CN113354956A - 一种氧醚链连接的近红外双方酸染料及其制备与应用 - Google Patents
一种氧醚链连接的近红外双方酸染料及其制备与应用 Download PDFInfo
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Abstract
本发明公开了一种氧醚链连接的近红外双方酸染料及其制备与应用,其是以氧醚链连接的2‑甲基苯并噻唑衍生物以及二氰乙烯基修饰的半方酸衍生物为原料制得。该近红外双方酸染料具有较好的稳定性及优异的光学性能,尤其是磺酸基团和氧醚链的引入可增强染料的水溶性。将该近红外双方酸染料用于G‑四联体的检测时,G‑四联体可与该染料分子相互作用,在不引起G‑四联体拓扑结构改变的同时引发染料吸收光谱和荧光光谱的改变,从而使其可作为G‑四联体检测的荧光探针。
Description
技术领域
本发明属于分析化学领域,具体涉及一种氧醚链连接的近红外双方酸染料及其制备方法与其在G-四联体荧光检测中的应用。
背景技术
G-四联体DNA(以下简称为G-四联体)的研究起源于1958年,研究人员从poly(rI)的X射线衍射结果推测:碱基通过氢键形成了一个环状结构,由此推断可能是产生了三螺旋或四螺旋结构,随后证实为四螺旋结构。进一步的研究发现poly(rG)也能形成类似的四螺旋结构(方晔. 四螺旋DNA[J]. 生命的化学, 1994, 014(002): 18–19.)。在真核生物染色体末端,含有较为简单的、串联的DNA重复序列,即所谓的调聚序列,在调聚序列的真正末端,含有一个富含鸟嘌呤的单链DNA尾巴,它在体内的超螺旋应力作用下,可自身回折形成Hoogsteen G-G碱基配对,两个DNA分子或者染色体分子可以彼此连接起来形成一个局部的四联体结构。四个碱基在一个正方形平面内通过氢键彼此配对形成一个四碱基体,由于这四个碱基皆为鸟嘌呤,故将其称为G-四分体,在G-四分体中,其中心有四个带负电的羟基氧原子围成的“口袋”,被认为是与阳离子相互作用的位点(刘定燮, 王昌才. DNA的G-四联体螺旋结构[J]. 生命的化学, 1997, 017(002): 2–4.)。一般来说,G-四联体是由两个或两个以上的G-四分体组成的。
方酸染料是一种具有缺电子中心四元环母核的共振稳定的两性离子结构的有机染料。该类型染料于1965年被Triebs和Jacob首次合成。方酸染料是由高度缺乏电子的方酸核衍生出来的,在四元环的完全相反的两侧有供电子的芳香族或杂环化合物,在近红外波段具有很强的吸收和发射能力。现如今,中心四元环两侧芳香族或杂环化合物的种类越来越丰富,致使方酸染料的用途也越来越广泛。人们不仅仅局限于改变中心四元环两侧连接的供电子基团去调整方酸染料的性质,还会利用亲核基团修饰中心四元环,以改善方酸染料的光化学性质。本发明即是利用二氰乙烯基修饰中心四元环,以改善染料的光化学性质,使方酸染料具有极强的吸收带,高的摩尔吸收系数,在近红外波段吸收窄,光稳定性优异。同时,通过对方酸染料的结构进行优化,合成了氧醚链连接的双方酸染料,增强了其水溶性,将其应用在G-四联体荧光检测中,具有良好的发展前景。
发明内容
本发明的目的在于提供一种氧醚链连接的近红外双方酸染料及其制备方法与其在G-四联体荧光检测中的应用。
为了实现上述目的,本发明采用如下的技术方案:
一种氧醚链连接的的近红外双方酸染料,其结构式如下:
近红外双方酸染料的制备方法包括以下步骤:
(2)反应结束后冷却至室温,减压除去溶剂,得粗产品;
(3)将所得粗产品经硅胶柱层析纯化,得到所述的近红外方酸染料;
其中,步骤(1)中所用氧醚链连接的2-甲基苯并噻唑衍生物和二氰乙烯基修饰的半方酸衍生物的摩尔比为1:2;所述溶剂为正丁醇、甲苯、吡啶按体积比10:10:1组成的混合溶液,所述回流反应的温度为145℃,时间为36小时;
