CN108623624A - 一种用探针s-f裸眼鉴别含氟牙膏的方法 - Google Patents
一种用探针s-f裸眼鉴别含氟牙膏的方法 Download PDFInfo
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Abstract
本发明涉及一种用探针S‑F裸眼鉴别含氟牙膏的方法。探针结构为:
Description
技术领域
本发明涉及的一种荧光分子探针S-F及其对含氟牙膏的检测,属于荧光分析检测领域。
技术背景
作为最小的阴离子,氟离子在生物、医疗、化学过程中扮演着重要角色,尤其在预防龋齿方面氟离子功不可没。增强抗龋力的关键是增加牙釉质表面的氟浓度,使氟离子能与牙釉质中的羟磷灰石发生反应取代磷灰石结晶的羟离子从而形成难溶于水的氟磷灰石,增强抗酸能力。牙釉质表面的氟的主要来源是摄入全身的氟化物有少量通过唾液腺分泌到唾液中,另外就是局部涂氟。此外,氟化物是有效的抗酶剂,氟可以通过牙体组织向外或通过唾液向内的两个途径进入菌斑,抑制糖酵解为有机酸的酶,从而减少了有机酸的形成,因此,在牙膏中添加一定量的氟离子能够很好地预防龋齿。然而,由于氟离子极易被机体吸收却很难被代谢,过度接触氟化物会导致氟中毒,引起诸如肾脏疾病和氟斑牙等疾病,因此在含氟量较高的地区使用含氟牙膏反而会使这一情况加剧。而现今大部分市售的牙膏在其成分表内并未标明其是否含氟,而鉴别一些功能牙膏是否含氟一般要使用仪器分析的方法检测,很难完成现场牙膏是否含氟的测试。
发明内容
鉴于上述,本发明的目的在于提供一种探针S-F,其结构为:
。
本发明的另一目的用探针S-F检测、裸眼鉴别含氟牙膏的方法,可以快速鉴别氟离子是否存在。鉴别过程既可以裸眼识别,也可以通过紫外灯照射的方式。
本发明的目的是通过以下技术方案来实现:
1. 合成探针S-F
探针S-F的合成路线
S-F的合成方法:将咪唑1.0 g溶于30 mL二氯甲烷中,向体系中依次加入1.0 g对羟基苯甲醛和2.0 g叔丁基二甲基氯硅烷(TBSCl),室温下反应2小时后,用10mL二氯甲烷萃取3次,加入5g无水硫酸钠,干燥,蒸出溶剂,得到浅黄色油状产物化合物Ⅰ; 称取1.0g化合物Ⅰ,溶于30 mL无水甲醇,在冰浴下向体系中缓慢加入0.4 g硼氢化钠,反应30分钟后,将反应得到的粗产物用10 mL二氯甲烷萃取3次,加入5 g无水硫酸钠,干燥,蒸出溶剂,得到无色油状产物Ⅱ; 称取0.2 g化合物Ⅱ,溶于20 mL干燥的二氯甲烷中,在冰浴和氮气保护下向体系中滴加0.1 g三溴化磷,反应10分钟后,将体系用10 mL二氯甲烷萃取3次,加入5 g无水硫酸钠,干燥,蒸出溶剂,得到无色油状产物Ⅲ; 将0.1 g碳酸钾与0. 1g试卤灵加入10mL N,N-二甲基甲酰胺中,在30-40℃下搅拌30分钟,然后在氮气保护下加入0.2 g无色油状产物Ⅲ,继续反应1小时,用10 mL二氯甲烷萃取反应液,用饱和碳酸氢钠溶液洗涤,然后再用超纯水洗涤;使用硅胶色谱柱纯化上述反应得到的粗产物,淋洗剂为乙酸乙酯 : 石油醚 = 1:1,干燥后得到橘黄色固体产物S-F,其分子量为433.1782。
2.用探针S-F裸眼鉴别含氟牙膏的方法,其步骤是:称取10 mg的含氟牙膏与无氟牙膏,将其分别分散于1.0 ml,10 μM S-F的二甲基亚砜(DMSO)溶液中,向体系分别滴加3滴pH值为9.0的4-羟乙基哌嗪乙磺酸水溶液(HEPES),摇晃使牙膏分散均匀,然后在60℃水浴下反应5分钟结果表明无氟牙膏不能使体系颜色发生变化,而含氟牙膏使体系颜色由浅黄色变为淡粉色,且在365nm紫外光下含氟牙膏实验组产生强烈的红色荧光,无氟牙膏实验组无荧光发射。
探针S-F检测氟离子的机理
探针S-F检测氟离子的机理:
探针S-F是基于氟离子与硅原子的强亲和力设计的,其亲和力的来源是因为Si-C键、Si-O键、Si-F键的解离能依次升高,分别为69,103,141 kcal/mol。当S-F与氟离子作用后,氟离子破坏了探针S-F的Si-O键,生成叔丁基二甲基氟硅烷(TBSF),同时连接基团对苯醌也被脱除,释放出荧光团试卤灵,体系荧光得以恢复。本反应特异性良好,不会受到其他因素影响。试卤灵在碱性条件下荧光量子产率高达75%,具有较高的灵敏度。
