CN107033176B - 杯[4]芳烃苯硼酸衍生物/多壁碳纳米管复合材料的制备方法及其应用 - Google Patents
杯[4]芳烃苯硼酸衍生物/多壁碳纳米管复合材料的制备方法及其应用 Download PDFInfo
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- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 239000002048 multi walled nanotube Substances 0.000 title claims abstract description 29
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- 238000002360 preparation method Methods 0.000 title claims abstract description 7
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- -1 aromatic hydrocarbons dibromo compound Chemical class 0.000 claims abstract description 12
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- 229910000027 potassium carbonate Inorganic materials 0.000 claims abstract description 6
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
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- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
- C07F5/027—Organoboranes and organoborohydrides
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- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/416—Systems
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Abstract
杯[4]芳烃苯硼酸衍生物/多壁碳纳米管复合材料的制备方法及其应用。具体为:第一步将3‑羟基苯硼酸和碳酸钾溶于无水乙腈中,油浴搅拌加热。将杯[4]芳烃二溴化合物和碘化钾溶于乙腈中,油浴搅拌加热。一段时间后,分批向杯[4]芳烃二溴化合物和碘化钾的乙腈溶液中加入含有3‑羟基苯硼酸和碳酸钾的乙腈溶液,回流加热。所得粗产物进行萃取,水洗有机相至中性。旋转蒸发除去二氯甲烷和微量残余蒸馏水后得到黄色的固体粉末,分离纯化。第二步将多壁碳纳米管在4mol·L‑1硝酸中加热回流,离心,反复洗涤,直至pH值接近中性,烘干。称取多壁碳纳米管和杯[4]芳烃苯硼酸衍生物于乙醇溶剂中超声分散,得到杯[4]芳烃苯硼酸衍生物/多壁碳纳米管复合材料。
Description
技术领域
本发明涉及一种杯[4]芳烃苯硼酸衍生物、杯[4]芳烃苯硼酸衍生物/多壁碳纳米管复合材料的制备方法及其应用。
背景技术