步骤(3)所述硅胶柱层析采用体积比为5:1的二氯甲烷-甲醇混合溶液作为洗脱剂。
进一步地,所述氧醚链连接的2-甲基苯并噻唑衍生物的合成方法为:将四乙二醇双(对甲苯磺酸酯)与2-甲基苯并噻唑按摩尔比1:2混合,在通入氮气的条件下150℃加热反应24小时,反应结束后冷却至室温,过滤,用甲醇溶解所得固体后,经硅胶柱层析纯化得到目标产物;其中,所述硅胶柱层析采用体积比为7:1的二氯甲烷-甲醇混合溶液作为洗脱剂。
进一步地,所述二氰乙烯基修饰的半方酸衍生物的合成方法为:将半方酸衍生物、丙二腈、三乙胺以摩尔比1:1:1混合,然后加入溶剂,35℃反应6小时,反应结束后冷却至室温,抽滤除去固体后,旋蒸除去溶剂,所得物质经硅胶柱层析纯化得到目标产物;其中,所用溶剂为苯和甲醇以体积比2:1组成的混合溶液,所用丙二腈与苯的摩尔比为1:28.2;所述硅胶柱层析采用体积比为10:1的二氯甲烷-甲醇混合溶液作为洗脱剂。
进一步地,所述半方酸衍生物的合成方法为:将方酸二乙酯、磺酸基团修饰的2-甲基苯并噻唑衍生物以及三乙胺按摩尔比1:1:1混合后加入溶剂,30℃反应10小时,反应结束后冷却至室温,旋蒸除去溶剂,所得物质经硅胶柱层析纯化得到产物;其中,所述溶剂为无水乙醇;所述硅胶柱层析采用体积比为15:1的二氯甲烷-甲醇混合溶液作为洗脱剂。
同时,所述方酸二乙酯的合成方法包括如下步骤:
a)将方酸溶于溶剂中,加热回流反应3小时;
b)旋蒸除去溶剂,再加入溶剂加热回流反应30分钟;
c)重复步骤b)三次,反应结束冷却至室温;
d)所得产物经硅胶柱层析纯化,得到所述方酸二乙酯;
其中,所用溶剂为乙醇,回流反应的温度为80℃;所述硅胶柱层析采用体积比为2:1的石油醚-乙酸乙酯混合溶液作为洗脱剂。
所述磺酸基团修饰的2-甲基苯并噻唑衍生物的合成方法为:将2-甲基苯并噻唑与1,3-丙磺酸内酯按摩尔比1:2.48混合后,加入无水乙腈,在通入氮气的条件下100℃反应15小时,反应结束后冷却至室温,抽滤除去溶液,所得白色物质用二氯甲烷洗涤,干燥,得到白色粉末。
上述所得氧醚链连接的近红外双方酸染料可作为荧光响应的G-四联体探针,用于溶液中G-四联体的荧光检测。
本发明将氧醚链连接的2-甲基苯并噻唑衍生物以及磺酸基团修饰的2-甲基苯并噻唑衍生物连接到二氰乙烯基方酸骨架上,得到了一种氧醚链连接的对称型近红外双方酸染料。其中,氧醚链和磺酸基团的引入大大提高了染料的水溶性,二氰乙烯基的引入能提升染料的光稳定性。同时二氰乙烯基能使染料具有顺式构象,这种V型构象能提升染料对平行G-四联体的选择性。当染料单独存在于水溶液中时,处于H-聚集状态,此时荧光猝灭,一旦加入G-四联体,则会与之相互作用,染料解聚集,荧光恢复,从而实现对G-四联体的检测。
本发明所得的双方酸染料合成简单,对G-四联体有较好的选择性,且在检测G-四联体的同时不会破坏G-四联体的拓扑结构,即便在存在大量单链DNA的缓冲溶液中,也能选择性地与平行G-四联体结合,能很好地区分G-四联体与单、双链DNA。利用荧光滴定实验得出,该染料对G-四联体的检测限为7.2-52 nM。
附图说明
图1为在氧醚链连接的双方酸染料(5 μM)的缓冲溶液中滴加不同浓度(0-20 μM)DNA时的吸收光谱图。
图2为在氧醚链连接的双方酸染料(5 μM)的缓冲溶液中滴加不同浓度(0-20 μM)DNA时的荧光光谱图(λex= 680 nm, slit= 5 nm/ 5 nm, PMT= 650 V)。
图3-1为氧醚链修饰的双方酸染料(5 μM)在715 nm处的荧光强度与pu22浓度的线性关系图(λex= 680 nm, slit= 5 nm/ 5 nm, PMT= 650 V);
图3-2为氧醚链修饰的双方酸染料(5 μM)在715 nm处的荧光强度与pu27浓度的线性关系图(λex= 680 nm, slit= 5 nm/ 5 nm, PMT= 650 V);
