CN111330646A - 一种高分子@Cu-MOF复合手性膜催化剂的制备方法和应用 - Google Patents
一种高分子@Cu-MOF复合手性膜催化剂的制备方法和应用 Download PDFInfo
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Abstract
本发明公开了一种高分子@Cu‑MOF复合手性膜催化剂的制备方法及基于该催化剂作为同时电化学识别酪氨酸和色氨酸对映体的应用，属于纳米材料合成技术、电化学手性识别技术领域。其主要步骤是IPDI溶液与CHI凝胶共混，干燥制得高分子膜；将高分子膜于醋酸铜溶液和配体溶液中循环浸渍，烘箱55℃过夜活化，制得高分子@Cu‑MOF复合手性膜催化剂。该催化剂制备所用原料成本低，反应能耗低，具有很好的工业前景。将该催化剂作为同时电化学识别酪氨酸和色氨酸对映体的应用，具有灵敏度高、设备简单和电化学稳定性高等优势。
Description
技术领域
本发明公开了一种高分子@Cu-MOF复合手性膜催化剂的制备方法及基于该催化剂作为同时电化学识别酪氨酸和色氨酸对映体的应用，属于纳米材料合成技术、电化学手性识别技术领域。
背景技术
手性是不对称结构中一个重要的特征。研究不称结构对于理解以对映选择性方式起作用的活生物体中发生的过程至关重要。氨基酸、糖和蛋白质等生物活性化合物是参与这些生物中起作用的物质。药品或食品添加剂中的手性对映体对生物体的作用不同。例如，有机体对消旋药物的对映异构体的分化可能会引起不同的治疗活性，这通常由一种对映异构体的理想治疗活性来解释，而另一种对映异构体则无效或是起不良作用。另一个例子，手性化合物的对映体形式的确定可能是食品工业中质量保证和安全性的宝贵指标。天然产物中D-氨基酸的检测可以评估为细菌污染的迹象。样品中D-或L-乳酸的存在可指示着细菌种类。从另一个角度来看，临床测试结果表明，单一对映体的使用可降低药物剂量，并提高治疗效果。它为我们提供了避免与其他药物发生有害相互作用的机会，并减少了由于不符合预期的对映异构体产生的毒性。在这种情况下，现代药物的设计出现了新的趋势。所以，开发廉价且更方便的技术来进行手性识别以及手性分子的定量化是极为必要的。
电化学手性识别因其成本低、特异性高、灵敏度高、响应时间快和易还原的优点引起广泛的关注。然而，在电化学手性识别中，寻找高灵敏度、高稳定性的手性催化剂成为当前研究热点。
壳聚糖（CHI）是几丁质的脱乙酰基衍生物，是一种光学活性的天然多糖。 CHI的优异性能，如亲水性、生物相容性、生物降解性、抗菌性和无毒性，使其成为识别对映异构体的手性选择剂的理想选择。壳聚糖中葡萄糖胺单元的胺基是金属离子的重要螯合位点，可用于某些金属纳米材料的合成。壳聚糖基的MOF材料为为新兴生物纳米复合材料。该纳米复合材料的物理、光学和电子特性，与其尺寸、表面形貌均具有密切的关联。
发明内容
本发明的技术任务之一是为了弥补现有技术的不足，提供了一种高分子@Cu-MOF复合手性膜催化剂的制备方法，该催化剂制备所用原料成本低，反应能耗低，具有很好的工业前景。
本发明的技术任务之二是提供所述催化剂的用途，即将高分子@Cu-MOF复合手性膜催化剂作为同时电化学识别酪氨酸和色氨酸对映体的应用，具有灵敏度高、设备简单和电化学稳定性高等优势。
为实现上述目的，本发明采用的技术方案如下：
1. 一种高分子@Cu-MOF复合手性膜催化剂的制备方法
