CN115521308B - 光敏化合物、其制备及其应用和甲醛光谱化学传感器 - Google Patents
光敏化合物、其制备及其应用和甲醛光谱化学传感器 Download PDFInfo
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Abstract
本发明涉及甲醛荧光探针分子领域,具体而言,涉及一种光敏化合物、其制备及其应用和甲醛光谱化学传感器。光敏化合物的结构式如下所示:其中,R1选自含氮的亲水基团、取代羟基和取代硫醇基中的任意一种,R2选自多元醇基团或含糖苷的基团,探针分子具有红光发射荧光,其与甲醛作用后其紫外光谱和荧光都发生了显著的蓝移,同时伴随明显的颜色变化。探针分子对甲醛具有快速的荧光响应、良好的抗干扰能力、较低的检测限,其快速的荧光响应和裸眼识别效用和较低的检测限将为其在食品、药品中甲醛的实时检测创造了良好的条件。
Description
技术领域
本发明涉及甲醛荧光探针分子领域,具体而言,涉及一种光敏化合物、其制备及其应用和甲醛光谱化学传感器。
背景技术
甲醛是一种高度危害人体健康的室内污染物,它强烈刺激人眼、皮肤和粘膜。国际癌症研究机构(IARC)将甲醛归类为导致人类致癌物质和白血病物质之一。因此,对甲醛的进行快速有效的实时监控具有非常重要的现实意义。
甲醛属于卫生部规定的禁止在食品中使用的非食用物质目录中。但目前不少食品中都不同程度检出甲醛。甲醛测定一般采用分光光度法、液相色谱法、气相色谱法和荧光法。分光光度法检测灵敏度不高,一般用于定性测定。色谱法灵敏度高,但是处理过程繁琐,且检测时间较长,不利于快速检测。普通的荧光法于分光光度法相似,灵敏度不够,但是,寻找甲醛选择性的荧光分子传感技术可以高效、快捷、简便,并大大提高荧光光度法的检测灵敏度,同时,有机荧光传感器结合甲醛后可能具有可裸眼识别的优点,将为甲醛快速检测提供可能。然而,基于荧光传感技术探测甲醛分子信号的相关研究还不成熟。因此,构建并合成系列对甲醛分子具有选择性裸眼识别功能的荧光化学传感分子,通过对传感分子进行修饰,并研究其在生活用水、食品和食品包装材料中甲醛含量测定中的应用将具有重要的现实意义和应用价值。
发明内容
本发明提供了一种光敏化合物、其制备及其应用和甲醛光谱化学传感器,该光敏化合物具有良好的化学稳定性,光稳定性好,其对甲醛的识别过程伴随有明显的颜色变化,这种显著的传感识别伴随的颜色变化为其对甲醛的快速便捷检测提供了可能,且对其它金属和非金属离子表现出良好的抗干扰性能,改善了甲醛光谱化学传感器短波发射的不足的问题。
本发明是这样实现的:
第一方面,本发明实施例提供了一种光敏化合物,其结构式如下所示:
其中,R1选自含氮的亲水基团、取代羟基和取代硫醇基中的任意一种,R2选自多元醇基团或含糖苷的基团。
第二方面,本发明实施例提供了一种光敏化合物的制备方法,参照下述合成路径合成所述光敏化合物:
第三方面,本发明实施例提供了一种甲醛光谱化学传感器,其利用上述光敏化合物制备得到。
第四方面,本发明实施例提供了一种上述光敏化合物在检测甲醛中的应用。
本发明的有益效果是:1)本发明提供的光敏化合物具有良好的化学稳定性,光稳定性好,其对甲醛的识别过程伴随有明显的颜色变化,这种显著的传感识别伴随的颜色变化为其对甲醛的快速便捷检测提供了可能。
2)本发明提供的苝光敏化合物对甲醛传感选择性好,该光敏化合物对其它金属和非金属离子表现出良好的抗干扰性能,其快速的光谱响应和低的检测限值为其在食品检测方面的应用提供了可能。
