAL1在特异性识别并检测环境和生物体系中甲醛和pH的应用。
步骤为:将Tris-HCl缓冲溶液和二甲基亚砜等体积混合,得溶液A,然后向荧光比色皿中加入2940 μL的溶液A和30 μL的探针FAL1的DMSO溶液,再加入30 μL的待检测溶液,在440 nm处激发条件下,在荧光光谱仪上检测534 nm处的荧光发射强度。
所述Tris-HCl缓冲溶液的pH为7.4、浓度为10 mM,探针FAL1的DMSO溶液的浓度为1mM。
本发明具有以下有益效果:
(1)本申请所选用的荧光团萘酰亚胺衍生物分子结构具有较大的共轭体系,分子结构中存在着一个大的吸-供电子共轭体系,易受到光的照射而发生跃迁,从而产生很强的荧光,这类荧光分子具有原料简单易得、光化学稳定性强、较高的量子效率,易于进行化学修饰的优点。另外,该类探针识别甲醛后荧光发射波长在可见光区内、斯托克斯位移大(94nm)使得荧光探针FAL1具有背景干扰低、对生物样品的光损伤小、样品穿透性强、检测灵敏度高等诸多优点。
(2)本申请的探针FAL1识别甲醛的机理是探针FAL1分子结构中的氨基与甲醛发生特异性缩合反应生成席夫碱,分子内电荷发生重排,释放出荧光实现了对甲醛的特异性识别。作为对照,该探针不易于其他常见活性小分子物质发生反应,溶液体系荧光没有变化,从而实现了对甲醛的特异性识别。具体识别反应机理为:
;
通过高分辨质谱对探针FAL1识别甲醛后的最终产物进行了确证(附图8),实验结果表明,FAL1-HCHO正离子模式下理论计算值为311.1508, HR-MS结果显示为311.1501,高分辨质谱实验结果验证了识别机理。
(3)在440 nm处激发条件下,单独的探针FAL1 (10 µM)在pH值分别为3.0,3.5,4.0,4.5,5.0,5.5,6.0,6.5,7.0,7.5,8.0的混合溶液A1-A11中534 nm处具有荧光发射强度呈现较好的线性(R 2 =0.824),溶液体系荧光发射强度随着pH值增强逐渐降低,证明了该探针可以用于精确检测pH值变化。
(4)本申请的探针FAL1与pH响应的机理如下:
在DMSO-Tris-HCl溶液体系中,质子受体二甲氨基乙胺基团引入1,8-萘酸酐中,形成萘酰亚胺核心支架,具有光致电子转移(PET)效应的pH调控荧光开关。酸性条件下,探针结构中二甲氨基质子化导致光诱导电子转移作用受到抑制,荧光团释放出强烈的荧光;碱性条件下电子从供体转移到激发态荧光团,荧光团荧光淬灭。
附图说明
为了更清楚地说明本发明实施例或现有技术中的技术方案,下面将对实施例或现有技术描述中所需要使用的附图作简单地介绍,显而易见地,下面描述中的附图仅仅是本发明的一些实施例,对于本领域普通技术人员来讲,在不付出创造性劳动的前提下,还可以根据这些附图获得其他的附图。
图1为本发明的荧光探针FAL1核磁共振氢谱图。
图2为本发明的荧光探针FAL1核磁共振碳谱图。
图3为本发明的荧光探针FAL1高分辨质谱图。
图4为本发明的荧光探针FAL1荧光选择性图,激发波长440 nm。
图5为本发明的荧光探针FAL1识别甲醛的竞争性实验图,激发波长440 nm,发射波长534 nm。
图6为本发明的荧光探针FAL1识别甲醛的荧光滴定图,激发波长440 nm。
图7为本发明的荧光探针FAL1识别甲醛的最低检测限图,激发波长440 nm,发射波长534 nm。
图8为本发明的荧光探针FAL1识别甲醛的高分辨质谱验证机理图,测试溶剂为甲醇。
图9为本发明的荧光探针FAL1识别不同pH的荧光发射强度图,激发波长440 nm,发射波长534 nm。
具体实施方式
下面将结合本发明实施例,对本发明的技术方案进行清楚、完整地描述,显然,所描述的实施例仅仅是本发明一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有付出创造性劳动前提下所获得的所有其他实施例,都属于本发明保护的范围。
实施例1
用于甲醛和pH双功能检测的荧光探针FAL1的制备方法,具体步骤为:
(1)中间体1的制备方法为:将4-溴-1,8-萘酐(2.77 g, 10 mmol)和二甲基二胺(2.644 g, 30 mmol)溶解于乙醇(50 mL)中,回流条件下搅拌反应4小时,冷却至室温后析出大量固体,抽滤得到1.384g淡黄色固体即为中间体1,产率40%;
