Simultaneous analysis of non‐steroidal anti‐inflammatory drugs using electrochemically controlled solid‐phase microextraction based on nanostructure molecularly imprinted polypyrrole film coupled to ion mobility spectrometry

A simple, rapid, and highly sensitive method for simultaneous analysis of anti‐inflammatory drugs (naproxen, ibuprofen, and mefenamic acid) in diluted human serum was developed using the electrochemically controlled solid‐phase microextraction coupled to ion mobility spectrometry. A conducting molecularly imprinted polymer film based on polypyrrole was synthesized for the selective uptake and release of drugs. The film was prepared by incorporation of a template molecule (naproxen) during the electropolymerization of pyrrole onto a platinum electrode using cyclic voltammetry method. The measured ion mobility spectrometry intensity was related to the concentration of analytes taken up into the films. The calibration graphs (naproxen, ibuprofen, and mefenamic acid) were linear in the range of 0.1–30 ng/mL and detection limits were 0.07–0.37 ng/mL and relative standard deviation was lower than 6%. On the basis of the results obtained in this work, the conducting molecularly imprinted polymer films as absorbent have been applied in the electrochemically controlled solid‐phase microextraction and ion mobility spectrometry system for the selective clean‐up and quantification of trace amounts of anti‐inflammatory drugs in human serum samples. Scanning electron microscopy has confirmed the nano‐structure morphology of the polypyrrole film.     

Isolation and determination of estrogens in water samples by solid‐phase extraction using molecularly imprinted polymers and HPLC

Advanced SPE with molecularly imprinted polymers (MIP) was used in this study. A noncovalent imprinting approach was applied to separate 17β‐estradiol, estriol, and estrone from water samples. Polymer material was prepared by bulk polymerization with methacrylic acid as a functional monomer, divinylbenzene and ethyleneglycol dimethacrylate as crosslinkers, and acetonitrile, acetonitrile/toluene (3:1, v/v) or isooctane/toluene (1:99, v/v) as a porogen. We also prepared an MIP film on a silica gel surface with methacrylic acid and ethyleneglycol dimethacrylate as monomers and acetonitrile as a solvent. Qualitative and quantitative hormone analyses were carried out by HPLC with various detection techniques, including UV/visible spectroscopic detection (diode array detection) and electrochemical detection (CoulArray). The results of the study indicate that MIP technology is an excellent method for the quality control of estrogens in environmental analyses with a low quantification limit for 17β‐estradiol of around 26 (diode array detection) and 0.25 ng/mL (electrochemical detection). The proposed method was found to be suitable for routine determinations of the analyzed compound in environmental laboratories.     

Selective separation of lambdacyhalothrin by porous/magnetic molecularly imprinted polymers prepared by Pickering emulsion polymerization

Porous/magnetic molecularly imprinted polymers (PM‐MIPs) were prepared by Pickering emulsion polymerization. The reaction was carried out in an oil/water emulsion using magnetic halloysite nanotubes as the stabilizer instead of a toxic surfactant. In the oil phase, the imprinting process was conducted by radical polymerization of functional and cross‐linked monomers, and porogen chloroform generated steam under the high reaction temperature, which resulted in some pores decorated with easily accessible molecular binding sites within the as‐made PM‐MIPs. The characterization demonstrated that the PM‐MIPs were porous and magnetic inorganic–polymer composite microparticles with magnetic sensitivity (M_s = 0.7448 emu/g), thermal stability (below 473 K) and magnetic stability (over the pH range of 2.0–8.0). The PM‐MIPs were used as a sorbent for the selective binding of lambdacyhalothrin (LC) and rapidly separated under an external magnetic field. The Freundlich isotherm model gave a good fit to the experimental data. The adsorption kinetics of the PM‐MIPs was well described by pseudo‐second‐order kinetics, indicating that the chemical process could be the rate‐limiting step in the adsorption of LC. The selective recognition experiments exhibited the outstanding selective adsorption effect of the PM‐MIPs for target LC. Moreover, the PM‐MIPs regeneration without significant loss in adsorption capacity was demonstrated by at least four repeated cycles.     