3)本发明提供的光敏化合物可通过修饰所包含R1基团的种类,实现分子低毒性、良好的生物兼容性和稳定的化学结构为其在生物显微成像或者作为生物光谱诊断具有潜在的应用价值。
附图说明
为了更清楚地说明本发明实施方式的技术方案,下面将对实施方式中所需要使用的附图作简单地介绍,应当理解,以下附图仅示出了本发明的某些实施例,因此不应被看作是对范围的限定,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相关的附图。
图1是本发明检测例1提供的紫外灯下(365nm)实施例2的光敏化合物在滴加含有甲醛前(左)后(右)的颜色变化图;
图2是本发明实施例2光敏化合物对甲醛的分子“开-关”机理;
图3是本发明检测例2提供的实施例2光敏化合物对甲醛的浓度响应荧光递增光谱图C光敏化合物=1×10-6mol/L);
图4是本发明检测例2提供的实施例2光敏化合物对甲醛的荧光响应线性拟合曲线及检测限计算3σ/slope=0.12μM;
图5是本发明检测例3提供的实施例2光敏化合物对各种分子与离子(1-15,1'-15')Br-,Cl-,SO4 2-,CO3 2-,F-,PO4 3-,H2O2,Fe3+,Ag+,Co2+,CN-,Ni2+,Cu2+,Zn2+,Cd2+后再与甲醛作用荧光的(600nm)柱状图,CSY-CON=1×10-6mol/L)。
具体实施方式
为使本发明实施例的目的、技术方案和优点更加清楚,下面将对本发明实施例中的技术方案进行清楚、完整地描述。实施例中未注明具体条件者,按照常规条件或制造商建议的条件进行。所用试剂或仪器未注明生产厂商者,均为可以通过市售购买获得的常规产品。
第一,本发明实施例提供了一种光敏化合物,其结构式如下所示:
其中,R1选自含氮的亲水基团、取代羟基和取代硫醇基中的任意一种,R2选自多元醇基团或含糖苷的基团。
本发明实施例提供的光敏化合物(下文也称为甲醛荧光探针分子)的构筑主要是基于苝酰亚胺弯位和酰胺位进行共轭修饰,通过醛和活泼甲基的缩合反应制备具有近红外发射的长程共轭荧光给-受体分子,弯位的另外一侧接具有给电子作用的发色团。
具体地,本发明实施例提供的甲醛荧光探针分子对甲醛显示了明显的识别作用,探针分子具有红光发射荧光,其与甲醛作用后其紫外光谱和荧光都发生了显著的蓝移,同时伴随明显的颜色变化。探针分子对甲醛具有快速的荧光响应、良好的抗干扰能力、较低的检测限,其快速的荧光响应和裸眼识别效用和较低的检测限将为其在食品、药品中甲醛的实时检测创造了良好的条件。
进一步地,R1选自乙醇基团、六氢吡啶基、乙硫醇基和中的任意一种;R2选自聚乙二醇基或葡萄糖基。
更进一步地,光敏化合物为
本发明实施例苝酰亚胺设计并合成了一系列具有能力给体和能量受体的光敏化合物,光敏基团基于苯氧杂环,在紫外灯或酸性条件下,分子氧杂环实现开关效应,同时伴随明显的光谱吸收和发射变化。
第二方面,本发明实施例提供上述光敏化合物的制备方法,参照下述合成路径合成所述光敏化合物:
该制备方法将具有耐强酸强碱的苝酰亚胺作为发光本体结构,通过在苝酰亚胺的弯位修饰实现分子功能化修饰,继而合成具有优异的光化学稳定性、对甲醛具有选择性识别的近红外发射荧光探针分子。
具体地,将苝酐类化合物、胺类化合物和第一溶剂混合进行反应;其中,所述苝酐类化合物和所述胺类化合物的摩尔比为1:1.8-2.2;反应温度为100-150℃,反应时间为24-48小时;所述第一溶剂选自咪唑、DMF、DMAc、丙酸和乙醇中的至少一种。