(2)探针FAL1的制备方法为:将中间体1(347.2 mg,1 mmol)和80%水合肼(363 μL,6 mmol)溶解于乙二醇单甲醚(15 mL)溶液中,加热回流条件下反应15小时,冷却至室温后,将混合溶液倒入纯净水中析出大量固体,抽滤并用乙二醇单甲醚洗涤所得固体,最终得到149 mg橙色固体即为用于甲醛检测的荧光探针FAL1,产率50%。
核磁共振氢谱测定:1H NMR (DMSO-d 6 , 400 MHz) δ 2.19 (s, 6 H), 3.35 (s, 2H), 4.10 (s, 2 H), 4.66 (s, 2 H), 7.22 (s, 1 H), 7.60 (s, 1 H), 8.26 (s, 1H), 8.37 (s, 1 H), 8.58 (s, 1 H), 9.11 (s, 1 H)。
核磁共振碳谱测定:13C NMR (DMSO-d 6 , 100 MHz) δ 37.62, 45.87, 57.16,104.42, 107.76, 118.85, 122.12, 124.53, 128.69, 129.75, 131.02, 134.67,153.63, 163.32, 164.22。
高分辨质谱测定:HR-ESI-MS calcd for C16H19N4O2 +: 299.1508, found299.1505 [M+H+]+。
实施例2
用于甲醛和pH双功能检测的荧光探针FAL1的制备方法,具体步骤为:
(1)中间体1的制备方法为:将4-溴-1,8-萘酐(2.77 g, 10 mmol)和二甲基二胺(3.525 g, 40 mmol)溶解于乙醇(50 mL)中,回流条件下搅拌反应6小时,冷却至室温后析出大量固体,抽滤得到1.73 g淡黄色固体即为中间体1,产率50%;
(2)探针FAL1的制备方法为:将中间体1(347.2 mg,1 mmol)和80%水合肼(242 μL,4 mmol)溶解于乙二醇单甲醚(15 mL)溶液中,加热回流条件下反应12小时,冷却至室温后,将混合溶液倒入纯净水中析出大量固体,抽滤并用乙二醇单甲醚洗涤所得固体,最终得到89.4 mg橙色固体即为用于甲醛检测的荧光探针FAL1,产率30%。
核磁共振氢谱测定:1H NMR (DMSO-d 6 , 400 MHz) δ 2.19 (s, 6 H), 3.35 (s, 2H), 4.10 (s, 2 H), 4.66 (s, 2 H), 7.22 (s, 1 H), 7.60 (s, 1 H), 8.26 (s, 1H), 8.37 (s, 1 H), 8.58 (s, 1 H), 9.11 (s, 1 H)。
核磁共振碳谱测定:13C NMR (DMSO-d 6 , 100 MHz) δ 37.62, 45.87, 57.16,104.42, 107.76, 118.85, 122.12, 124.53, 128.69, 129.75, 131.02, 134.67,153.63, 163.32, 164.22。
高分辨质谱测定:HR-ESI-MS calcd for C16H19N4O2 +: 299.1508, found299.1505 [M+H+]+。
实施例3
用于甲醛和pH双功能检测的荧光探针FAL1的制备方法,具体步骤为:
(1)中间体1的制备方法为:将4-溴-1,8-萘酐(2.77 g, 10 mmol)和二甲基二胺(7.05 g, 80 mmol)溶解于乙醇(50 mL)中,回流条件下搅拌反应8小时,冷却至室温后析出大量固体,抽滤得到2.08 g淡黄色固体即为中间体1,产率60%;
(2)探针FAL1的制备方法为:将中间体1(347.2 mg,1 mmol)和80%水合肼(484 μL,8 mmol)溶解于乙二醇单甲醚(15 mL)溶液中,加热回流条件下反应10小时,冷却至室温后,将混合溶液倒入纯净水中析出大量固体,抽滤并用乙二醇单甲醚洗涤所得固体,最终得到119.2 mg橙色固体即为用于甲醛检测的荧光探针FAL1,产率40%。
