CN109293707B - 一种l-组氨酸缩乙二醛双席夫碱镍配合物的制备方法 - Google Patents
一种l-组氨酸缩乙二醛双席夫碱镍配合物的制备方法 Download PDFInfo
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Abstract
本发明公开了一种L‑组氨酸缩乙二醛双席夫碱镍配合物的制备方法。以L‑组氨酸和乙二醛为原料，以甲醇为溶剂，不需要加催化剂，即可制备L‑组氨酸缩乙二醛双席夫碱，再以L‑组氨酸缩乙二醛双席夫碱为配体，在甲醇水溶液中，与氯化镍反应，制备L‑组氨酸缩乙二醛双席夫碱镍配合物。本发明方法具有不需加催化剂，工艺简单、重复性好、产率高等优点，应用于光催化降解亚甲基蓝溶液，效果良好。
Description
技术领域
本发明属于有机合成领域，具体涉及一种L-组氨酸缩乙二醛双席夫碱镍配合物的制备方法。
背景技术
科技进步，工业发展，生活水平的提高，有机染料的需求量越来越大。有机染料成分复杂、色度高、排放量大、毒性大、可生化性差，排入水体后，改变了水体的化学、物理、生物或者放射性等特征，造成水质恶化，甚至威胁人类的健康。目前，处理有机染料废水的方法主要有生物降解，化学氧化，絮凝，过滤，吸附和光催化等。光催化技术因具有降解率高、工艺简单、操作条件可控，降解有机染料无选择性等特点，已成为研究的热点之一。Saleh R等合成了铁掺杂纤锌矿ZnO纳米粒子，在紫外光照射下，掺杂铁的ZnO纳米粒子，其光催化活性明显提高，且对甲基橙的降解效果优于亚甲基蓝。Sonia S等采用简单的水热法制备了高稳定性的CuO纳米粒子，CuO纳米粒子具有优良的光催化性能，在紫外光照射下，对亚甲基紫的降解效率高达96％。Mohamed A等以聚丙烯腈(PAN)、碳纳米管(CNT)和表面功能化TiO2纳米粒子为基础，制备了复合纳米纤维。与其他研究相比，在较短时间，较低功率的紫外光条件下，复合纳米纤维对亚甲基蓝和靛蓝具有较好降解效果，稳定性研究结果显示，复合纳米纤维对亚甲基蓝和靛蓝光降解五次循环后，降解效率可保持在99％左右。Alamelu K等合成了TiO2纳米粒子和石墨烯-TiO2复合材料，研究结果表明，与纯TiO2纳米粒子相比，石墨烯-TiO2复合材料对刚果红和亚甲基蓝染料的降解率分别提高了15倍和3.5倍。迄今为止，文献报道的大多都是TiO2，ZnO，CuO及其复合材料，而对席夫碱配合物在光催化降解有机染料领域的研究相对较少。
L-组氨酸是人体的一种半必需氨基酸，价格低廉，易于购买。以L-组氨酸为原料合成的共轭双席夫碱，具有多个O、N活性位点，可以与多种金属盐发生配位，形成稳定的金属配合物。亚甲蓝(MB)是一种常见的有机染料，化学名称是3,7-双(二甲氨基)吩噻嗪-5-鎓氯化物，属于杂环芳香族化合物。亚甲蓝广泛存在于纺织废水中，亚甲蓝会降低光的穿透性，减弱光合作用，破坏水体的生态平衡。
本发明公开了一种L-组氨酸缩乙二醛双席夫碱镍配合物的制备方法。所述方法是以L-组氨酸和乙二醛为原料，不需要加催化剂，即可制备L-组氨酸缩乙二醛双席夫碱，再以L-组氨酸缩乙二醛双席夫碱为配体，与氯化镍反应，制备L-组氨酸缩乙二醛双席夫碱镍配合物。本发明所述的制备方法具有不需加催化剂，工艺简单、重复性好、产率高等优点。L-组氨酸缩乙二醛双席夫碱镍配合物应用于对亚甲蓝溶液的光催化降解，效果良好。
发明内容
本发明的目的是提供一种L-组氨酸缩乙二醛双席夫碱镍配合物的制备方法。
具体步骤为：
(1)称取1.6292g(10mmol)L-组氨酸置于三口烧瓶中，加入20mL无水甲醇，形成白色浊液，边搅拌边缓慢滴加10mL 0.5892g(10mmol)KOH无水甲醇溶液，白色浊液变澄清。
(2)再向(1)的澄清溶液中，逐滴滴加5mL 0.2902g(5mmol)乙二醛无水甲醇溶液，氮气保护下，55℃回流搅拌4h，自然冷却至室温，得到黄色溶液，将其置于冰箱挥发，一周后有黄色球状晶体析出，抽滤，得沉淀。
(3)将(2)中获得的沉淀，用无水甲醇洗涤3次，无水甲醇每次用量10mL，25℃真空干燥，即得到L-组氨酸缩乙二醛双席夫碱。
