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INTERNATIONAL JOURNAL OF MOLECULAR SCIENCES · 2020 ·Vol. 21 ·期 24 ·9529 · IF 4.556

A Facile Strategy for Immobilizing GOD and HRP onto Pollen Grain and Its Application to Visual Detection of Glucose

Shanxia Jin,Liping Liu,Mengying Fan,Yaru Jia,Ping Zhou

Pollen grain was explored as a new carrier for enzyme immobilization. After being modified with boric acid-functionalized titania, the pollen grain was able to covalently immobilize glycosylated enzymes by boronate affinity interaction under very mild experimental conditions (e.g., pH 7.0, ambient temperature and free of organic solvent). The glucose oxidase and horse radish peroxidase-immobilized pollen grain became a bienzyme system. The pollen grain also worked as an indicator of the cascade reaction by changing its color. A rapid, simple and cost-effective approach for the visual detection of glucose was then developed. When the glucose concentration exceeded 0.5 mM, the color change was observable by the naked eye. The assay of glucose in body fluid samples exhibited its great potential for practical application.Keywords:enzyme immobilization;boronate affinity;pollen grain;glucose detection

研究领域: 生物化学 · 分析化学 · 生物技术
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SEPARATION AND PURIFICATION TECHNOLOGY · 2024 · IF 8.1

Engineering flower-shaped hierarchical micromotors on a sustainable biotemplate by teamed boronate affinity-based surface imprinting for effective separation of shikimic acid

Yao Zhu,Ziyu Yuan,Jian Rong,Tao Zhang,Dongya Yang,Jianming Pan,Fengxian Qiu

Self-propelled nano/micromotors are the frontier of separation materials because they are capable of converting external energy in the surrounding environment into kinetic energy for their autonomous movement. In this work, a bioinspired flower-shaped hierarchical teamed boronate affinity (TBA)-imprinted Pt-free micromotor is introduced based on waste rape pollen as a biotemplate due to its merits of sustainability, rich source and low price. Such micromotor, composed of MnO 2 nanosheets as a catalytic medium, Mg-Al layered double hydroxides (LDH) nanosheets as large surface area substrate and functional surface imprinted polymers as identification subject, exhibits autonomic motor behavior powdered by oxygen bubbles generated by the decomposition of H 2 O 2 and selective recognition and separation for shikimic acid (SA). The hierarchical flower-shaped structure affords more accessible recognition sites for SA, which thus facilitates the separation process. Moreover, in combination with the TBA strategy, the micromotor can precisely recognize the target via boronate affinity between boronic acids and cis -diols from SA while showing strong binding capacity under neutral conditions. Benefiting from the pluripotent role of pioneering boronate affinity-covalent imprinted technique, hydrogen bonds interaction and nanoconfinement effect, the resulting affinity towards SA is evidently enhanced with maximal adsorption capacity of 129.51 mg g −1 at neutral pH in the presence of H 2 O 2 . After five capture/release cycles, the adsorption capacity remains above 85 %. This proposed flower-shaped hierarchical micromotor expands the scope of potential materials for the adsorption of SA and provides a new and promising direction for fabricating adsorbents applied in the separation and purification of natural products.

研究领域: 材料科学 · 生物工程
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SENSORS AND ACTUATORS B-CHEMICAL · 2018 · IF 5.667

A detachable and recyclable electrochemical sensor for high-performance detection of glucose based on boronate affinity

Xuechao Xu,Xiangheng Niu,Shuwen Wu,Xiaobo Zou,Jianming Pan

In this work, we reported a detachable and recyclable electrochemical sensor for high-performance determination of glucose based on the interaction of the analyte with a magnetic boronate. The new sensor was fabricated by incorporating poly(4-vinylphenylboronic acid) (P(4-VBA)) with Fe 3 O 4 -modified graphene oxide (MGO) together via atom transfer radical polymerization. The large surface and good electrical conductivity of the fabricated MGO-P(4-VBA) as well as the unique boronate affinity recognition synergistically contributed to the sensitive and selective sensing of glucose in physiological environments. As verified, glucose in the concentration range of 1–15 mM was detected, along with a detection limit of as low as 39 μM. More attractively, with the aid of an external magnetic field and the convertible affinity recognition upon pH, the sensor could be conveniently disassembled and recycled, providing an excellent reusability in practical applications.