将0.18-0.22 mmol壳聚糖CHI和1.0-1.5 mmol的醋酸铜与7-10 mL 质量分数为2%的冰醋酸共混，搅拌25-30 min，得到CHI凝胶；
将0.18-0.22 μL异佛尔酮二异氰酸酯IPDI溶于由1-2mL水和8-9 mL N, N-二甲基甲酰胺DMF组成的混合溶剂中，180 W超声2-4 min，得到IPDI溶液；
将1.0-1.5 mmol的醋酸铜与10-12 mL水共混，180 W超声2-4 min，得到澄清的醋酸铜溶液;
将1.0-1.5 mmol 的配体H2sala和1.0-1.2 mmol 的LiOH加入到10-12 mL水中，搅拌25-30 min, 得到澄清的配体溶液;
将IPDI溶液与CHI凝胶共混，继续搅拌10 min，将混合液倒入2.0 cm × 4.0 cm
聚四氟乙烯模具中，55 ℃干燥12 h，得到CHI-IPDI膜；
将CHI-IPDI膜于醋酸铜溶液中浸渍3 min后，室温干燥3-10 min，再浸渍在配体溶液中浸渍3 min后，室温干燥3-10 min；按此顺序循环10-30 次，得到CHI-IPDI@Cu-MOF复合手性膜材料，将CHI-IPDI@Cu-MOF复合手性膜材料于烘箱55 ℃过夜活化，得到活化的CHI-IPDI@Cu-MOF复合手性膜材料，即高分子@Cu-MOF复合手性膜催化剂。
所述高分子，是CHI-IPDI膜，是IPDI中的高活性异氰酸酯基-NCO与CHI中的氨基和羟基化学反应生成的手性高分子交联膜基材复合材料。
所述高分子@Cu-MOF复合手性膜催化剂，是CHI-IPDI膜与Cu2+配位形成的高分子交联膜基材负载Cu-MOF纳米晶体的复合材料。
所述Cu-MOF，其基本结构单元为[{Cu(sala)(H2O)}2]·2H2O，是由一个Cu2+，一个配体sala2-，2个主体水分子和2个客体水分子构成；所述sala2-，其构造式如下：
2.如上所述的制备方法制备的高分子@Cu-MOF复合手性膜催化剂作为同时电化学识别酪氨酸和色氨酸对映体的应用，步骤如下：
（1）配制标准溶液
采用浓度为0.5 M的KOH水溶液，分别配制系列浓度的D-酪氨酸、L-酪氨酸、D-色氨酸和L-色氨酸标准溶液；
（2）构建高分子@Cu-MOF复合手性膜电化学传感器
将高分子@Cu-MOF复合手性膜催化剂为工作电极、铂片为辅助电极、甘汞电极为参比电极，构建高分子@Cu-MOF复合手性膜电化学传感器；
（3）检测D-酪氨酸、L-酪氨酸、D-色氨酸和L-色氨酸对映体
采用线性扫描循环伏安法，分别测定步骤（1）中各浓度的D-酪氨酸、L-酪氨酸、D-色氨酸和L-色氨酸标准溶液的电流值，绘制基于高分子@Cu-MOF复合手性膜电化学传感器的D-酪氨酸、L-酪氨酸、D-色氨酸和L-色氨酸对映体的工作曲线；
将含有D-酪氨酸、L-酪氨酸、D-色氨酸和L-色氨酸混合物的待测样品溶液代替标准溶液，测得D-酪氨酸、L-酪氨酸、D-色氨酸和L-色氨酸对映体的识别效果和含量。
该手性传感器的电化学数据同时出现了D-酪氨酸、L-酪氨酸、D-色氨酸和L-色氨酸的氧化峰，实现了同时对酪氨酸和色氨酸对映体的电化学手性识别，对D-酪氨酸和L-酪氨酸对映体溶液的检测范围为0.1～2.3×10-8 g/L；对D-色氨酸和L-色氨酸对映体溶液的检测范围为0.1～3.2×10-6 g/L。
本发明有益的技术效果如下：