快速鉴别牙膏是否含氟
鉴别步骤如下:称取10 mg 无氟牙膏1与10 mg含氟牙膏2,将无氟牙膏与含氟牙膏分别分散于1mL,10μM探针 S-F的二甲基亚砜溶液中,向体系分别滴加3滴pH= 9.0的4-羟乙基哌嗪乙磺酸水溶液(HEPES),摇晃使无氟牙膏与含氟牙膏尽量分散均匀,然后在60℃水浴下加热5-10分钟。向牙膏样品中加入探针后,可通过裸眼或荧光光谱仪鉴别牙膏是否含氟。结果表明无氟牙膏1不能使体系颜色发生变化,而含氟牙膏2使体系颜色由浅黄色变为淡粉色。在普通紫外光下照射,含氟牙膏2产生强烈的红色荧光。这是由于探针S-F与含氟牙膏中的氟离子作用后,脱除了叔丁基二甲基氟硅烷(TBSF),同时连接基团对苯醌也被脱除,释放出荧光团试卤灵。在弱碱性条件下(pH=9.0),试卤灵羟基结构发生去质子化,颜色从橘黄色变为粉色,同时发射出强烈的荧光。
本发明的优点和产生的有益效果:
本发明合成探针S-F以高荧光量子产率的试卤灵作为荧光团,高荧光量子产率的荧光团使得探针具有良好的灵敏度。氟离子的脱硅烷化作用是具有特异性的和具有高选择性,不受其他因素的干扰。反应释放出的试卤灵在弱碱性条件下(pH>7)颜色由橘黄色变为粉红色,向牙膏样品中加入探针后,可通过裸眼或荧光光谱仪鉴别是否含氟牙膏。此外,与传统检测氟离子的方法(包括电化学方法和离子色谱法)相比,本发明合成的荧光分子探针S-F光学性质稳定,储存时间长,操作简单,可用于裸眼鉴别,所需时间短,快速鉴别含氟牙膏与无氟牙膏效果良好。
附图说明
图1为本发明所合成的S-F的1H谱。
图2为本发明所合成的S-F的13C谱。
图3为本发明所合成的S-F的高分辨质谱图。
图4为本发明所合成的S-F的吸收光谱及发射光谱,其中:图4a为S-F的吸收光谱,图4b为S-F的发射光谱。
图5为本发明所合成的S-F和F-的响应时间及pH的影响图,其中:图5a为S-F与氟离子的响应时间图,图5b为不同pH对S-F的发射强度的影响。
图6为本发明所合成的S-F的选择性实验图。
图7为本发明所合成的S-F和不同浓度F﹣作用时的荧光光谱变化图,其中:图7a是S-F的荧光滴定曲线,图7b是实验组荧光强度与对照组荧光强度之比对氟离子浓度的散点图。
图8为本发明所合成的S-F荧光强度变化与F﹣浓度( 0.1-10.0μM )的线性关系。
图9为快速鉴别牙膏现象图。a.可见光及b.365nm紫外光下探针与无氟牙膏1样品及含氟牙膏2作用后的现象,0,1,2分别为S-F,S-F与无氟牙膏样品作用后的体系,S-F与含氟牙膏样品作用后的体系。测试条件:(HEPES, pH9.0):DMSO=1:9。
本发明用核磁共振氢谱、核磁共振碳谱以及高分辨质谱对荧光分子探针S-F的结构进行了表征。氢谱(图1)证明有27个氢原子,其化学位移数据为:
1H NMR(400MHz,CDCl3): δ =7.71 (d, J = 8.9 Hz, 1H), 7.45 – 7.40 (m, 1H),7.32 – 7.29 (m, 2H), 7.01 (dd, J = 8.9, 2.6 Hz, 1H), 6.90 – 6.86 (m, 3H),6.86 – 6.82 (m, 1H), 6.33 (t, J = 1.9 Hz, 1H), 5.09 (s, 2H), 1.00 – 0.98 (m,9H), 0.22 – 0.20 (m, 6H).
碳谱(图2)证明有19种碳原子,其化学位移数据为:13C NMR (101 MHz, CDCl3 ):δ =186.33, 162.79, 156.04, 149.83, 145.55, 134.69, 134.19, 131.56, 129.26,128.41, 127.92, 120.37, 114.34, 106.71, 100.97, 70.78, 25.38, 18.20, -4.42.
高分辨质谱(图3)显示其[M+1]峰为:434.1782,found:434.1777.
