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MICROCHIMICA ACTA · 2016 ·Vol. 183 ·期 5 ·1779-1786 · IF 4.831

Binary boronic acid-functionalized attapulgite with high adsorption capacity for selective capture of nucleosides at acidic pH values

Li Huihui,Zhu Shuqiang,Cheng Ting,Wang Shuxia,Zhu Bin,Liu Xiaoyan,Zhang Haixia

Boronate affinity materials have been widely used for selective capture of cis-diols such as nucleosides. Adsorbents with features of low binding pH and high adsorption capacity are highly desired. However, most reported materials only possess one of the two features. We have synthesized a 1,3,5-triazine-containing binary boronic acid by reacting cyanuric chloride with 3-aminophenylboronic acid, and the product was then grafted onto attapulgite (a fibrous aluminum-magnesium silicate). The resulting functionalized attapulgite exhibit low binding pH (5.0) and display high adsorption capacity (19.5 ± 1.1 mg⋅g −1 for adenosine). The material exhibits high selectivity for cis-diols even in the presence of a 1000-fold excess of interferences. It was applied to the selective extraction of nucleosides from human urine. Typical features of the method include (a) limits of detection in the range from 4 to 17 ng⋅mL −1 , (b) limits of quantification between 13 and 57 ng⋅mL −1 , (c) relative standard deviations of ≤9.1 %, and (d) recoveries of nucleosides from spiked human urine between 85.0 and 112.9 %. In our perception, the material and method offer a promising strategy for selective capture of cis-diols in the areas of proteomics, metabolomics and glycomics. We have prepared 1,3,5-triazine-containing binary boronic acid-functionalized attapulgite. The material exhibited low binding pH (5.0) and high adsorption capacity (19.5 ± 1.1 mg⋅g‾ 1 for adenosine).

研究领域: 生物化学 · 分析化学 · 材料科学
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ELECTROANALYSIS · 2017 ·Vol. 29 ·期 10 ·2307-2315 · IF 2.851

Disposable Sandwich-type Electrochemical Sensor for Selective Detection of Glucose Based on Boronate Affinity

Jian Li,Zhanming Bai,Yanjun Mao,Qingqing Sun,Xiaohui Ning,Jianbin Zheng

A disposable sandwich-type electrochemical sensor for selective detection of glucose was established. The primary receptor, 3-aminophenylboronic acid was grafted covalently onto the surface of screen-printed carbon electrodes through an in situ-generated diazo-reaction. Glucose was first captured by boronic acid group on the electrode, followed by captureing an electroactive ferroceneboronic acid (FcBA) as the secondary receptor to form bidentate glucose-boronic complex. Electrochemical impedance spectroscopy was applied to characterize the construction of sandwich-type disposable sensor. In the sandwich assay, current response of captured FcBA on the electrode was dependent on the concentration of glucose. The sandwich assay showed higher selectivity for glucose than that for fructose, mannose, galactose and other electroactive interferences including uric acid, ascorbic acid and dopamine, and exhibited a dynamic concentration range of glucose from 0.5 to 20.0 mmol L −1 . The disposable sensor demonstrated a good reproducibility with 2.2 % relative standard deviation (RSD). In addition, the disposable glucose sensor was used in detection of the trace glucose in the clinical urine samples.

研究领域: 生物医学工程 · 分析化学
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ANALYTICA CHIMICA ACTA · 2017 · IF 4.95

Silica stationary phase functionalized by 4-carboxy-benzoboroxole with enhanced boronate affinity nature for selective capture and separation of cis-diol compounds

Hengye Li,Xuemeng Zhang,Lin Zhang,Weihua Cheng,Fenying Kong,Dahe Fan,Lei Li,Wei Wang

4-Carboxy-benzoboroxole was designed and synthesized. It was then combined with the modification effect of polyethyleneimine (PEI) for the preparation of boronate affinity silica stationary phase. The stationary phase showed improved binding strength with dissociation constant ( K d ) towards xanthosine as low as 2.48 × 10 −4  M. The column showed excellent selectivity , high binding capacities (88.3 μmol adenosine g −1 , pH 7.0) and the lowest binding pH (4.0 for cytidine and as low as 2.24 for xanthosine). These binding properties were superior to the existing boronate affinity materials, facilitating the selective extraction of trace cis -diol compounds in complex samples and greatly expanding the application scope of boronate affinity chromatography . In addition, the column showed secondary separation capability under acidic conditions and this secondary separation capability was investigated thoroughly. It was found that the separation was pH-dependent and mainly determined by binding strength with the possibility of involvement of other interaction, providing alternative strategy for the separation of cis -diol compounds. The feasibility and practicability were demonstrated through the selective enrichment of nucleosides in urine samples and the results indicated the excellent performance and great potential for the extraction of trace cis -diol compounds in complex samples.

研究领域: 分析化学 · 生物化学
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JOURNAL OF CHROMATOGRAPHY A · 2014 · IF 4.258

Online micro-solid-phase extraction based on boronate affinity monolithic column coupled with high-performance liquid chromatography for the determination of monoamine neurotransmitters in human urine

Xiaoting Yang,Yufei Hu,Gongke Li

Quantification of monoamine neurotransmitters is very important in diagnosing and monitoring of patients with neurological disorders. We developed an online analytical method to selectively determine urinary monoamine neurotransmitters, which coupled the boronate affinity monolithic column micro-solid-phase extraction with high-performance liquid chromatography (HPLC). The boronate affinity monolithic column was prepared by in situ polymerization of vinylphenylboronic acid (VPBA) and N , N ′-methylenebisacrylamide (MBAA) in a stainless capillary column. The prepared monolithic column showed good permeability, high extraction selectivity and capacity. The column-to-column reproducibility was satisfactory and the enrichment factors were 17–243 for four monoamine neurotransmitters. Parameters that influence the online extraction efficiency, including pH of sample solution, flow rate of extraction and desorption, extraction volume and desorption volume were investigated. Under the optimized conditions, the developed method exhibited low limit of detection (0.06–0.80   μg/L), good linearity (with R 2 between 0.9979 and 0.9993). The recoveries in urine samples were 81.0–105.5% for four monoamine neurotransmitters with intra- and inter-day RSDs of 2.1–8.2% and 3.7–10.6%, respectively. The online analytical method was sensitive, accurate, selective, reliable and applicable to analysis of trace monoamine neurotransmitters in human urine sample.

研究领域: 分析化学 · 医学诊断 · 神经科学
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