（1）本发明高分子@Cu-MOF复合手性膜催化剂的制备，是IPDI溶液与CHI凝胶共混，干燥制得CHI-IPDI膜；将CHI-IPDI膜于醋酸铜溶液和配体溶液中循环浸渍，烘箱55 ℃过夜活化，制得CHI-IPDI@Cu-MOF复合手性膜催化剂。该催化剂制备所用原料成本低，反应能耗低，具有很好的工业前景。
（2）本发明基于该高分子@Cu-MOF复合手性膜催化剂，含手性壳聚糖CHI分子中的多活性氨基、羟基位点，还含有因CHI-IPDI膜与Cu2+配位形成的负载Cu-MOF纳米晶手性位点。因IPDI中的高活性异氰酸酯基-NCO与CHI中的氨基和羟基化学反应生成的手性高分子交联，使得该复合手性膜不需要其他辅助材料例如玻碳电极、金属网等作为支撑电极，该CHI-IPDI@Cu-MOF复合手性膜作为同时电化学识别酪氨酸和色氨酸对映体的应用，电化学数据同时出现了D-酪氨酸、L-酪氨酸、D-色氨酸和L-色氨酸的氧化峰，实现了同时对酪氨酸和色氨酸对映体的电化学手性识别。该传感器具有灵敏度高、催化效率高、设备简单和电化学稳定性高等优势。
具体实施方式
下面结合实施例对本发明作进一步描述，但本发明的保护范围不仅局限于实施例，该领域专业人员对本发明技术方案所作的改变，均应属于本发明的保护范围内。
实施例1 一种高分子@Cu-MOF复合手性膜催化剂的制备方法
将0.18 mmol壳聚糖CHI和1.0 mmol的醋酸铜与7 mL 质量分数为2%的冰醋酸共混，搅拌2min，得到CHI凝胶；
将0.18 μL异佛尔酮二异氰酸酯IPDI溶于由1mL水和8 mL N, N-二甲基甲酰胺DMF组成的混合溶剂中，180 W超声2 min，得到IPDI溶液；
将1.0 mmol的醋酸铜与10 mL水共混，180 W超声2 min，得到澄清的醋酸铜溶液;
将1.0 mmol 的配体H2sala和1.0 mmol 的LiOH加入到10 mL水中，搅拌25 min, 得到澄清的配体溶液;
将IPDI溶液与CHI凝胶共混，继续搅拌10 min，将混合液倒入2.0 cm × 4.0 cm
聚四氟乙烯模具中，55 ℃干燥12 h，得到CHI-IPDI膜；
将CHI-IPDI膜于醋酸铜溶液中浸渍3 min后，室温干燥3 min，再浸渍在配体溶液中浸渍3 min后，室温干燥3 min；按此顺序循环10 次，得到CHI-IPDI@Cu-MOF复合手性膜材料，将CHI-IPDI@Cu-MOF复合手性膜材料于烘箱55 ℃过夜活化，得到活化的CHI-IPDI@Cu-MOF复合手性膜材料，即高分子@Cu-MOF复合手性膜催化剂。
实施例2一种高分子@Cu-MOF复合手性膜催化剂的制备方法
将0.20 mmol壳聚糖CHI和1.3 mmol的醋酸铜与8.5 mL 质量分数为2%的冰醋酸共混，搅拌27 min，得到CHI凝胶；
将0.20 μL异佛尔酮二异氰酸酯IPDI溶于由1.5 mL水和8.5 mL N, N-二甲基甲酰胺DMF组成的混合溶剂中，180 W超声3 min，得到IPDI溶液；
将1.2 mmol的醋酸铜与11 mL水共混，180 W超声3 min，得到澄清的醋酸铜溶液;
将1.2 mmol 的配体H2sala和1.1 mmol 的LiOH加入到11 mL水中，搅拌27 min, 得到澄清的配体溶液;
将IPDI溶液与CHI凝胶共混，继续搅拌10 min，将混合液倒入2.0 cm × 4.0 cm
聚四氟乙烯模具中，55 ℃干燥12 h，得到CHI-IPDI膜；