为了进一步解释探针S-F对氟离子具有良好的特异性识别能力,下面利用荧光发射光谱实验对荧光分子探针S-F对氟离子的检测性能进行了试验。
如图4所示,5 μM 探针S-F与25 μM氟离子作用前后,其吸收光谱和荧光光谱均发生了变化,具体表现为原本在468nm处的强吸收峰消失,在561nm,575nm及592nm处出现了三组依次增强的强吸收峰,其吸收光谱的特征与荧光团试卤灵非常相似。测定探针S-F的荧光光谱时选择550nm作为激发波长,加入氟离子之前,探针S-F无荧光发射,加入氟离子后,在598nm处出现最强发射峰,探针荧光显著增强。除此以外,S-F与氟离子作用后在可见光下溶液的颜色由浅黄色变为粉红色,因此可以通过裸眼检测该测试体系中的氟离子。
响应时间及pH对探针S-F的影响
发现该探针S-F在37℃,pH7.4条件下,与氟离子在1小时响应完全(见图5a),颜色由橘黄色变为粉色。而在pH9.0,60℃水浴下与含氟牙膏样品在5分钟即出现颜色变化。响应非常迅速。随后在不同的pH条件下对探针S-F与5μM氟离子响应前后的荧光强度进行了测试(图5b)。当pH≥7.4时,加入5μM四丁基氟化铵(TBAF)后,探针S-F的荧光强度随pH的升高而急剧增强,并且在可见光下溶液由淡黄色变为淡粉色。由于试卤灵在碱性条件下其荧光发射不再随pH升高而变化,因此在碱性条件下,S-F与氟离子作用效果更好。
选择性实验
图6为本发明所合成的S-F的选择性实验图。为了研究探针S-F对氟离子的识别能力。本发明将5 μM探针 S-F分别与50 μM 的氟离子及牙膏中干扰物作用,然后用荧光分光光度计记录荧光发射光谱的变化。探针S-F与氟离子及牙膏中干扰物反应一小时后,S-F对于氟离子响应良好,荧光发射增强超过40倍,而其他干扰物没有引起荧光发射的显著变化,证明S-F对于氟离子有非常良好的选择性。
浓度滴定实验
图7为本发明所合成的S-F和不同浓度F﹣作用时的荧光光谱变化图。从图7中可以看出:随着加入叔丁基氟化铵(TBAF)浓度的升高,荧光强度逐渐增强,最强发射位于波长598nm处,并且溶液颜色由橘黄色变为粉红色,达到了裸眼识别氟离子的目的。本发明用598nm处的相对荧光强度F/F0(F为实验组的荧光强度,F0为空白探针的荧光强度)对加入的氟离子浓度作图,并进行线性拟合,线性范围为0-10.0μM。用公式LOD=3σ/k计算检出限,(σ代表平行测试九次的空白探针的标准差,k代表拟合曲线的斜率)计算得到的检出限为84nM(见图8)。
在系统的研究了S-F的光学性质以后,本发明将其应用于鉴别无氟牙膏与含氟牙膏。为了加快鉴别的速度,本发明选用pH9.0,水浴60℃,响应时间为5分钟作为作用条件。本发明直接用于鉴定市售的两种牙膏1和牙膏2,其中1为无氟牙膏,2为含氟牙膏。
分别称取10.0 mg无氟牙膏1的与含氟牙膏2,将其分别分散于1ml,10μM S-F的二甲基亚砜(DMSO)溶液中,向体系分别滴加3滴4-羟乙基哌嗪乙磺酸(HEPES),pH值为9.0,摇晃使牙膏分散均匀,然后在60℃水浴下反应5分钟。向牙膏样品中加入探针后,可通过裸眼或荧光光谱仪鉴别牙膏是否含氟。结果表明无氟牙膏1不能使体系颜色发生变化,而含氟牙膏2使体系颜色由浅黄色变为淡粉色,且在365nm紫外光下体系无氟牙膏1无荧光发射,含氟牙膏2产生强烈的红色荧光。证明S-F可以应用于牙膏是否含氟的鉴别(参见图9)。
Claims (2)
1.一种探针S-F,其结构式为:
。
2.用权利要求1所合成荧光分子探针S-F裸眼鉴别含氟牙膏的方法,其步骤是:称取10mg的含氟牙膏与无氟牙膏,将其分别分散于1.0 ml,10 μM S-F的二甲基亚砜溶液中,向体系分别滴加3滴pH值为9.0的4-羟乙基哌嗪乙磺酸水溶液,摇晃使牙膏分散均匀,然后在60℃水浴下反应5分钟,结果表明:向牙膏样品中加入探针后,可通过裸眼或荧光光谱仪鉴别牙膏是否含氟;无氟牙膏不能使体系颜色发生变化,而含氟牙膏使体系颜色由浅黄色变为淡粉色,并且在365nm紫外光下含氟牙膏实验组产生强烈的红色荧光,无氟牙膏实验组无荧光发射。
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Citations (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2008145830A2 (fr) * | 2006-12-29 | 2008-12-04 | Quidd | Nouveaux composes pro-fluorescents |
WO2013172544A1 (ko) * | 2012-05-17 | 2013-11-21 | 포항공과대학교 산학협력단 | 새로운 이광자 흡수 형광체 및 이를 이용한 기질 감지 방법 |
CN103805170A (zh) * | 2014-01-26 | 2014-05-21 | 大连理工常熟研究院有限公司 | 一种用于识别硫化氢的特异性荧光探针及其应用 |
