β-环糊精的示波行为及其应用研究
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摘要
本论文主要研究了β-环糊精的示波特性及其对金属离子和有机药物的包结作用,并建立了β-环糊精及其被包结物的二次微分简易示波伏安法测定法。该研究能使一些在示波测定中灵敏度不高或本身没有示波活性的物质得以间接测定,从而拓宽示波分析的应用领域。全文共分为五章,作者的贡献主要有以下几个方面:
     一、在0.2mol/LNaOH底液中,β-环糊精在示波计时电位曲线阴极支-0.38V处产生一可逆切口,且阴极支的切口深度随β-环糊精量的增加而加深,据此建立了β-环糊精的二次微分简易示波伏安测定法。
     二、在0.2mol/L NaOH底液中,β-环糊精产生的灵敏切口随Cu~(2+)的加入其切口深度减小。根据β-环糊精的这一示波特性,建立了硅黄铜中铜含量测定的二次微分简易示波伏安法。当Cu~(2+)浓度在1.0×10~(-6)~2.0×10~(-5)mol/L范围内与β-环糊精二次微分峰高的降低呈线性关系,回归方程为h(V)=-3.861×10~4C+4.819(mol/L);R=-0.9992,检出限为8.0×10~(-7)mol/L,对7.0×10~(-6)mol>L Cu~(2+)五次测定结果的RSD为2.1%,平均回收率为102.4%(n=5)。并用二次微分简易示波伏安法测定了β-CD与Cu~(2+)包络物的包结比。与其它方法相比,本方法具有装置简单便宜,方法直观易行等特点。
     三、β-环糊精特殊的分子结构及其示波特性,使得L-苯丙氨酸,L-酪氨酸等没有示波活性及苯巴比妥、芦丁等有示波活性的物质在0.2mol/L NaOH底液中能与β-环糊精迅速形成包结物,从而使β-环糊精的二次微分峰高降低,据此建立了测定L-苯丙氨酸、L-酪氨酸、苯巴比妥、芦丁含量的二次微分简易示波伏安法并根据相等摩尔连续变化法和Job法测得了包结反应的包结比和包结常数,探讨了包结反应的包结机理。实验结果表明:对于一些在示波测定中灵敏度不高或本身
    
    冠穿北大学闷吐d匕学位论文
    摘要
     没有示波活性的药物,可以利用其与p一环糊精生成包结物的方法间接测定,从而
     提高药物测定的灵敏度、拓宽示波分析应用领域。
     四、根据阿莫西林在NaOH底液中水解产物轻氨卞青霉唆哇酸与p一环糊精形
    成包结物的示波特性,建立了阿莫西林的间接示波测定法,并采用等摩尔连续变化
    法和Job法分别测得p一CD与阿莫西林形成包络物的包络比为1:1、包络常数为6.0
    X 10。。
Oscillographic characteristic of 3 -cyclodextrin and its inclusion action with metal ion, some amino acid and some organic medicament were studied in this thesis. β-cyclodextrin and substance included were determined by second order differential simple Oscillographic voltammetry. This thesis consisted of four chapters, and main contents are as follows:
    1 . β-Cyclodextrin can caused a reversible incision at -0.38V(vs. SCE) on dE/dt - E curve in 0.2mol/L NaOH, and incision depth on the cathodic branch of dE/dt - E curve was deepen with the increase of β-Cyclodextrin. Based on this oscillgraphic characteristic, a method of second order differential simple oscillgraphic voltammetry for determination of β-Cyclodextrin was founded.
    2. In 0.2mol/L NaOH, the sensitive incision of P-CD would get shallow with increase of the inclusion complex formed between Cu2+ and p-CD. Based on this oscillgraphic characteristic, a method of second order differential simple oscillgraphic voltammetry for determination of Cu2+ in silicon brass was presented. The linear range for Cu2+ and and the detection limit for Cu2+ is 1.0×10-6-2.0×l0-5mol/L and 8.0×10-7mol/L, respectively. The regressive equation and correlation coefficient are h(v)=-3.861×l04C+4.819(mol/L) and (r=-0.9992), respectively. The RSD for determination of 7.0×10-6mol/L Cu2+ is 2.1%(n=5), and average recovery is 102.4%(n=5). Inclusion ratio of Cu2+ and P-CD was determined by second order differential simple oscillgraphic voltammetry. Compared with other methods, this method has the advantage of cheap equipment, simple operation and no need especial pretreatment for the sample.
    
    
    
    3. Because of especial molecule structure and oscillgraphic characteristic of β-CD, L-Phenylalanine and L-Tyrosine with Non- oscillographic active substances and Phenobarbital and Rutin with oscillographic active substances can form inclusion complex rapidly with P-CD in 0.2mol/L NaOH, and the peak height on second order differential simple oscillogram of β-CD would decrease. Based on this oscillgraphic characteristic, a second order differential simple oscillographic voltammetry for the determination of L-Phenylalanine, L-Tyrosine, Phenobarbital and Rutin was founded. Inclusion ratio and inclusion constant were determined with equal mol continuous change and Job method, and inclusion mechanism was discussed elementary. The experimental results showed that indirect determination method of inclusion system would be used successfully when the direct determination of medicine is not so sensitive or the medicine has no oscillographic active. As a result, the sensitivity of the determination for the medicine can be improved significantly and the application field of oscillographic analysis is enlarged accordingly.
    4. Based on the characteristic of the inclusion complex formed between p-CD and the hydrolysate of Amoxicillin in 0.2mol/L NaOH, a second order differential simple oscillographic voltammetry for the indirect determination of Amoxicillin was founded, and with equal mol continuous change and Job method, the inclusion ratio and the inclusion constant determined is 1 : 1 and 6. 0×105, respectively.
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