图3-3为氧醚链修饰的双方酸染料(5 μM)在715 nm处的荧光强度与pu18浓度的线性关系图(λex= 680 nm, slit= 5 nm/ 5 nm, PMT= 650 V);
图3-4为氧醚链修饰的双方酸染料(5 μM)在715 nm处的荧光强度与bcl-22345浓度的线性关系图(λex= 680 nm, slit= 5 nm/ 5 nm, PMT= 650 V);
图3-5为氧醚链修饰的双方酸染料(5 μM)在715 nm处的荧光强度与G4TTA浓度的线性关系图(λex= 680 nm, slit= 5 nm/ 5 nm, PMT= 650 V);
图3-6为氧醚链修饰的双方酸染料(5 μM)在715 nm处的荧光强度与22CTA浓度的线性关系图(λex= 680 nm, slit= 5 nm/ 5 nm, PMT= 650 V);
图3-7为氧醚链修饰的双方酸染料(5 μM)在715 nm处的荧光强度与Bom17浓度的线性关系图(λex= 680 nm, slit= 5 nm/ 5 nm, PMT= 650 V)。
图4为1小时内氧醚链连接的双方酸染料(5 μM)溶液中加入平行G-四联体pu22(20μM)后715 nm处的荧光强度随时间变化图(λex= 680 nm, slit= 5 nm/ 5 nm, PMT= 650V)。
图5为不同比例氧醚链连接的双方酸染料与平行G-四联体pu22 (2.5 µM)的圆二色谱图(λex= 680 nm, slit= 5 nm/ 5 nm, PMT= 650 V)。
图6为氧醚链连接的双方酸染料与不同G-四联体的Job’s plot图(λex= 680 nm,slit= 5 nm/ 5 nm, PMT= 650 V)。
图7为氧醚链连接的双方酸染料(2 μM)中加入平行G-四联体pu22(4 μM)后在715nm波长处的荧光强度随体系中单链DNA ss-SCR浓度的变化图(λex= 680 nm, slit= 5nm/ 5 nm, PMT= 650 V)。
具体实施方式
为了使本发明所述的内容更加便于理解,下面结合具体实施方式对本发明所述的技术方案做进一步的说明,但是本发明不仅限于此。
实施例1
在50 mL圆底烧瓶中先加入20 mL乙醇,再加入方酸(2.00 g,17.5 mmol),80℃下回流反应3小时,待方酸全部溶解后减压旋蒸除去乙醇。再次加入20 mL乙醇于烧瓶中,回流0.5小时,旋蒸除去溶剂,如此反复操作三次。反应结束后,用硅胶柱层析分离,洗脱剂为石油醚-乙酸乙酯(2:1,v/v)混合溶液,得到浅黄色油状液体产物:2.09 g,产率为70%。1H NMR(400 MHz, CDCl3) δ 4.74 (q, J=7.1 Hz, 4H), 1.48 (t, J=7.1 Hz, 6H)。
实施例2
在25mL二口瓶中加入2-甲基苯丙噻唑(720 mg,4.83 mmol),1,3-丙磺酸内酯(1.47 g,12.0 mmol),5 mL乙腈,通氮气10分钟后,于100℃条件下回流反应15小时。反应结束,有白色物质析出,反应液冷却至室温,抽滤,用二氯甲烷多次洗涤白色物质,再置于真空干燥箱过夜,得目标物的白色粉末:916 mg,产率为70%。1H NMR (400 MHz, d6-DMSO) δ8.43 (d, J = 7.7 Hz, 2H), 7.91 (t, J = 7.8 Hz, 1H), 7.81 (t, J = 7.7 Hz, 1H),4.93 (d, J = 16.0 Hz, 2H), 3.22 (s, 3H), 2.65 (t, J = 6.4 Hz, 2H), 2.18 (dt,J = 14.1, 7.2 Hz, 2H)。
实施例3