作为与人体健康状况联系密切的葡萄糖,它在各个方面对生物体而言均具有不可替代的作用。它是生命活动过程所需能量的主要来源,其对人体能量的贡献占到70%。葡萄糖是人体血液的成分之一,血液中葡萄糖含量的异常预示着疾病的发生。在医学上,正常人在空腹血糖浓度为3.61~6.11mmol/L,空腹血糖浓度超过7.0mmol/L则被诊断为高血糖,血糖浓度低于3.61mmol/L则被诊断为低血糖。与血糖水平联系最紧密的疾病就是糖尿病,其诊断的唯一标准就是血液中葡萄糖含量。世界卫生组织的糖尿病数据显示:目前全世界至少已经有1.8亿多人患有糖尿病,这一数字到2030年将上升到3.6亿。糖尿病已经成为了继肿瘤、心血管病之后的第三大严重威胁人类健康的慢性疾病。因此,简便、易操作的葡萄糖的定量检测技术对于糖尿病的诊断与治疗有着十分重大的意义。
最近几年,含有硼酸的大分子化合物在化学、生物医药领域等受到了很大的关注,很多研究集中在含有硼酸的大分子化合物对糖类的传感方面,但是含有硼酸的大分子化合物对葡萄糖的识别的光谱检测方法往往存在信号变化小的缺点。为了克服这一缺点,有研究合成出含硼酸基团的超分子与金纳米离子结合,检测葡萄糖,但是也存在检测材料昂贵、信号变化不明显等缺点。因此,改用其他检测手段优化葡萄糖的检测至关重要,电化学传感器的原理是当待测物质与分子识别元件结合后会发出复合物的特征信号,然后再经信号转换器转变成电的可输出信号,从而达到检测葡萄糖的目的,与其他检测方法相比,电化学传感器可以实现对特定底物的检测,同时识别元件本身易操作、省时高效、实用性强,电化学检测手段已发展成为传感检测领域十分活跃的一种检测手段,倍受各领域研究者的关注。
发明内容
本发明的目的在于提供一种可以测定葡萄糖的杯[4]芳烃苯硼酸衍生物/多壁碳纳米管复合材料,并研究该杯[4]芳烃苯硼酸衍生物/多壁碳纳米管复合材料作为电化学传感器用于测定葡萄糖。
本发明的目的可以通过以下技术方案来实现:
1.杯[4]芳烃苯硼酸衍生物的化学式为C62H78B2O10。以3-羟基苯硼酸为辅配体,杯[4]芳烃二溴化合物为主配体,如此构成了下式杯[4]芳烃苯硼酸衍生物:
根据权利要求1的所述的杯[4]芳烃苯硼酸衍生物与多壁碳纳米管掺杂得到杯[4]芳烃苯硼酸衍生物/多壁碳纳米管复合物,其特征在于,其中所述衍生物具有下式结构:
所述的杯[4]芳烃苯硼酸衍生物/多壁碳纳米管复合材料的制备方法,其特征在于,该方法包括以下步骤:
(1)合成杯[4]芳烃二溴化合物,得到白色粉末。圆底烧瓶中依次分别加入3.2g对叔丁基杯[4]芳烃,10.1g 1,3-二溴丙烷,1.73g无水碳酸钾,125mL的无水乙腈;通氮气,油浴加热回流48小时,停止加热,冷却至室温,旋转蒸发得剩余物;向剩余物中依次加入100mL5%的HCl和200mL的氯仿,分液萃取多次,分出有机相,用饱和食盐水和蒸馏水反复洗涤至pH值为中性。加无水硫酸钠干燥24小时,过滤,旋转蒸发除去溶剂后得到白色粉末状粗产品。柱色谱分离纯化(V石油醚:V乙酸乙酯=4:3),得到白色粉末状产品。
(2)在圆底烧瓶中,加入(1)步骤处理得到的产品0.1780g(约0.2mmol),0.0266g(约0.16mmol)KI,5mL乙腈,油浴搅拌加热30min。取另一个圆底烧瓶,加入0.2g(约1.44mmol)无水碳酸钾,0.0662g(约0.48mmol)3-羟基苯硼酸,3mL乙腈,油浴搅拌加热30min。将第二个圆底烧瓶中的溶液分批加入第一个烧瓶中,油浴搅拌回流48小时,反应完全后停止加热,冷至室温,旋转蒸发除去部分溶剂。
(3)将步骤(2)所得的产品使用二氯甲烷和5%的稀盐酸溶液萃取分液,合并有机相,用蒸馏水洗有机相至pH为中性。旋转蒸发除去二氯甲烷和极少量的水后得到黄色的固体粉末,将固体粉末放于烘箱中40℃烘干,得到粗产品。
(4)将步骤(3)处理得到的粗产品用硅胶大板分离纯化(V乙酸乙酯:V石油醚=1:4),得到20mg黄色固体粉末,产率为10%。
(5)称取0.3g多壁碳纳米管,在4mol/L的硝酸中回流24h,回流结束后,将纯化的碳纳米管离心后倾析除去上层清液,加入二次蒸馏水,反复离心洗涤直至pH为中性,放入干燥箱于60℃烘12h。。