将CHI-IPDI膜于醋酸铜溶液中浸渍3 min后，室温干燥7 min，再浸渍在配体溶液中浸渍3 min后，室温干燥7 min；按此顺序循环20 次，得到CHI-IPDI@Cu-MOF复合手性膜材料，将CHI-IPDI@Cu-MOF复合手性膜材料于烘箱55 ℃过夜活化，得到活化的CHI-IPDI@Cu-MOF复合手性膜材料，即高分子@Cu-MOF复合手性膜催化剂。
实施例3一种高分子@Cu-MOF复合手性膜催化剂的制备方法
将0.22 mmol壳聚糖CHI和1.5 mmol的醋酸铜与10 mL 质量分数为2%的冰醋酸共混，搅拌30 min，得到CHI凝胶；
将0.22 μL异佛尔酮二异氰酸酯IPDI溶于由2mL水和9 mL N, N-二甲基甲酰胺DMF组成的混合溶剂中，180 W超声4 min，得到IPDI溶液；
将1.5 mmol的醋酸铜与12 mL水共混，180 W超声4 min，得到澄清的醋酸铜溶液;
将1.5 mmol 的配体H2sala和1.2 mmol 的LiOH加入到12 mL水中，搅拌30 min, 得到澄清的配体溶液;
将IPDI溶液与CHI凝胶共混，继续搅拌10 min，将混合液倒入2.0 cm × 4.0 cm
聚四氟乙烯模具中，55 ℃干燥12 h，得到CHI-IPDI膜；
将CHI-IPDI膜于醋酸铜溶液中浸渍3 min后，室温干燥10 min，再浸渍在配体溶液中浸渍3 min后，室温干燥10 min；按此顺序循环30 次，得到CHI-IPDI@Cu-MOF复合手性膜材料，将CHI-IPDI@Cu-MOF复合手性膜材料于烘箱55 ℃过夜活化，得到活化的CHI-IPDI@Cu-MOF复合手性膜材料，即高分子@Cu-MOF复合手性膜催化剂。
实施例4 CHI-IPDI膜构造
实施例1-3所述CHI-IPDI膜，是IPDI中的高活性异氰酸酯基-NCO与CHI中的氨基和羟基化学反应生成的手性高分子交联膜基材复合材料。
实施例5 高分子@Cu-MOF复合手性膜催化剂构造
实施例1-3所述高分子@Cu-MOF复合手性膜催化剂，是CHI-IPDI膜与Cu2+配位形成的高分子交联膜基材负载Cu-MOF纳米晶体的复合材料。
实施例6 Cu-MOF结构单元
实施例1-3所述Cu-MOF，其基本结构单元为[{Cu(sala)(H2O)}2]·2H2O，是由一个Cu2+，一个配体sala2-，2个主体水分子和2个客体水分子构成；所述sala2-，其构造式如下：
实施例7
实施例1制备的高分子@Cu-MOF复合手性膜催化剂作为同时电化学识别酪氨酸和色氨酸对映体的应用，步骤如下：
（1）配制标准溶液
采用浓度为0.5 M的KOH水溶液，分别配制系列浓度的D-酪氨酸、L-酪氨酸、D-色氨酸和L-色氨酸标准溶液；
（2）构建高分子@Cu-MOF复合手性膜电化学传感器
将高分子@Cu-MOF复合手性膜催化剂为工作电极、铂片为辅助电极、甘汞电极为参比电极，构建高分子@Cu-MOF复合手性膜电化学传感器；
（3）检测D-酪氨酸、L-酪氨酸、D-色氨酸和L-色氨酸对映体
采用线性扫描循环伏安法，分别测定步骤（1）中各浓度的D-酪氨酸、L-酪氨酸、D-色氨酸和L-色氨酸标准溶液的电流值，绘制基于高分子@Cu-MOF复合手性膜电化学传感器的D-酪氨酸、L-酪氨酸、D-色氨酸和L-色氨酸对映体的工作曲线；
将含有D-酪氨酸、L-酪氨酸、D-色氨酸和L-色氨酸混合物的待测样品溶液代替标准溶液，测得D-酪氨酸、L-酪氨酸、D-色氨酸和L-色氨酸对映体的识别效果和含量。