(4)将0.1662g(0.5mmol)步骤(3)制得的L-组氨酸缩乙二醛双席夫碱溶于10mL甲醇溶液中，得到黄色浊液，将其转入三口烧瓶，逐滴滴加10mL 0.1188g(0.5mmol)氯化镍甲醇溶液，浊液逐渐变为绿色澄清溶液，100℃回流反应18h，自然冷却至室温，于冰箱中静置挥发，得到浅绿色沉淀，过滤，用无水甲醇洗涤3次，无水甲醇每次用量10mL，25℃真空干燥，即得到L-组氨酸缩乙二醛双席夫碱镍配合物。
本发明方法具有不需加催化剂，工艺简单、重复性好、产率高等优点，应用于光催化降解亚甲基蓝溶液，效果良好。
附图说明
图1为本发明实施例中L-组氨酸缩乙二醛双席夫碱的红外光谱图。
图2为本发明实施例中L-组氨酸缩乙二醛双席夫碱镍配合物的红外光谱图。
图3为本发明实施例中L-组氨酸缩乙二醛双席夫碱镍配合物的紫外-可见漫反射光谱。
图4为本发明实施例中L-组氨酸缩乙二醛双席夫碱镍配合物的K-M转换图。
具体实施方式
实施例：
(1)称取1.6292g(10mmol)L-组氨酸置于三口烧瓶中，加入20mL无水甲醇，形成白色浊液，边搅拌边缓慢滴加10mL 0.5892g(10mmol)KOH无水甲醇溶液，白色浊液变澄清。
(2)再向(1)的澄清溶液中，逐滴滴加5mL 0.2902g(5mmol)乙二醛无水甲醇溶液，氮气保护下，55℃回流搅拌4h，自然冷却至室温，得到黄色溶液，将其置于冰箱挥发，一周后有黄色球状晶体析出，抽滤，得沉淀。
(3)将(2)中获得的沉淀，用无水甲醇(10mL×3)洗涤，25℃真空干燥，即得到0.2342g黄色L-组氨酸缩乙二醛双席夫碱，产率为14.09％，熔点为274.4～275.3℃。
(4)将0.1662g(0.5mmol)步骤(3)制得的L-组氨酸缩乙二醛双席夫碱溶于10mL甲醇溶液中，得到黄色浊液，将其转入三口烧瓶，逐滴滴加10mL 0.1188g(0.5mmol)氯化镍甲醇溶液，浊液逐渐变为绿色澄清溶液，100℃回流反应18h，自然冷却至室温，于冰箱中静置挥发，得到浅绿色沉淀，过滤，无水甲醇(10mL×3)洗涤，25℃真空干燥，即得到L-组氨酸缩乙二醛双席夫碱镍配合物。
采用500MHz超导核磁共振波谱仪，以氘代二甲基亚砜(DMSO)和氘代水为溶剂，对L-组氨酸缩乙二醛双席夫碱配体进行了核磁共振氢谱(1H NMR)的测试。可知，7.67ppm处的单重峰为两个咪唑环中―CH＝N―的两个氢原子峰，6.97ppm处的单重峰为两个咪唑环―CH＝C―的两个氢原子峰，3.89～3.91ppm处的多重峰为两个―CH―CH―中的两个氢原子峰，3.13～3.16ppm处的多重峰为两个―CH2―中四个氢原子峰，3.01～3.12ppm处的多重峰为两个―CH―中的两个氢原子峰，13.00ppm左右没有发现两个咪唑环中―NH―的氢原子峰，是由于在测试的过程中，―NH―的氢原子被氘代试剂氘代。11.00ppm左右处没有发现―COOH中氢原子的峰，是因为在碱性条件下，羧基以―COO-存在。4.71ppm处的峰为所用溶剂氘代水中残余氢原子的峰。核磁共振氢谱分析结果与L-组氨酸缩乙二醛双席夫碱构造式相吻合。
L-组氨酸缩乙二醛双席夫碱的红外光谱分析(附图1)：1641cm-1是席夫碱基的C＝N的伸缩振动吸收峰，3003cm-1是N―H伸缩振动吸收峰，2877cm-1是亚甲基―CH2―的C―H伸缩振动吸收峰，1467cm-1是亚甲基―CH2―的C―H面内弯曲振动吸收峰，1250cm-1归属为羧基C―O的伸缩振动吸收峰，622cm-1归属为羧基―COOH的弯曲振动吸收峰。
L-组氨酸缩乙二醛双席夫碱镍配合物的红外光谱分析(附图2)：1634cm-1是席夫碱基的C＝N的伸缩振动吸收峰，与配体相比，发生了蓝移，说明席夫碱基的N与Ni2+发生配位。1257cm-1归属为羧基C―O的伸缩振动吸收峰，622cm-1归属为羧基―COOH的弯曲振动吸收峰，与双席夫碱配体相比，均发生了一定的红移，这可能是因为配体中的―COO-与Ni2+发生了配位，使配体分子周边的电子云密度发生了改变而造成的。
本发明对双席夫碱镍配合物的紫外-可见漫反射光谱进行了测试：取适量BaSO4固体粉末置于样品槽中，用黑色塑料柱轻轻旋转压实压平，使BaSO4固体粉末刚好充满整个样品槽，得到标准白板；再将适量用玛瑙研钵研磨好的L-组氨酸缩乙二醛双席夫碱镍配合物粉末置于标准白板上，再次用黑色塑料柱压实压平，得到样品板。用标准白板扫描背景后，样品板在200～800nm的范围内，利用紫外可见近红外光谱仪进行扫描，即可得到紫外-可见漫反射光谱(见附图3)。通过库贝尔卡-蒙克(Kuelka-Munk)方法，将紫外-可见漫反射光谱转换为F与E的关系图(附图4)，得到镍配合物的能带隙值(Eg)。转换的过程为：利用紫外漫反射光谱数据分别求F值和E值，然后以F对E作图，将图中直线部分外推至横坐标轴，交点即为Eg。其中F＝(αhν)1/2，E＝hv＝hc/λ，h为普朗克常量，c为光速，λ为光的波长，α为吸光度。如附图4所示，镍配合物的Eg为1.91eV，表明镍配合物具有半导体性质，在紫外光区，镍配合物具有选择性吸收。