Preparation and evaluation of a novel molecularly imprinted SPE monolithic capillary column for the determination of auramine O in shrimp

A novel method combining molecular imprinting and SPE was developed in a capillary column for the determination of auramine O in shrimp. The capillary monolithic column was prepared by UV‐initiated in situ polymerization, using auramine O as template and methacrylic acid and ethylene dimethacrylate as functional monomer and cross‐linker, respectively. The properties of the prepared capillary monolithic column were investigated under the optimized conditions coupled with HPLC, and then the morphologies of the inner polymers were characterized by SEM. The calibration curve was expressed as A = 103C + 19.8 (r = 0.9992) with a linear range of 0.25–25.0 μg/mL, and the recoveries of auramine O at different concentrations in shrimp ranged from 90.5 to 92.4% with RSDs ranging from 2.1 to 4.4%. The capacities of the molecularly imprinted polymer and nonimprinted polymer columns were 0.722 and 0.147 μg/mg, respectively, and the LOD (S/N = 3) of auramine O in shrimp was 17.85 μg/kg. Under the selected conditions, the enrichment factors obtained were higher than 70‐fold. The results indicate that the prepared molecularly imprinted capillary monolithic column was reliable and applicable to the analysis of auramine O in shrimp.     

Highly selective determination of rhodium(III) using silica gel surface-imprinted solid-phase extraction

A novel Rh(III)-imprinted amino-functionalised silica gel sorbent was prepared by a surface imprinting technique for preconcentration and separation of Rh(III) prior to its determination by inductively coupled plasma atomic emission spectrometry (ICP-AES). Compared with the traditional solid sorbents and non-imprinted polymer particles, the ion-imprinted polymers (IIPs) had higher adsorption capacity and selectivity for Rh(III). The maximum static adsorption capacity of the imprinted and non-imprinted sorbent for Rh(III) was 29.86?mg?g^?1 and 11.23?mg?g^?1, respectively. The imprinted Rh(III) was removed with 2?mL of 3% thiourea?+?2?mol?L^?1 HCl. The obtained imprinted particles exhibited excellent selectivity and rapid kinetics process for Rh(III). The relatively selective factor (α_r) values of Rh(III)/Ru(III), Rh(III)/Au(III), Rh(III)/Pt(IV), Rh(III)/Ir(IV), Rh(III)/Pd(II) were 26.7, 39.0 29.2, 28.1, 43.7, respectively, which were greater than 1. The detection limit (3σ) of the method was 0.26?µg?L^?1. The relative standard deviation of the method was 1.79% for eight replicate determination of 10?µg of Rh³⁺ in 200?mL water sample. The method was validated by analysing standard reference material (GBW 07293), the results obtained is in good agreement with standard values. The developed method was also successfully applied to the determination of trace rhodium(III) in geological samples with satisfactory results.     

分子烙印亲和色谱与质谱联用实现中草药活性成分分离鉴定一体化

以骆驼蓬种籽中抗肿瘤活性化合物哈尔明及哈马灵的结构类似物哈尔满作为模 板,用非共价键法制备了对哈尔明及哈马灵具有强亲和性的分子烙印聚合物。此分 子烙印聚合物作为液相色谱固定相与大气压电离飞行时间质谱联用,直接分离鉴定 了草药骆驼蓬种籽甲醇粗提物中所含的哈尔明及哈灵两种抗肿瘤活性成分。实验结 果证明了通过分子烙印亲和色谱与质谱联用方法,快速有效地对中草药活性成分分 离鉴定是可能是。     

Picolinamide-Cu(Ac)2-imprinted polymer with high potential for recognition of picolinamide-copper acetate complex

In this report, with semi-empirical quantum method, we have studied the conformation and energy of supermolecule composed of picolinamide and its positional isomers with methacrylic acid. We tried to explore the reason why picolinamide was not likely to show imprinting effect when using methacrylic acid as functional monomer in our previous work. In order to produce imprinting effect, which was not achieved based on hydrogen bonding interaction, we have synthesized a molecular-imprinted polymer (MIP) based on copper ion coordination in prepolymerization. The complex in prepolymerization was composed of copper(II), acetate, picolinamide and 4-vinylpyridine (4-Vpy). Suprisingly, the MIP had high selectivity to picolinamide-copper acetate complex, and changes of either copper ion, picolinamide or acetate would result in decrease in the imprinting effect. This is also the first example where the high selective recognition of the MIP to its template was achieved mainly by inhibiting the binding of non-template rather than enhancing the binding of the template. And this report can be also looked upon as a first step towards the solution to the problem of imprinting of template that contains intramolecular hydrogen bond.     