核磁共振氢谱测定:1H NMR (DMSO-d 6 , 400 MHz) δ 2.19 (s, 6 H), 3.35 (s, 2H), 4.10 (s, 2 H), 4.66 (s, 2 H), 7.22 (s, 1 H), 7.60 (s, 1 H), 8.26 (s, 1H), 8.37 (s, 1 H), 8.58 (s, 1 H), 9.11 (s, 1 H)。
核磁共振碳谱测定:13C NMR (DMSO-d 6 , 100 MHz) δ 37.62, 45.87, 57.16,104.42, 107.76, 118.85, 122.12, 124.53, 128.69, 129.75, 131.02, 134.67,153.63, 163.32, 164.22。
高分辨质谱测定:HR-ESI-MS calcd for C16H19N4O2 +: 299.1508, found299.1505 [M+H+]+。
实施例4
用于甲醛和pH双功能检测的荧光探针FAL1的制备方法,具体步骤为:
(1)中间体1的制备方法为:将4-溴-1,8-萘酐(2.77 g, 10 mmol)和二甲基二胺(8.813 g, 100 mmol)溶解于乙醇(50 mL)中,回流条件下搅拌反应10小时,冷却至室温后析出大量固体,抽滤得到2.42 g淡黄色固体即为中间体1,产率70%;
(2)探针FAL1的制备方法为:将中间体1(347.2 mg,1 mmol)和80%水合肼(968 μL,16 mmol)溶解于乙二醇单甲醚(15 mL)溶液中,加热回流条件下反应24小时,冷却至室温后,将混合溶液倒入纯净水中析出大量固体,抽滤并用乙二醇单甲醚洗涤所得固体,最终得到178.8 mg橙色固体即为用于甲醛检测的荧光探针FAL1,产率60%。
核磁共振氢谱测定:1H NMR (DMSO-d 6 , 400 MHz) δ 2.19 (s, 6 H), 3.35 (s, 2H), 4.10 (s, 2 H), 4.66 (s, 2 H), 7.22 (s, 1 H), 7.60 (s, 1 H), 8.26 (s, 1H), 8.37 (s, 1 H), 8.58 (s, 1 H), 9.11 (s, 1 H)。
核磁共振碳谱测定:13C NMR (DMSO-d 6 , 100 MHz) δ 37.62, 45.87, 57.16,104.42, 107.76, 118.85, 122.12, 124.53, 128.69, 129.75, 131.02, 134.67,153.63, 163.32, 164.22。
高分辨质谱测定:HR-ESI-MS calcd for C16H19N4O2 +: 299.1508, found299.1505 [M+H+]+。
实施效果例
荧光选择性实验:
配制pH为7.4、浓度为10 mM的Tris-HCl缓冲溶液,用上述缓冲溶液和二甲基亚砜(DMSO)配置体积比为1:1的混合溶液A,并用DMSO配制浓度为1 mM的探针FAL1溶液。用荧光光谱仪考察了探针FAL1对甲醛和其他常见小分子分析物在混合溶液A中的选择性。如图4所示,在440 nm处激发条件下,单独的探针FAL1 (10 µM)在混合溶液A中并在室温条件下在534 nm处具有微弱的荧光发射强度。同等条件下,当加入甲醛(100 µM)后,在534 nm处的荧光发射强度明显增强,但是加入其它活性小分子(各类醛类、氨基酸类、过氧化物等)(100 µM) 时,溶液体系的荧光发射强度与单独探针体系的荧光发射强度相比没有明显变化。以上实验结果表明,探针FAL1对甲醛在混合溶液A中具有较好的荧光专一选择性。
抗干扰性实验:
配制pH为7.4、浓度为10 mM的Tris-HCl缓冲溶液,用上述缓冲溶液和二甲基亚砜(DMSO)配置体积比为1:1的混合溶液A,并用DMSO配制浓度为1 mM的探针FAL1溶液。用荧光光谱仪考察了探针FAL1在其他活性小分子存在的条件下对甲醛在混合溶液A中的竞争选择性实验。在20个干净的荧光比色皿中,分别加入2940 μL的混合溶液A和30 μL的探针FAL1的DMSO溶液,再分别加入10个摩尔当量的甲醛和10个摩尔当量的其他分析物(各类醛类、氨基酸类、过氧化物等),在荧光光谱仪上检测,在440 nm处激发条件下,绘制不同分析物对应的534 nm荧光强度的柱状图,得到荧光发射柱状图(附图5)。