实施例8
步骤同实施例7，仅将实施例1中的高分子@Cu-MOF复合手性膜催化剂替换为实施例2中的高分子@Cu-MOF复合手性膜催化剂。
实施例9
步骤同实施例7，仅将实施例1中的高分子@Cu-MOF复合手性膜催化剂替换为实施例3中的高分子@Cu-MOF复合手性膜催化剂。
实施例10
实施例7-9制得的手性传感器的电化学数据同时出现了D-酪氨酸、L-酪氨酸、D-色氨酸和L-色氨酸的氧化峰，实现了同时对酪氨酸和色氨酸对映体的电化学手性识别，对D-酪氨酸和L-酪氨酸对映体溶液的检测范围为0.1～2.3×10-8 g/L；对D-色氨酸和L-色氨酸对映体溶液的检测范围为0.1～3.2×10-6 g/L。
Claims (5)
1.一种高分子@Cu-MOF复合手性膜催化剂的制备方法，其特征在于，步骤如下：
将0.18-0.22 mmol壳聚糖CHI和1.0-1.5 mmol的醋酸铜与7-10 mL 质量分数为2%的冰醋酸共混，搅拌25-30 min，得到CHI凝胶；
将0.18-0.22 μL异佛尔酮二异氰酸酯IPDI溶于由1-2mL水和8-9 mL N, N-二甲基甲酰胺DMF组成的混合溶剂中，180 W超声2-4 min，得到IPDI溶液；
将1.0-1.5 mmol的醋酸铜与10-12 mL水共混，180 W超声2-4 min，得到澄清的醋酸铜溶液;
将1.0-1.5 mmol 的配体H2sala和1.0-1.2 mmol 的LiOH加入到10-12 mL水中，搅拌25-30 min, 得到澄清的配体溶液;
将IPDI溶液与CHI凝胶共混，继续搅拌10 min，将混合液倒入2.0 cm × 4.0 cm
聚四氟乙烯模具中，55 ℃干燥12 h，得到CHI-IPDI膜；
将CHI-IPDI膜于醋酸铜溶液中浸渍3 min后，室温干燥3-10 min，再浸渍在配体溶液中浸渍3 min后，室温干燥3-10 min；按此顺序循环10-30 次，得到CHI-IPDI@Cu-MOF复合手性膜材料，将CHI-IPDI@Cu-MOF复合手性膜材料于烘箱55 ℃过夜活化，得到活化的CHI-IPDI@Cu-MOF复合手性膜材料，即高分子@Cu-MOF复合手性膜催化剂。
2.根据权利要求1所述的一种高分子@Cu-MOF复合手性膜催化剂的制备方法，其特征在于，所述高分子，是CHI-IPDI膜，是IPDI中的高活性异氰酸酯基-NCO与CHI中的氨基和羟基化学反应生成的手性高分子交联膜基材复合材料。
3.根据权利要求1所述的一种高分子@Cu-MOF复合手性膜催化剂的制备方法，其特征在于，所述高分子@Cu-MOF复合手性膜催化剂，是CHI-IPDI膜与Cu2+配位形成的高分子交联膜基材负载Cu-MOF纳米晶体的复合材料。
4.根据权利要求1所述的一种高分子@Cu-MOF复合手性膜催化剂的制备方法，其特征在于，所述Cu-MOF，其基本结构单元为[{Cu(sala)(H2O)}2]·2H2O，是由一个Cu2+，一个配体sala2-，2个主体水分子和2个客体水分子构成；所述sala2-，其构造式如下：
5.根据权利要求1所述的制备方法制备的高分子@Cu-MOF复合手性膜催化剂作为同时电化学识别酪氨酸和色氨酸对映体的应用。
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Application publication date: 20200626 |