本发明对双席夫碱镍配合物对光催化降解亚甲蓝溶液进行了测试：准确称取5mg镍配合物置于50mL 10mg·L-1的亚甲蓝(MB)溶液中，放入数控超声波清洗器中，室温下超声震荡半个小时，确保镍配合物与MB达到吸附-解吸平衡。打开光催化平行合成仪的紫外灯，调节循环冷凝水的流速，使温度维持在25℃，再将混合液置于光催化平行合成仪中，每隔20min取2.5mL上层液体，在250-800nm的范围内测试紫外光谱。在同样的条件下，研究了0.05mg·mL-1，0.1mg·mL-1，0.15mg·mL-1，0.2mg·mL-1，0.25mg·mL-1，0.3mg·mL-1镍配合物对亚甲蓝紫外光催化降解情况，按下列公式，计算降解率。
ηt(％)＝(C0-C)/C0
式中，ηt表示时间为t min时的降解率，C0为亚甲蓝的初始浓度(mg·L-1)，C为亚甲蓝在时间为t min时的浓度。
实验结果表明，紫外光照射了220min之后，未加镍配合物，只有少量亚甲蓝(MB)溶液发生降解。而加入了0.05mg·mL-1，0.1mg·mL-1，0.15mg·mL-1，0.2mg·mL-1，0.25mg·mL-1，0.3mg·mL-1镍配合物，亚甲蓝(MB)溶液均发生了较大程度的降解，降解率分别为76.09％，78.30％，58.35％，53.71％，49.88％，43.34％。镍配合物用量为0.05～0.1mg·mL-1时，MB的降解率增加；当镍配合物用量为0.1-0.3mg·mL-1时，随着镍配合物用量的增加，降解效果反而降低了，这是因为镍配合物用量超过0.1mg·mL-1后，阻碍了紫外光的穿透，降低了降解效果。由此可知，镍配合物用量为0.1mg·mL-1对10mg·L-1亚甲蓝(MB)溶液光催化降解效果最好。
Claims (1)
1.一种L-组氨酸缩乙二醛双席夫碱镍配合物的制备方法，其特征在于具体步骤为：
（1）称取1.6292 gL-组氨酸置于三口烧瓶中，加入20 mL无水甲醇，形成白色浊液，边搅拌边缓慢滴加10 mL 含0.5892 g KOH的无水甲醇溶液，白色浊液变澄清；
（2）再向（1）的澄清溶液中，逐滴滴加5 mL 含0.2902 g乙二醛的无水甲醇溶液，氮气保护下，55℃回流搅拌4h，自然冷却至室温，得到黄色溶液，将其置于冰箱挥发，一周后有黄色球状晶体析出，抽滤，得沉淀；
（3）将（2）中获得的沉淀，用无水甲醇洗涤3次，无水甲醇每次用量10 mL，25℃真空干燥，即得到L-组氨酸缩乙二醛双席夫碱；
（4）将0.1662 g步骤（3）制得的L-组氨酸缩乙二醛双席夫碱溶于10 mL甲醇溶液中，得到黄色浊液，将其转入三口烧瓶，逐滴滴加10 mL 含0.1188 g氯化镍的甲醇溶液，浊液逐渐变为绿色澄清溶液，100 ℃回流反应18 h，自然冷却至室温，于冰箱中静置挥发，得到浅绿色沉淀，过滤，用无水甲醇洗涤3次，无水甲醇每次用量10 mL，25℃真空干燥，即得到L-组氨酸缩乙二醛双席夫碱镍配合物。
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Application publication date: 20190201 Assignee: GUANGXI GUOBO TECHNOLOGY Co.,Ltd. Assignor: GUILIN University OF TECHNOLOGY Contract record no.: X2022450000462 Denomination of invention: Preparation of a nickel complex with L-histidine glyoxal bis Schiff base Granted publication date: 20201222 License type: Common License Record date: 20221228 |