于50 mL二口瓶中加入方酸二乙酯(403 mg,2.37 mmol),磺酸基团修饰的2-二甲基苯并噻唑(642 mg,2.37 mmol),3 mL无水乙醇,三乙胺(237 mg,2.37 mmol),30℃反应10小时。TLC薄层色谱追踪,反应结束后冷却至室温,旋蒸除去溶剂,所得物质用硅胶柱层析分离,洗脱剂为二氯甲烷-甲醇(15:1,v/v)混合溶液,得黄色固体:472 mg,产率为80%。1H NMR(400 MHz, d6-DMSO) δ 7.80 (d, J = 7.7 Hz, 1H), 7.59 (d, J = 8.2 Hz, 1H), 7.40(t, J = 7.7 Hz, 1H), 7.21 (t, J = 7.5 Hz, 1H), 5.64 (s, 1H), 4.75 (q, J = 7.0Hz, 2H), 4.32 (t, J = 7.3 Hz, 2H), 3.09 (q, J = 7.2 Hz, 6H), 2.61 (t, J = 7.0Hz, 2H), 2.08-1.88 (m, 2H), 1.44 (t, J = 7.0 Hz, 3H), 1.18 (t, J = 7.2 Hz,9H); 13C NMR (100 MHz, d6-DMSO) δ 192.86, 185.39, 184.89, 172.62, 159.63,141.42, 127.63, 126.30, 123.97, 122.74, 112.65, 79.61, 69.74, 4.34, 46.16,44.60, 23.29, 16.14, 9.03; HRMS(ESI): Calcd for C17H17NO6S2 +([M+H]+): 396.0570,Found: 396.0566。
实施例4
于25 mL二口瓶中加入丙二腈(79.2 mg,1.20 mmol),3 mL苯(33.8 mmol),1.5 mL甲醇,半方酸衍生物(595 mg,1.20 mmol),三乙胺(120 mg,1.20 mmol),35℃反应6小时。TLC薄层色谱跟踪,反应结束后冷却至室温,旋蒸除去溶剂,所得物质用硅胶柱层析分离,洗脱剂为二氯甲烷-甲醇(10: 1,v/v)混合溶液,得橙色固体:556 mg,产率为75%。1H NMR(400 MHz, d6-DMSO) δ 7.65 (d, J = 7.6 Hz, 1H), 7.37 (d, J = 8.1 Hz, 1H), 7.31(t, J = 7.6 Hz, 1H), 7.09 (t, J = 7.4 Hz, 1H), 5.91 (s, 1H), 4.08 (t, J = 7.0Hz, 2H), 3.10 (q, J = 7.3 Hz, 12H), 2.59-2.51 (m, 2H), 2.06-1.93 (m, 2H),1.18 (t, J = 7.3 Hz, 18H); 13C NMR (100 MHz, d6-DMSO) δ 191.04, 186.34,174.33, 168.47, 153.84, 142.03, 127.13, 126.33, 122.73, 122.33, 119.94,118.92, 111.18, 81.84, 48.56, 46.21, 44.27, 23.11, 9.06; HRMS(ESI): Calcd forC18H11N3O5S2 2-([M]2-/2): 206.5076, Found: 206.5066。
实施例5