(6)取步骤(5)所得物5mg和步骤(4)得到的产物5mg溶于10mL乙醇中,超声分散3h,得到杯[4]芳烃苯硼酸衍生物/多壁碳纳米管复合材料。
杯[4]芳烃苯硼酸衍生物/多壁碳纳米管复合材料应用,该复合物可测定葡萄糖。
杯[4]芳烃苯硼酸衍生物/多壁碳纳米管复合材料测定葡萄糖,实验结果表明:杯芳烃的特异识别增强了对葡萄糖的识别能力,电化学信号强度有明显增强,灵敏度得到提高,抗干扰性强。
进行了氢谱(1H NMR)、电喷雾质谱(ES-MS)和红外光谱(IR)表征。利用电化学检测手段,使用所设计合成的杯[4]芳烃苯硼酸衍生物/多壁碳纳米管复合材料测定葡萄糖。
附图说明
图1是本发明所获取的杯[4]芳烃苯硼酸衍生物/多壁碳纳米管复合材料的SEM图;
图2是本发明所获取的在Na2HPO4-NaH2PO4离子缓冲剂溶液中,杯[4]芳烃苯硼酸衍生物/多壁碳纳米管复合材料修饰电极对比多壁碳纳米管修饰电极电流-时间曲线图;
图3是本发明所获取的在Na2HPO4-NaH2PO4离子缓冲剂溶液中,对比不同电极与葡萄糖作用的差分脉冲伏安图;
图4是本发明所获取的在Na2HPO4-NaH2PO4离子缓冲剂溶液中,不同修试剂用量的影响图;
图5是本发明所获取的在Na2HPO4-NaH2PO4离子缓冲剂溶液中,不同pH的影响图;
图6是本发明所获取的在Na2HPO4-NaH2PO4离子缓冲剂溶液中,抗干扰能力图
图7本发明所获取的在Na2HPO4-NaH2PO4离子缓冲剂溶液中,电极稳定性图
具体实施方式
以下结合实施例对本发明进行详细的描述。
实施例1
新型杯[4]芳烃苯硼酸衍生物的合成
1、圆底烧瓶中依次分别加入3.2g对叔丁基杯[4]芳烃,10.1g 1,3-二溴丙烷,1.73g无水碳酸钾,125mL的无水乙腈;通氮气,油浴加热回流48小时,停止加热,冷却至室温,旋转蒸发得剩余物;向剩余物中依次加入100mL 5%的HCl和200mL的氯仿,分液萃取多次,分出有机相,用饱和食盐水和蒸馏水反复洗涤至pH值为中性。加无水硫酸钠干燥24小时,过滤,旋转蒸发除去溶剂后得到白色粉末状粗产品。柱色谱分离纯化(V石油醚:V乙酸乙酯=4:3),得到白色粉末状产品。
2、在圆底烧瓶中,加入步骤(1)处理得到的产品0.1780g(约0.2mmol),0.0266g(约0.16mmol)KI,5mL乙腈,油浴搅拌加热30min。取另一个圆底烧瓶,加入0.2g(约1.44mmol)无水碳酸钾,0.0662g(约0.48mmol)3-羟基苯硼酸,3mL乙腈,油浴搅拌加热30min。将第二个圆底烧瓶中的溶液分批加入第一个烧瓶中,油浴搅拌回流48小时,反应完全后停止加热,冷至室温,旋转蒸发除去部分溶剂。
3、将步骤2所得的产品使用二氯甲烷和5%的稀盐酸溶液萃取分液,合并有机相,用蒸馏水洗有机相至pH为中性。旋转蒸发除去二氯甲烷和极少量的水后得到黄色的固体粉末,将固体粉末放于烘箱中40℃烘干,得到粗产品。
4、将步骤3处理得到的粗产品用硅胶大板分离纯化(V乙酸乙酯:V石油醚=1:4),得到20mg黄色固体粉末,产率为10%。
IR(KBr):υ/cm-1
1H NMR(400MHz,CDCl3)δ
9.89(s,2H,ArH),
7.87(s,2H,BOH),
7.84(s,2H,BOH),
7.74(s,2H,OH),
7.26(s,2H,ArH),
7.10(s,2H,ArH),
7.09(s,4H,ArH),
7.06(s,2H,ArH),
4.51(t,4H,BrCH2CH2CH2),
4.27(s,2H,ArCH2Ar),
4.24(s,2H,ArCH2Ar),
4.16(t,4H,BrCH2CH2CH2),
3.39(s,2H,ArCH2Ar),
3.16(s,2H,ArCH2Ar),
2.38(m,4H,BrCH2CH2CH2),
1.32(s,18H,C(CH3)3),
1.04(s,18H,C(CH3)3).