将溴代苝酰亚胺衍生物、对醛基硼酯、催化剂、碱性物质和第二溶剂混合进行反应;其中,所述催化剂为钯类物质,优选为四三苯基膦钯;所述碱性物质为碳酸类化合物,优选为碳酸钾或碳酸钠;所述第二溶剂为DMSO、DMF和DMAc中的至少一种;所述溴代苝酰亚胺衍生物和所述对醛基硼酯的摩尔比为1:0.8-1.2;所述溴代苝酰亚胺衍生物和所述碱性物质的摩尔比为1:1.2-1.8;反应温度75-95℃,反应时间为12-48小时。
将苝酰亚胺-苯甲醛类化合物、烯丁基氟化硼酯衍生物、金属粉末以及第三溶剂混合进行反应形成中间体;其中,所述苝酰亚胺-苯甲醛类化合物和所述烯丁基氟化硼酯衍生物的摩尔比为1:1.1-1.2;所述金属粉末为锌粉;所述第三溶剂为无水THF;反应时间为12-36小时,反应温度为60-80℃。
将含炔基的化合物在一价铜离子作用下与中间体发生点击反应;其中,反应时间为24-48小时;所述中间体与所述含炔基的化合物的摩尔比为1:1-1.2。
第三方面,本发明实施例提供了一种甲醛光谱化学传感器,其利用上述光敏化合物制备得到。
第四方面,本发明实施例提供了一种上述光敏化合物在检测甲醛中的应用。
以下结合具体实施例对本发明提供的一种光敏化合物进行具体说明。
实施例1
本实施例提供一种光敏化合物,其结构式如下所示:
参照下述合成路径合成中间物SH-BY:
具体地,在250mL两口瓶中加入1-哌啶-7-二溴代苝四甲酸酐2.7g(5.6mmol),化合物SY-A 5.0g(11.2mmol),丙酸100mL,120~140℃油浴锅中反应24~48h。通过薄层层析板检测反应进程,反应结束后,冷却至室温,将反应液倒入100mL水中,调节pH至酸性,有大量红色固体洗出,用乙醇/DMF重结晶得化合物SY-BY,7.2g,产率:91%。1H NMR(400MHz,CDCl3)δ9.60-9.58(d,J=6Hz,4H),9.30(s,2H),8.88-8.84(d,J=9Hz,4H),8.82-8.78(d,J=9Hz,4H),3.66-3.62(t,12H),2.22-1.52(t,10H)。
参照下述合成路径合成中间物SY-BH:
具体地,氮气保护下,向100mL两口瓶中,加入化合物SY-BY 4.0g(2.8mmol),对醛基苯硼酯0.7g(3.0mmol),碳酸钾0.6g(4.3mmol),四三苯基膦钯0.005g溶于80mL DMSO中,80~95℃油浴锅中反应12~48h。通过薄层层析板检测反应进程,反应结束后,冷却至室温,将反应液倒入50mL水中,有大量红色固体析出,得到的固体真空烘箱烘干,硅胶柱层析纯化,洗脱剂为二氯甲烷/甲醇(1:5~1:10),得化合物SY-BH,3.1g,产率:77%。1H NMR(400MHz,CDCl3)δ9.58-9.56(d,J=6Hz,4H),9.24(s,2H),8.84-8.82(d,J=9Hz,4H),8.78-8.72(d,J=9Hz,4H),7.78-7.74(t,8H),7.68-7.64(t,24H),3.64-3.58(t,12H),2.22-1.52(t,10H)。
参照下述合成路径合成中间物SY-NH:
具体地,氮气保护下,将化合物溴代苝酰亚胺衍生物SY-BH(2.5g,1.7mmol)、烯丁基氟化硼钾(0.33g,2.0mmol)、锌粉溶于100mL无水THF中,60~80℃回流12~36h,色谱检测跟踪反应进程,反应结束后,将反应液倒入50mL冰水中,分别用100mL二氯甲烷萃取两次。用二氯甲烷/甲醇做流动相柱层析得红色固体SY-NH,1.8g,产率:72%。1H NMR(400MHz,CDCl3)δ9.58-9.56(d,J=6Hz,4H),9.24(s,2H),8.84-8.82(d,J=9Hz,4H),8.78-8.72(d,J=9Hz,4H),7.78-7.74(t,8H),7.68-7.64(t,24H),6.16-6.12(d,4H),6.12-6.02(d,2H),4.62(t,2H),4.02(t,4H),3.64-3.58(t,12H),2.82(NH2,s,4H),2.22-1.52(t,10H)。