研究领域: 分析化学 · 生物医学工程
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CHEMICAL ENGINEERING JOURNAL · 2018 · IF 6.735

Selective recognition and separation of luteolin based on the molecular imprinted hollow SnO2 and boronate affinity

Qiang Jia,Yue Ma,Yinxian Peng,Yanhong Liu,Wenli Zhang

Molecular imprinted hollow SnO 2 microspheres (Ho-SnO 2 @MIPs) integrated with boronate affinity ability were fabricated via atom transfer radical polymerization, and then they were adopted as ideal adsorbents for cis -diol containing luteolin (LTL) recognition and separation. Ho-SnO 2 @MIPs possessed uniform size (200 nm), porous and hollow structure, appropriate BET surface area (118.6 m 2  g −1 ), and high-density boronate affinity sites (0.22 mg m −2 ), endowing them highly specific uptake and fast separation properties. Due to the merit of pH responsive boronate affinity, the reversible interaction of boronic acid groups and LTL was regulated by the pH value facilely, which was benefit for the controlled recognition and release. In the batch mode experiments, the quick binding equilibrium (within 60 min) and a rather high specific binding capacity (46.81 mg g −1 ) at 298 K were observed, and Ho-SnO 2 @MIPs also displayed high rebinding selectivity to LTL. By a purification process, a commercially available LTL with 85% purity could be easily extracted and concentrated to 95.28% purity by Ho-SnO 2 @MIPs, and the purified products possessed the similar antibacterial performance with standard substance.

研究领域: 材料科学 · 生物化学
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ANALYTICAL CHEMISTRY · 2022 · IF 8.008

Electrochemical Detection of Femtomolar DNA via Boronate Affinity-Mediated Decoration of Polysaccharides with Electroactive Tags

Qiong Hu,Jianwen Wan,Yilin Luo,Shiqi Li,Xiaojing Cao,Wenxing Feng,Yiyi Liang,Wei Wang,Li Niu

In view of their high efficiency and cost-effectiveness, polymers are of great promise as carriers for signal tags in amplified detection. Herein, we present a polysaccharide-amplified method for the electrochemical detection of a BRCA1 breast cancer gene-derived DNA target at the femtomolar levels. Briefly, peptide nucleic acid (PNA) with a complementary sequence was tethered as the capture probe for the DNA target, to which carboxyl group-containing polysaccharides were then attached via facile phosphate-Zr(IV)-carboxylate crosslinking, followed by the decoration of polysaccharide chains with electroactive ferrocene (Fc) signal tags via affinity coupling between a cis-diol site and phenylboronic acid (PBA) group. As the polysaccharide chain contains hundreds of cis-diol sites, boronate affinity can enable the site-specific decoration of each polysaccharide chain with hundreds of Fc signal tags, efficiently transducing each target capture event into the decoration of many Fc signal tags. As polysaccharides are cheap, renewable, ubiquitous, and biodegradable natural biopolymers, the use of polysaccharides for signal amplification offers the benefits of high efficiency, cost-effectiveness, excellent biocompatibility, and environmental friendliness. The linear range of the polysaccharide-amplified method for DNA detection was demonstrated to be from 10 fM to 10 nM (R2 = 0.996), with the detection limit as low as 2.9 fM. The results show that this method can also discriminate single base mismatch with satisfactory selectivity and can be applied to DNA detection in serum samples. In view of these merits, the polysaccharide-amplified PNA-based electrochemical method holds great promise in DNA detection with satisfactory sensitivity and selectivity.