ESI-MS:m/z-=1005.62,(M+H+)
实施例2
杯[4]芳烃苯硼酸衍生物/多壁碳纳米管的合成
1、称取0.3g多壁碳纳米管,在4mol/L的硝酸中回流24h,回流结束后,将纯化的碳纳米管离心后倾析除去上层清液,加入二次蒸馏水,反复离心洗涤直至pH为中性,放入干燥箱于60℃烘12h。。
2、取步骤实例1所得物5mg和上一步得到的产物5mg溶于10mL乙醇中,超声分散3h,得到杯[4]芳烃苯硼酸衍生物/多壁碳纳米管复合材料。
实施例3
杯[4]芳烃苯硼酸衍生物/多壁碳纳米管复合材料测定葡萄糖的电化学传感实验:
实验仪器:CHI660C电化学分析仪
支持电解液:配制0.1mol/L的磷酸盐缓冲溶液,根据需要调到所需pH得到支持电解液。用所配得的缓冲溶液配制0.01mol/L的葡萄糖溶液,实验时,根据需要用缓冲溶液稀释到所需浓度。
实验方法:差分脉冲伏安法循环伏安法电流-时间曲线
仪器参数:差分脉冲伏安法初始电位:0.6V,终止电位:-0.8V,灵敏度:1×10-4。循环伏安法:高电位:0.6V,低电位:-1.4V,扫描速度0.1mv/s,灵敏度:1×10-4。电流-时间曲线:起始电位:-0.4V,灵敏度:1×10-4,运行时间:400s。
修饰电极的制备:依次用1-6号的金相砂纸将玻碳电极表面抛光,然后在麂皮上依次用0.3μm、0.05μm的三氧化二铝粉末抛光呈镜面,每次抛光后分别用无水乙醇和去离子水超声清洗30秒。在0.5-1.0mol/L的硫酸溶液中进行活化处理,用循环伏安法反复扫描直至得到稳定的循环福安图为止,扫描速率为100mV/s,扫描范围为-1.0-1.0V。
将在乙醇中分散的杯[4]芳烃苯硼酸衍生物/多壁碳纳米管复合材料采用滴涂法修饰在电极表面,修饰前将修饰液超声10min,用微量进样器吸取上述悬浊液,均匀滴涂在玻碳电极的表面,然后将电极放在阴凉处自然晾干备用。用同样方法制得未经修饰杯芳烃的碳纳米管的修饰电极。
结果表明:杯[4]芳烃苯硼酸衍生物/多壁碳纳米管修饰电极能够测定葡萄糖。
Claims (1)
1.一种杯[4]芳烃苯硼酸衍生物/多壁碳纳米管的制备方法,其特征在于,所述衍生物的化学式为C62H78B2O10,以杯[4]芳烃二溴化合物主配体,3-羟基苯硼酸为辅配体,其结构式如下:
具体步骤如下:
一、预备步骤
(1)合成杯[4]芳烃二溴化合物,得到白色粉末;
圆底烧瓶中依次分别加入3.2g对叔丁基杯[4]芳烃,10.1g1,3-二溴丙烷,1.73g无水碳酸钾,125mL的无水乙腈;
通氮气,油浴加热回流48小时,停止加热,冷却至室温,旋转蒸发得剩余物;
向剩余物中依次加入100mL5%的HCl和200mL的氯仿,分液萃取多次,分出有机相,用饱和食盐水和蒸馏水反复洗涤至pH值为中性;
加无水硫酸钠干燥24小时,过滤,旋转蒸发除去溶剂后得到白色粉末状粗产品;柱色谱分离纯化,得到纯白色粉末状的杯[4]芳烃二溴化合物固体3.0g;
二、杯[4]芳烃苯硼酸衍生物的反应步骤:
(1)在圆底烧瓶中,加入预备步骤处理得到的产品0.1780g,0.0266gKI,5mL乙腈,油浴搅拌加热30min;取另一个圆底烧瓶,加入0.2g无水碳酸钾,0.0662g3-羟基苯硼酸,3mL乙腈,油浴搅拌加热30min;将第二个圆底烧瓶中的溶液分批加入第一个烧瓶中,油浴搅拌回流48小时,反应完全后停止加热,冷至室温,旋转蒸发除去部分溶剂;
(2)将步骤(1)所得的产品使用二氯甲烷和5%的稀盐酸溶液萃取分液,合并有机相,用蒸馏水洗有机相至pH为中性,旋转蒸发除去二氯甲烷和极少量的水后得到黄色的固体粉末,将固体粉末放于烘箱中40℃烘干,得到粗产品;
(3)将步骤(2)处理得到的粗产品用硅胶大板分离纯化,V乙酸乙酯:V石油醚=1:4,得到20mg黄色固体粉末,产率为10%;
三、杯[4]芳烃苯硼酸衍生物/多壁碳纳米管复合材料的合成步骤:
(1)称取0.3g多壁碳纳米管,在4mol/L的硝酸中回流24h,回流结束后,将纯化的碳纳米管离心后倾析除去上层清液,加入二次蒸馏水,反复离心洗涤直至pH为中性,放入干燥箱于60℃烘12h;
(2)取本合成步骤中步骤(1)所得物5mg和步骤(3)得到的产物5mg溶于10mL乙醇中,超声分散3h,得到杯[4]芳烃苯硼酸衍生物/多壁碳纳米管复合物。
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