参照下述合成路径合成终产物:
具体地,氮气保护下,将含有化合物SY-NH(1.0mmol,1.5g)、乙二醇-炔化合物(1.2mmol,0.19g)、碘化亚铜(1.2mmol,0.23g)24-48h。反应完成后向反应液添加60mL水,二氯甲烷萃取,层析分离(CHCl3/methanol=2:1-5:1)得灰绿色固体SY-NON 1.2g,产率:67%。1H NMR(400MHz,CDCl3)δ9.58-9.56(d,J=6Hz,4H),9.24(s,2H),8.84-8.82(d,J=9Hz,4H),8.78-8.72(d,J=9Hz,4H),7.78-7.74(t,8H),7.68-7.64(t,24H),6.32-6.24(s,2H),6.16-6.12(d,4H),6.12-6.02(d,2H),4.62(t,2H),4.02(t,4H),3.64-3.58(t,12H),3.44-3.08(t,36H),2.82(NH2,s,4H)。TOF-MS-ES:m/z.Calculated:([M+H])+=1793.7835,found:1793.7832。
实施例2
本实施例提供一种光敏化合物,其结构式如下所示:
参照下述合成路径合成中间物SY-CH:
具体地,得化合物SY-CH,6g,产率:88%。1H NMR(400MHz,CDCl3)δ9.60-9.58(d,J=6Hz,4H),9.30(s,2H),8.88-8.84(d,J=9Hz,4H),8.82-8.78(d,J=9Hz,4H),3.62-3.62(m,2H),2.22-1.52(t,3H)。
参照下述合成路径合成中间物SY-COH:
得化合物SY-COH,3.5g,产率:75%。1H NMR(400MHz,CDCl3)δ9.58-9.56(d,J=6Hz,4H),9.24(s,2H),8.84-8.82(d,J=9Hz,4H),8.78-8.72(d,J=9Hz,4H),7.78-7.74(t,8H),7.68-7.64(t,24H),3.62-3.62(m,2H),2.22-1.52(t,3H)。
参照下述合成路径合成中间物SY-CNH:
得红色固体SY-CNH,2.5g,产率:70%。1H NMR(400MHz,CDCl3)δ9.58-9.56(d,J=6Hz,4H),9.24(s,2H),8.84-8.82(d,J=9Hz,4H),8.78-8.72(d,J=9Hz,4H),7.78-7.74(t,8H),7.68-7.64(t,24H),6.16-6.12(d,4H),6.12-6.02(d,2H),4.62(t,2H),4.02(t,4H),3.62-3.62(m,2H),2.82(NH2,s,4H),2.22-1.52(t,3H)。
参照下述合成路径合成终产物:
得灰红色固体SY-CON 9.0g,产率:68%。1H NMR(400MHz,CDCl3)δ9.58-9.56(d,J=6Hz,4H),9.24(s,2H),8.84-8.82(d,J=9Hz,4H),8.78-8.72(d,J=9Hz,4H),7.78-7.74(t,8H),7.68-7.64(t,24H),6.32-6.24(s,2H),6.16-6.12(d,4H),6.12-6.02(d,2H),4.62(t,2H),4.02(t,4H),3.64-3.58(t,12H),3.44-3.08(t,28H),2.82(NH2,s,4H),2.22-1.52(t,3H)。TOF-MS-ES:m/z.Calculated:([M+H])+=1754.7362,found:1754.7364。