经实验证明,探针FAL1对甲醛在混合溶液A中的识别不受上述其他分析物的干扰,具有较好的抗干扰性。
最低检出限实验:
良好的检出限是衡量荧光探针是否具有实际应用价值的重要标准之一。配制pH为7.4、浓度为10 mM的Tris-HCl缓冲溶液,用上述缓冲溶液和二甲基亚砜(DMSO)配置体积比为1:1的混合溶液A,并用DMSO配制浓度为1 mM的探针FAL1溶液。固定探针FAL1浓度为10 µM,测定其对不同浓度的甲醛的荧光发射响应强度,随着甲醛浓度的增加,体系荧光发射强度在534 nm处不断增强(附图6),研究发现溶液荧光发射强度在甲醛浓度为0.1-0.7 µM间呈线性(R 2 = 0.995)(附图7),经计算(3σ/k)得出该探针分子对甲醛的检出限为38 nM。
酸碱度作用范围实验:
配制pH分别为3.0,3.5,4.0,4.5,5.0,5.5,6.0,6.5,7.0,7.5,8.0浓度为10 mM的Tris-HCl缓冲溶液,用上述缓冲溶液和DMSO配置体积比为1:1的混合溶液A1, A2, A3, A4,A5, A6, A7, A8, A9, A10, A11 并用DMSO配制浓度为1 mM的探针FAL1溶液。用荧光光谱仪考察了单独探针FAL1 (10 µM)在混合溶液A1-A11中的荧光发射强度。如图9所示,在440nm处激发条件下,单独的探针FAL1 (10 µM)在pH值分别为3.0,3.5,4.0,4.5,5.0,5.5,6.0,6.5,7.0,7.5,8.0的混合溶液A1-A11中534 nm处具有荧光发射强度呈现较好的线性(R 2 =0.824),溶液体系荧光发射强度随着pH值增强逐渐降低,证明了该探针可以用于精确检测pH值变化。
实际水中分析应用
为了进一步考察探针FAL1在实际样品中的应用价值,将探针应用于城市自来水中进行加标回收试验。控制实验条件保持一致,在自来水样品中分别添加入不同浓度的甲醛(0.8 µM、1.0 µM、1.2 µM),通过工作曲线测算出相应的甲醛浓度(0.651 µM、0.836 µM、0.948 µM),回收率均在80 %~120%之间(见表1):
表1自来水中甲醛的添加回收检测结果
*平均数 ± 标准偏差
该检测结果充分体现该探针在实际的城市自来水样品中检测甲醛的实际应用价值。
以上所述仅为本发明的较佳实施例而已,并不用以限制本发明,凡在本发明的精神和原则之内,所作的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
Claims (7)
1.荧光探针FAL1在特异性、非疾病诊断和治疗为目的的识别并检测环境和生物体系中pH的应用,其特征在于:所述荧光探针FAL1结构式如下:
;
检测步骤为:将Tris-HCl缓冲溶液和二甲基亚砜等体积混合,得溶液A,然后向荧光比色皿中加入2940 μL的溶液A和30 μL的探针FAL1的DMSO溶液,再加入30 μL的待检测溶液,在440 nm处激发条件下,于荧光光谱仪上检测534 nm处的荧光发射强度。
2.根据权利要求1的应用,其特征在于,所述荧光探针FAL1的制备方法如下:
(1)将4-溴-1,8-萘酐和N,N-二甲基乙二胺溶解于乙醇中,回流条件下搅拌反应,冷却至室温后析出大量固体,经抽滤得淡黄色固体即为中间体Ⅰ;
(2)将步骤(1)的中间体Ⅰ和水合肼水溶液溶解于乙二醇单甲醚溶液中,加热回流条件下反应完全,冷却至室温后,将混合溶液倒入纯净水中析出大量固体,抽滤并用乙二醇单甲醚洗涤所得固体,最终得到橙色固体即为荧光探针FAL1。
3.根据权利要求2的应用,其特征在于:所述步骤(1)中4-溴-1,8-萘酐和N,N-二甲基乙二胺的物质的量比为1:(3-10)。
4.根据权利要求3的应用,其特征在于:所述步骤(1)中加热回流反应时间为4-10小时。
5.根据权利要求4的应用,其特征在于:所述步骤(2)中水合肼水溶液的质量分数为80%wt,中间体Ⅰ和水合肼的物质的量比为1:(4-16)。
6.根据权利要求5的应用,其特征在于:所述步骤(2)中加热回流反应的时间为12-24小时。
7.根据权利要求1所述的应用,其特征在于:所述探针FAL1DMSO溶液的浓度为1 mM。
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