于二口瓶中加入2-甲基苯并噻唑(2.00 g,13.4 mmol),四乙二醇双(对甲苯磺酸酯)(3.37 g,6.71 mmol),通10分钟氮气后,于150℃反应24小时,反应结束后冷却至室温,有固体析出,过滤,用甲醇溶解固体,再旋蒸除去溶剂,经硅胶柱层析分离,洗脱液为二氯甲烷-甲醇(7:1,v/v)混合溶液,得红色产物:1.29 g,产率为24%。1H NMR (400 MHz, CD3OD) δ8.29 (d, J = 8.0 Hz, 2H), 8.24 (d, J = 8.6 Hz, 2H), 7.88 (t, J = 7.3 Hz, 2H),7.80 (t, J = 7.3 Hz, 2H), 7.68 (d, J = 8.1 Hz, 4H), 7.20 (d, J = 8.0 Hz, 4H),5.01- 4.96 (m, 2H), 4.96-4.91 (m, 2H), 4.03 (m, 2H), 3.98-3.94 (m, 2H), 3.40(dd, J = 5.6, 3.3 Hz, 2H), 3.33 (dd, J = 3.0, 2Hz, 2H), 3.32-3.27 (m, 4H),3.21 (s, 4H), 3.05 (s, 2H), 2.35(s, 6H); 13C NMR (100 MHz, CD3OD) δ 178.08,142.57, 141.15, 140.32, 129.60, 128.99, 128.59, 128.40, 125.60, 123.98,116.85, 70.20, 69.90, 67.68, 49.90, 20.15, 16.61。
实施例6
于50 mL二口瓶中加入氧醚链连接的2-甲基苯并噻唑衍生物(106 mg,0.132mmol),二氰乙烯基修饰的半方酸衍生物(163 mg,0.264 mmol),12 mL甲苯-正丁醇(1:1,v/v)混合溶液,0.6 mL吡啶,加分水器,通10分钟氮气后,于145℃反应36小时。反应结束后冷却至室温,旋蒸除去溶剂,所得粗产品经硅胶柱层析分离,洗脱液为二氯甲烷-甲醇(5:1,v/v)的混合溶液,得绿色固体:82.4 mg,产率为50%。1H NMR (400 MHz, d6-DMSO) δ 7.96 (d,J = 7.8 Hz, 4H), 7.78 (d, J = 8.3 Hz, 4H), 7.56-7.49 (m, 4H), 7.36 (t, J =7.7 Hz, 4H), 6.16 (s, 4H), 4.36 (d, J = 7.0 Hz, 8H), 3.52 (d, J = 20.1 Hz,4H), 2.54 (d, J = 13.4 Hz, 4H), 2.11-2.00 (m, 8H), 1.69 (d, J = 8.5 Hz, 4H);13C NMR (400 MHz, d6-DMSO) δ 173.44, 167.03, 162.88, 160.70, 141.32, 127.89,125.19, 123.28, 119, 113.74, 86.33, 62.14, 48.20, 45.92, 40.88, 38.33, 23.97;HRMS(ESI): Calcd for C60H48N8O11S6 2-([M]2-/2): 624.0889, Found: 624.0886。
应用实施例
选取9种不同的DNA,其具体信息如表1。
表1 所使用的DNA的相关信息
1. 在含有5 μM实施例6所得近红外方酸染料的缓冲溶液中,进行DNA的吸收滴定实验(滴加DNA的浓度为0、1、3、5、7、10、12、15、20 μM),结果见图1。
当将该近红外方酸染料单独存在于缓冲溶液(10 mM Tris-HCl, 100 mM KCl, pH=7.4)中时,近红外方酸染料处于聚集状态,如图1可见,随着体系中加入G-四联体,其680nm附近的吸收增强,同时610nm附近的吸收降低,而对于非G-四联体则无明显变化。
2. 在含有5 μM实施例6所得近红外方酸染料的缓冲溶液中,进行DNA的荧光滴定实验(滴加DNA的浓度为0、1、3、5、7、10、12、15、20 μM),结果见图2、图3-1至图3-7。
当将该近红外方酸染料单独存在于缓冲溶液(10 mM Tris-HCl, 100 mM KCl, pH=7.4)中时,荧光猝灭,由图2可以看出,随着体系中G-四联体浓度的逐渐增加,其荧光强度也逐渐恢复,当体系中pu22、pu27、pu18这三种G-四联体的浓度达到20 μM时,其荧光强度分别提高了约65、118、55倍。