检测例1
分别在紫外灯下(365nm)检测滴加实施例2光敏化合物前后的甲醛溶液的颜色变化。
结果参见图1,根据图1可知,本发明实施例提供的光敏化合物能够有效与甲醛作用,能够有效检测甲醛,实施例2光敏化合物与甲醛作用的机理图参见图2。
检测例2
检测实施例2光敏化合物对甲醛的浓度荧光响应。检测结果参见图3和图4,根据图3和图4可知探针分子随着甲醛浓度的变化,其发射波强度逐渐增强。
检测例3
检测实施例2光敏化合物对不同分子和离子和甲醛进行荧光检测,结果参见图5,根据图5可知,探针分子对其它金属和非金属离子表现出良好的抗干扰性能。
以上所述仅为本发明的优选实施方式而已,并不用于限制本发明,对于本领域的技术人员来说,本发明可以有各种更改和变化。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 (13)
1.一种光敏化合物,其特征在于,其结构式如下所示:
。
2.一种权利要求1所述的光敏化合物的制备方法,其特征在于,参照下述合成路径合成所述光敏化合物:
;R1和R2为权利要求1所示的化合物对应的基团。
3.根据权利要求2所述的制备方法,其特征在于,将苝酐类化合物、胺类化合物和第一溶剂混合进行反应。
4.根据权利要求3所述的制备方法,其特征在于,所述苝酐类化合物和所述胺类化合物的摩尔比为1:1.8-2.2;
反应温度为100-150℃,反应时间为24-48小时;
所述第一溶剂选自咪唑、DMF、DMAc、丙酸和乙醇中的至少一种。
5.根据权利要求2所述的制备方法,其特征在于,将溴代苝酰亚胺衍生物、对醛基硼酯、催化剂、碱性物质和第二溶剂混合进行反应。
6.根据权利要求5所述的制备方法,其特征在于,所述催化剂为钯类物质;
所述碱性物质为碳酸类化合物;
所述第二溶剂为DMSO、DMF和DMAc中的至少一种;
所述溴代苝酰亚胺衍生物和所述对醛基硼酯的摩尔比为1:0.8-1.2;所述溴代苝酰亚胺衍生物和所述碱性物质的摩尔比为1:1.2-1.8;
反应温度75-95℃,反应时间为12-48小时。
7.根据权利要求5所述的制备方法,其特征在于,所述催化剂为四三苯基膦钯;所述碱性物质为碳酸钾或碳酸钠。
8.根据权利要求2所述的制备方法,其特征在于,将苝酰亚胺-苯甲醛类化合物、烯丁基氟化硼酯衍生物、金属粉末以及第三溶剂混合进行反应形成中间体。
9.根据权利要求8所述的制备方法,其特征在于,所述苝酰亚胺-苯甲醛类化合物和所述烯丁基氟化硼酯衍生物的摩尔比为1:1.1-1.2;
所述金属粉末为锌粉;
所述第三溶剂为无水THF;
反应时间为12-36小时,反应温度为60-80℃。
10.根据权利要求2所述的制备方法,其特征在于,将含炔基的化合物在一价铜离子作用下与中间体发生点击反应。
11.根据权利要求10所述的制备方法,其特征在于,反应时间为24-48小时;
所述中间体与所述含炔基的化合物的摩尔比为1:1-1.2。
12.一种甲醛光谱化学传感器,其特征在于,其利用权利要求1所述的光敏化合物制备得到。
13.一种权利要求1所述的光敏化合物在检测甲醛中的应用。
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