A bi-templates molecular imprinted polymers(MIPs) was prepared by using quercetin(QT) and rutin(RT) as co-templates. The preparation conditions were optimized. The effects of the molar ratio of two templates and the volume dosage of functional monomer and crosslinker on the adsorption property of MIPs were also studied. Structural characterization of the MIPs was performed by FTIR and SEM. The adsorption dynamics, adsorption isotherm, surface sites distribution and binding selectivity of the MIPs were explored. In addition, the applicability for the MIPs to separate target compound by MIPs solid phase extraction was studied. When the molar ratio of quercetin to rutin is 3:2 and the molar ratio of total templates to functional monomer to cross-linker is 1:8:10, the MIPs obtained possess the highest adsorption capacity toward two templates(47.86 mg/g for quercetin and 60.97 mg/g for rutin). The equilibrium of static adsorption is reached within 3.5 h implying a rapid adsorption dynamics. Scatchard analysis shows that there are four types of binding sites in the polymer matrix, i.e., two types of high affinity binding sites toward two templates and two types of non-selective recognition sites. The relative distribution coefficient(k=Kd(RT)/Kd(QT), Kd=qe/ρe, Kd—distribution coefficient, qe—equilibrium adsorption amount, ρe—equilibrium mass concentration) much higher than 1.0 reveals a high selectivity for the MIPs toward rutin. The highest relative distribution coefficient(6.669) and separation factor(α=qe (RT)/qe(QT))(25.02) are obtained when the concentration of rutin and quercetin in the model mixture is 0.07 and 0.03 mmol/L, respectively. When using acetonitrile, methanol and methanol-acetic acid mixture as effluents in sequence in the MIPs solid phase extraction of crude extract of sophora flower bud, quercetin and rution can be separately extracted with 96.70% and 94.67% recoveries, respectively.
Adsorption isotherm(A,B) and its scatchard analysis(inset) for the MIP5 toward quercetin(A) and rutin(B)
Types of sites
High affinity sites
Dissociation constant, K1/(mg·L-1)
Maximum apparent binding constant, Qmax1/(mg·g-1)
Low affinity sites
Dissociation constant, K2/(mg·L-1)
Maximum apparent binding constant, /(mg·g-1)
Scatchard analysis of adsorption isotherm for the MIP5 and binding sites distribution
Adsorption capacity of the MIP5 toward two compounds in quercetin-rutin model mixture solution
Composition of model mixture solution/ (mmol·L-1)
Distribution coefficients, relative distribution coefficients and separation factors for the MIP5 toward two templates in competitive adsorption test
Washing with 3.0 mL of acetonitrile
Elution with 3.0 mL of methanol/mg
Elution with 3.0 mL methanol-acetic acid mixture(volume ratio, 9:1)/mg
Loading and elution for MIPs solid phase extraction
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