CAS / MDL: 7791-03-9
研究领域: 生物化学 · 分子生物学 · 分析化学
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RSC Advances · 2021 ·Vol. 11 ·期 63 ·39821-39828 · IF 3.361

Boronate-modified polyethyleneimine dendrimer as a solid-phase extraction adsorbent for the analysis of luteolin via HPLC

Baoyue Zhang,Yukui Tong,Jianghua He,Baodong Sun,Feng Zhang,Miaomiao Tian

Luteolin (LTL) is a flavonoid containing a cis-diol, which has significant anti-inflammatory, anti-allergic, anti-diabetic, anti-cancer and neuroprotective activities. In this work, a silver modified boric acid affinity polyvinyl imine (PEI) dendritic adsorbent (PPEI-Ag@CPBA) was prepared on polystyrene (PS) for the rapid recognition and selective separation of LTL. A thin layer of polydopamine (PDA) was formed on the surface of the substrate by self-polymerization, and a PDA-coated PS material (PS@PDA) was obtained. PEI with sufficient active amino groups was grafted onto PS@PDA to obtain a PEI-modified material (PS@PDA@PEI), then AgNO3 was reduced with NaBH4, and PS@PDA@PEI was embedded on Ag. Finally, PPEI-Ag@CPBA was obtained through the condensation reaction of PEI with 4-carboxyphenyl boric acid (CPBA). The adsorption conditions were optimized, the optimal pH and the optimum amount of adsorbent were determined, and the maximum adsorption capacity was found to be 2.49 mg g−1. This method has been successfully applied to the selective identification of LTL in peanut shell samples, and provides a practical platform for the detection of LTL in complex substrates.

研究领域: 分析化学 · 药物化学 · 材料科学
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ANALYTICA CHIMICA ACTA · 2022 · IF 6.911

Boronate affinity paper spray mass spectrometry for determination of elevated levels of catecholamines in urine

Wei Luo,Teris A. van Beek,Bo Chen,Han Zuilhof,Gert IJ. Salentijn

The analysis of catecholamines, such as dopamine, epinephrine and norepinephrine in urine can be used in the diagnosis of certain pathologies, such as hormone-producing tumors. Here, a fast and simple quantitative boronate affinity paper spray tandem mass spectrometric (PS-MS/MS) method is established, which can improve selectivity and reduce ion suppression without needing any instrumental chromatography. We use here the property of boronic acids, which can selectively bind ortho -diol-containing compounds under alkaline conditions. Paper tip modification and catechol enrichment protocols were developed to selectively bind, clean up and subsequently desorb such catecholamines. Standard catecholamine solutions, as well as human urine samples were analyzed with the PS-MS(/MS) method, which is fast, cheap and easy-to-operate compared to HPLC-MS/MS. Despite its high simplicity, boronate affinity PS-MS/MS exhibits good performance compared to HPLC-MS/MS in human urine analysis in terms of precision (2.1%–7.2% vs. 1.1%–2.9%) and accuracy (−10.2%–9.3% vs. −4.8%–5.1%), and a physiologically relevant limit of detection (0.027–0.12 μg mL −1 ). The boronate affinity PS-MS/MS clearly achieved the detection limits that would allow the fast analysis of urine samples for clinical purposes, such as screening for pheochromocytoma (exceeding 0.5 μg mL −1 ).

研究领域: 医学诊断 · 分析化学 · 质谱技术
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SENSORS AND ACTUATORS B-CHEMICAL · 2025 · IF 7.7

Boronate affinity-mediated multi-mode visual sensing of cis-diol compounds in both biological and food samples

Mengzhen Jiang,Ruohan Xu,Chunyan Yang,Haili Wang,Jinyuan Cai,Yanrong Wen,Mingfu Ye,Tingxuan Yan,Shuangshou Wang