CN103923479A (zh) * | 2014-04-18 | 2014-07-16 | 大连理工大学 | 久洛尼定母核的氟离子荧光染料及其应用 |
CN104418875A (zh) * | 2013-08-28 | 2015-03-18 | 苏州罗兰生物科技有限公司 | 一种检测氟离子荧光分子探针及其合成与应用 |
CN104449677A (zh) * | 2014-12-29 | 2015-03-25 | 大连理工常熟研究院有限公司 | 一种用于识别氟离子的特异性荧光探针及其应用 |
CN104845611A (zh) * | 2015-04-28 | 2015-08-19 | 中国科学院理化技术研究所 | 一种新型氟离子比率荧光探针及应用 |
KR101549347B1 (ko) * | 2014-08-11 | 2015-09-01 | 경북대학교 산학협력단 | 신규한 화합물, 이의 제조 방법 및 이를 포함하는 화학 센서 |
CN105131935A (zh) * | 2015-08-27 | 2015-12-09 | 晋江尚京富本环保科技有限公司 | 快速高选择性氟离子比色探针及其制备方法 |
CN105419786A (zh) * | 2015-12-16 | 2016-03-23 | 南京大学 | 试卤灵为基础结构的新型荧光比率探针在检测h2s中的应用 |
CN105693651A (zh) * | 2016-03-14 | 2016-06-22 | 华南理工大学 | 一种检测零价钯的有机小分子探针及其制备方法 |
CN107365326A (zh) * | 2017-07-24 | 2017-11-21 | 湖北大学 | 一种用于检测活细胞内氟离子的荧光探针及其制备方法 |
-
2018
- 2018-06-12 CN CN201810601184.5A patent/CN108623624A/zh active Pending
Patent Citations (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2008145830A2 (fr) * | 2006-12-29 | 2008-12-04 | Quidd | Nouveaux composes pro-fluorescents |
WO2013172544A1 (ko) * | 2012-05-17 | 2013-11-21 | 포항공과대학교 산학협력단 | 새로운 이광자 흡수 형광체 및 이를 이용한 기질 감지 방법 |
CN104418875A (zh) * | 2013-08-28 | 2015-03-18 | 苏州罗兰生物科技有限公司 | 一种检测氟离子荧光分子探针及其合成与应用 |
CN103805170A (zh) * | 2014-01-26 | 2014-05-21 | 大连理工常熟研究院有限公司 | 一种用于识别硫化氢的特异性荧光探针及其应用 |
CN103923479A (zh) * | 2014-04-18 | 2014-07-16 | 大连理工大学 | 久洛尼定母核的氟离子荧光染料及其应用 |
KR101549347B1 (ko) * | 2014-08-11 | 2015-09-01 | 경북대학교 산학협력단 | 신규한 화합물, 이의 제조 방법 및 이를 포함하는 화학 센서 |
CN104449677A (zh) * | 2014-12-29 | 2015-03-25 | 大连理工常熟研究院有限公司 | 一种用于识别氟离子的特异性荧光探针及其应用 |
CN104845611A (zh) * | 2015-04-28 | 2015-08-19 | 中国科学院理化技术研究所 | 一种新型氟离子比率荧光探针及应用 |
CN105131935A (zh) * | 2015-08-27 | 2015-12-09 | 晋江尚京富本环保科技有限公司 | 快速高选择性氟离子比色探针及其制备方法 |
CN105419786A (zh) * | 2015-12-16 | 2016-03-23 | 南京大学 | 试卤灵为基础结构的新型荧光比率探针在检测h2s中的应用 |
CN105693651A (zh) * | 2016-03-14 | 2016-06-22 | 华南理工大学 | 一种检测零价钯的有机小分子探针及其制备方法 |
CN107365326A (zh) * | 2017-07-24 | 2017-11-21 | 湖北大学 | 一种用于检测活细胞内氟离子的荧光探针及其制备方法 |
Non-Patent Citations (1)
Title |
---|
SOON YOUNG KIM等,: "Chromogenic and Fluorescent Chemodosimeter for Detection of Fluoride in Aqueous Solution", 《ORG. LETT.》 * |
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