Construction of a QCM sensor for detecting diethylstilbestrol in water based on the computational design of molecularly imprinted polymers

Combining molecular imprinting technology and quartz crystal microbalance (QCM), the diethylstilbestrol-molecularly imprinted polymers (DES-MIPs) were designed. The LC-ωPBE/6-31G(d,p) method was chosen to predict the properties of DES-MIPs in this study. The calculated results showed that the complex formed from DES and methacrylic acid with molar ratio of 1:5 and ethylene dimethacrylate as cross-linking agent had the largest amount of hydrogen bonds, the lowest binding energy, and the optimal stability property. With the guidance of calculations, the DES-MIPs were used to prepare QCM electrode by embedding method to construct the DES-MIPs-QCM sensor. The experimental results displayed that the sensor had a high binding affinity for DES when the DES-MIPs was 15 mg and the coating volume was 10 µL. The minimum detection limit of the sensor for DES was 2.63 ng/mL in the range of 50 to 350 ng/mL. The DES-MIPs-QCM sensor exhibited high recognition capacity for DES compared to its structural analogs. The sensor had been successfully used for the determination of DES in the actual water samples.     

Rapid detection of pesticide residues in Chinese herbal medicines by molecularly imprinted membrane electrospray ionization mass spectrometry

Chinese herbal medicines(CHMs) play an increasingly important role in the field of medicine and affects public health in the world.Although more and more strict has been employed to ensure the quality and safety of CHMs,pesticide residues in CHMs remain a serious issue and are the bottleneck for the global development of CHMs.In this work,we applied molecularly imprinted membrane electrospray mass spectrometry(MIM-ESI MS) for rapid detecting 4 classes of pesticide residues in CHMs,including organophosphorus(OPP),carbamates,pyrethroids and neonicotinoids in CHMs.Compared with our previous ambient ionization method MESI,MIM-ESI is capable of achieving a ～50-fold increase in the detection limit of conventional analytical methods owing to the specificity recognition and unique enrichment of MIM.The optimal experimental conditions were determined,and the method was further validated for its sensitivity and specificity.Our data showed that MIM-ESI MS is applicable for the direct quantitation of pesticide residues in CHMs.This detection technology may help to ensure the quality of CHMs in the future.     

钯纳米粒子修饰的三甲氧苄啶分子印迹膜传感器的制备及其识别性能研究

采用N,N′-亚甲基双丙烯酰胺(MBA)为功能单体、钯纳米粒子为掺杂剂、马来松香丙烯酸乙二醇酯为交联剂,在玻碳电极上热聚合具有三甲氧苄啶(TMP)识别性能的钯纳米材料修饰的分子印迹传感膜.采用扫描电镜及红外光谱对合成的钯纳米材料、印迹传感膜的形貌及其结构进行了表征;采用循环伏安法(CV)、交流阻抗法(EIS)对钯纳米粒子掺杂的印迹电极与无掺杂电极的电化学性能进行了研究.结果表明,纳米粒子掺杂的印迹电极与无掺杂电极的表面形貌及电化学性能明显不同.差分脉冲伏安法(DPV)表征结果表明,TMP的浓度在5.0×10-7~4.0 ×10-3 mol/L范围内与脉冲峰电流呈良好的线性关系(R=0.9995),检出限为3.2×10-8 mol/L (S/N=3).此钯纳米粒子掺杂的印迹传感器具有较高的灵敏度.即时电流测定结果表明,新诺明(SMZ)、磺胺嘧啶(SDZ)、葡萄糖 (Glu)、尿素 (Urea)对三甲氧苄啶(TMP)的测定不产生干扰.将此印迹传感器用于实际样品中TMP的检测,加标回收率为96.8%~102.0%.