cis -Diol compounds are of great biological and clinical values, but their detection is usually instrument-inseparable. Herein, a flexible sensing strategy was proposed at the first time for multi-mode visualization of cis -diol compounds based on boronate affinity (BA)-mediated colorimetry and fluorometry. Boronic acid-decorated sensors with color-/fluorescence-derived binary responsivity were designed using cis -diol fluorescent dyes or dyes-fluorophore counterparts as response units, inducing competitive BA when cis -diol analytes were existed. Consequently, colors and fluorescence of sensors changed simultaneously, and both signals were linearly varied versus the dosages of cis -diol analytes in certain ranges. As proofs of concept, dual-mode visual sensing of glucose in normal/hyperglycemic human serum and sucrose in canned white fungus and edible mushroom plant beverage was achieved with sensing time as short as 1   min and limit of detection as low as 0.18   mg/mL. Furtherly, color information of colorimetric/fluorometric cards and tested sensors was picked by a smartphone APP for digital image analysis, by which the validity of dual-mode visual sensing assays was reinforced by avoiding possible errors from subjective judgement on colors and fluorescence. Besides, the credibility of visual sensing was cross-validated by fluorescent quantification and classical tools such as portable blood glucose meter and phenol-sulfuric acid method-based halochromic reaction.

研究领域: 分析化学 · 生物医学
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RSC Advances · 2021 ·Vol. 11 ·期 41 ·25524-25529 · IF 3.361

The molecular imprinting of magnetic nanoparticles with boric acid affinity for the selective recognition and isolation of glycoproteins

Bangjin Wang,Aihong Duan,Shengming Xie,Junhui Zhang,Liming Yuan,Qiue Cao

A strategy was designed for the molecular imprinting of magnetic nanoparticles with boric acid affinity (MNPs@MIP) which were then used for the selective recognition and isolation of glycoproteins. Fe3O4 nanoparticles were prepared by a solvothermal method and direct silanization by the condensation polymerization of aminopropyltriethoxysilane (APTES). Subsequently, phenylboric acid was functionalized by reductive amination between 2,3-difluoro-4-formyl phenylboric acid (DFFPBA) and the amido group. The resultant Fe3O4@SiO2–DFFPBA was then used for the selective adsorption of a glycoprotein template. Finally, a molecularly imprinted layer was covered on the surface nanoparticles by the condensation polymerization of tetraethyl orthosilicate (TEOS). The adsorption capacities of the resultant MNPs@MIP–HRP and MNPs@MIP–OVA to horseradish peroxidase (HRP) or ovalbumin (OVA) were significantly higher than non-imprinted particles (MNPs@NIP). Moreover, the adsorption capacities of MNPs@MIP–HRP and MNPs@MIP–OVA on non-template protein and non-glycoprotein bovine serum albumin (BSA) were significantly lower than those of their respective template proteins, thus indicating that both of the prepared MNPs@MIP exhibited excellent selectivity.

研究领域: 生物化学 · 材料科学 · 分析化学
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ANALYTICA CHIMICA ACTA · 2020 · IF 5.977

Gold nanoparticles enumeration with dark-field optical microscope for the sensitive glycoprotein sandwich assay

Yameng Han,Zhongju Ye,Langxing Chen,Lehui Xiao

Protein glycosylation is an important post-translational modification and glycoproteins are associated with many crucial metabolic progresses of life. In order to detect glycoproteins sensitively, we propose a gold nanoparticles (GNPs) enumeration method based on boronate affinity sandwich system, which is constructed between the boronic acid polymer functionalized magnetic nanoparticles (Fe 3 O 4 @MPS@VPBA NPs) and 4-mercaptophenylboronic acid modified GNPs (GNPs-MPBA) by the targeted glycoproteins as the linker. Therefore, the sandwich complex is formed, resulting in the decrease of GNPs-MPBA counts in the solution. Based on the dark-field microscope (DFM) imaging technique , the sensitive GNPs enumeration assay is developed for glycoproteins quantitation. Immunoglobulin (IgG), as one of the important glycoproteins, is introduced to evaluate the proposed method. A low detection limit of 1.22 ng mL −1 for IgG analysis is obtained. The result indicates that the proposed GNPs enumeration method offers a simple, effective, label-free and highly sensitive strategy without signal amplification. It also possesses great potential for various target molecules determination at the single-particle level in the future.