如图3-1至图3-7所示,该近红外方酸染料对不同G-四联体的检测限及线性范围为: pu22(9.9 nM, 1-10 μM)、pu27(7.2 nM, 1 -20 μM)、pu18(16 nM, 1-15 μM)、bcl-22345(9.3 nM, 1-15 μM)、G4TTA(16 nM, 1-15 μM)、22CTA(20 nM, 1-15 μM)、Bom17(52nM, 1-12 μM)。
3. 为了确定测试前的孵育时长,测定了1小时内在缓冲溶液中5 μM 方酸染料与20 μM G-四联体pu22相互作用的荧光强度变化,结果见图4。
如图4所示,在加入G-四联体的30分钟后,体系荧光强度基本不变,相互作用达到稳定,因而将反应孵育时长定为30分钟。
4. 测定不同比例下的G-四联体pu22 (2.5 µM)与双方酸染料的圆二色谱,结果见图5。
由图5证明了双方酸染料与G-四联体的结合并不会影响到G-四联体的拓扑结构类型。
5. 为了探究双方酸染料与G-四联体结合的化学计量比,对其进行了再一次的滴定实验。保持双方酸染料与G-四联体的总摩尔浓度为10-5 M,以双方酸染料的摩尔分数:χSQ-1为横坐标。对应测定的715 nm处的荧光强度变化为纵坐标,绘制Job’s plot图,从而计算双方酸染料与不同G-四联体的结合化学计量比,结果见图6。
由图6可知,pu27、pu18与双方酸染料化学计量比均为1:1。pu22、bcl-22345、G4TTA、Bom17与双方酸染料化学计量比为2:1。22CTA与双方酸染料化学计量比为4:1。
6. 测定了缓冲溶液中存在不同浓度单链DNA ss-SCR的条件下,2 μM方酸染料与4μM pu22在715 nm波长处的荧光强度随ss-SCR浓度的变化曲线,以确定存在单链DNA环境下,方酸染料是否仍然能与平行G-四联体有较好的相互作用,结果见图7。
由图7可知,即便在高浓度的单链DNA的干扰下,方酸染料对G-四联体仍有较好的特异性。
以上所述仅为本发明的较佳实施例,凡依本发明申请专利范围所做的均等变化与修饰,皆应属本发明的涵盖范围。
Claims (8)
3.根据权利要求2所述的近红外双方酸染料的制备方法,其特征在于:步骤(1)中所用氧醚链连接的2-甲基苯并噻唑衍生物和二氰乙烯基修饰的半方酸衍生物的摩尔比为1:2;
所述溶剂为正丁醇、甲苯、吡啶按体积比10:10:1组成的混合溶液,所述回流反应的温度为145℃,时间为36小时;
步骤(3)所述硅胶柱层析采用体积比为5:1的二氯甲烷-甲醇混合溶液作为洗脱剂。
4.根据权利要求2或3所述的近红外双方酸染料的制备方法,其特征在于:所述氧醚链连接的2-甲基苯并噻唑衍生物的合成方法为:将四乙二醇双(对甲苯磺酸酯)与2-甲基苯并噻唑按摩尔比1:2混合,在通入氮气的条件下150℃加热反应24小时,反应结束后冷却至室温,过滤,用甲醇溶解所得固体后,经硅胶柱层析纯化得到目标产物;
其中,所述硅胶柱层析采用体积比为7:1的二氯甲烷-甲醇混合溶液作为洗脱剂。
7.根据权利要求6所述的近红外双方酸染料的制备方法,其特征在于:所述磺酸基团修饰的2-甲基苯并噻唑衍生物的合成方法为:将2-甲基苯并噻唑与1,3-丙磺酸内酯按摩尔比1:2.48混合后,加入无水乙腈,在通入氮气的条件下100℃反应15小时,反应结束后冷却至室温,抽滤除去溶液,所得白色物质用二氯甲烷洗涤,干燥,得到白色粉末。
8.一种如权利要求1所述的氧醚链连接的近红外双方酸染料在G-四联体荧光检测中的应用,其特征在于:将所述氧醚链连接的近红外双方酸染料作为响应G-四联体的荧光探针。
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