研究领域: 生物化学 · 分析化学 · 医学检测
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CHEMICAL ENGINEERING JOURNAL · 2018 · IF 6.735

Magnetic nanoparticles combining teamed boronate affinity and surface imprinting for efficient selective recognition of glycoproteins under physiological pH

Hengjia Zhu,Hang Yao,Kexu Xia,Jinxin Liu,Xiulian Yin,Wenli Zhang,Jianming Pan

Boronate-functionalized surface imprinted nanoparticles that function under physiological pH would be highly desirable for specific enrichment of target glycoproteins. In this work, magnetic molecularly imprinted polymers integrated with low pKa teamed boronate affinity (Fe 3 O 4 @PGMA-TBA/MIPs) were fabricated for selective separation of glycoprotein at pH = 7.4. The teamed boronate affinity (TBA) was formed by boron-nitrogen (B-N) coordination between 1,6-hexamethylenediamine and 3-aminophenylboronic acid, and then was fixed on the surface of magnetic poly(glycidyl methacrylate) (Fe 3 O 4 @PGMA) through ring-opening reaction. After immobilizing the template glycoproteins (ovalbumin, OVA), surface imprinting layer was deposited onto Fe 3 O 4 @PGMA-TBA surface via redox polymerization of aniline, and Fe 3 O 4 @PGMA-TBA/MIPs with obvious core–shell-shell structure were prepared by removing template. Fe 3 O 4 @PGMA-TBA/MIPs were demonstrated with an imprinted polymer film (10–20 nm) and exhibited superparamagnetic property ( M s  = 32 emu g −1 ) and magnetic stability after multiple regenerations. Besides, the results of 11 B MAS NMR spectrum and zeta potentials confirmed the presence of TBA resulting from B-N coordination. Additionally, taking advantage of surface imprinting and TBA, as-prepared Fe 3 O 4 @PGMA-TBA/MIPs posed high binding capacity (190.7 mg g −1 ) and fast capture kinetics (50 min) toward OVA under physiological pH. More importantly, because of the TBA was electroneutral at pH = 7.4, Fe 3 O 4 @PGMA-TBA/MIPs not only exhibited superior specific recognition toward OVA (imprinting factor IF = 7.51), but also maintained the activity of OVA from practical samples analysis. Therefore, this work opened up a universal route for developing intelligent controllability molecular imprinting materials for the specific separation of glycoproteins in biomedical filed under physiological pH.

研究领域: 生物化学 · 材料科学 · 医学
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CHEMICAL ENGINEERING JOURNAL · 2016 · IF 5.31

Experimental investigation of a natural favonoid adsorption on macroporous polymers with intrinsic cis-diol moieties recognition function: Static and dynamic methods

Jianming Pan,Xiaobin Huang,Lin Gao,Yinxian Peng,Shucheng Liu,Runxing Gu

Macroporous polymers with boronate affinity ability (MPs-BA-1) were prepared via high internal phase emulsions (HIPEs) template and then applied to selective adsorption a natural favonoid luteolin (LTL). As-prepared MPs-BA-1 possessed macroporous polymer network and accessible binding sites for cis -diols, and its adsorption behaviors were studied using static and dynamic methods. In static conditions, adsorption amount of LTL increased rapidly in the first 30   min and reached to equilibrium in approximately 2.0   h. Superior conformity of the second-order model confirmed the chemical nature of the interaction between the LTL and binding sites. The fitting adsorption isotherm was a Langmuir type, and the maximum monolayer adsorption amounts at 298   K, 308   K and 318   K were 60.97   μmol   g −1 , 70.10   μmol   g −1 , and 55.03   μmol   g −1 , respectively. Dynamic adsorption incorporated with the analysis of response surface methodology (RSM) suggested that the optimal adsorption amount (73.47   μmol   g −1 ) achieved when the flow rate of LTL solution was 3.0   mL   min −1 , temperature was 28.28   °C and concentration of LTL solution was 30   mg   L −1 . MPs-BA-1 served the specific adsorption towards LTL, and the recognition mechanism based on borate affinity was also described. MPs-BA-1 retained the adsorption amounts for successive cycles, but the loss using dynamic method was larger than in the batch method.

研究领域: 化学工程 · 生物化学
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