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TALANTA · 2021 · IF 6.057

Post-synthesis modification of covalent organic frameworks for ultrahigh enrichment of low-abundance glycopeptides from human saliva and serum

Zehu Xie,Yinghua Yan,Keqi Tang,Chuan-Fan Ding

In this study, a novel type of covalent organic framework (COF) material rich in boronic acid sites was prepared through post-synthesis modification (TbBD@PEI@Au@4-MPBA). The surface of COF material had abundant carboxylic acid groups, which could bind a large amount of polyethyleneimine (PEI) through electrostatic interaction . At the same time, the amino groups on the PEI can be grafted with Au nanoparticles (Au NPs) in situ, and then 4-mercaptophenylboronic acid (4-MPBA) was modified by the reaction of Au and sulfhydryl groups. The massive grafting of boronic acid groups made the material's enrichment effect on glycopeptides expected. The results of experiments indicated that the composite material has high sensitivity (5 amol μL −1 ) and selectivity (1:1000). In addition, the material has outstanding stability and reusability, with a load capacity of about 100 mg g −1 and a recovery of 99.3 ± 2.2%. What's more, after enriched by TbBD@PEI@Au@4-MPBA, 56 endogenous glycopeptides from fresh human saliva were detected by MALDI-TOF MS, 56 unique glycopeptides corresponding to 31 glycoproteins from human saliva and 513 unique glycopeptides corresponding to 208 glycoproteins from serum of throat cancer patient were detected by nano-LC-MS/MS, respectively, which was expected to be applied to glycoproteomics research.

研究领域: 生物化学 · 医学诊断
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ACS Applied Materials & Interfaces · 2017 · IF 7.504

Ultrasensitive Sensing Material Based on Opal Photonic Crystal for Label-Free Monitoring of Transferrin

Enqi Wu,Yuan Peng,Xihao Zhang,Jialei Bai,Yanqiu Song,Houluo He,Longxing Fan,Xiaochen Qu,Zhixian Gao,Ying Liu,Baoan Ning

A new opal photonic crystal (PC) sensing material, allowing label-free detection of transferrin (TRF), is proposed in the current study. This photonic crystal was prepared via a vertical convective self-assembly method with monodisperse microspheres polymerized by methyl methacrylate (MMA) and 3-acrylamidophenylboronic acid (AAPBA). FTIR, TG, and DLS were used to characterize the components and particle size of the monodisperse microspheres. SEM was used to observe the morphology of the PC. The diffraction peak intensity decreases as the TRF concentration increase. This was due to the combination of TRF to the boronic acid group of the photonic crystal. After condition optimization, a standard curve was obtained and the linear range of TRF concentration was from 2 × 10–3 ng/mL to 200 ng/mL. Measurement of TRF concentration in simulated urine sample was also investigated using the sensing material. The results indicated that the PC provided a cheap, label-free, and easy-to-use alternative for TRF determination in clinical diagnostics.

CAS / MDL: 80-62-6 7727-21-1
研究领域: 生物医学工程 · 分析化学
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JOURNAL OF COLLOID AND INTERFACE SCIENCE · 2021 · IF 8.128

Molecularly imprinted colloidal array with multi-boronic acid sites for glycoprotein detection under neutral pH

Wei Chen,Zhiyang Guo,Hao Yu,Qingyun Liu,Min Fu

Glycoproteins play vital roles in living organisms and often serve as biomarkers for some disease. However, due to the low content of glycoprotein in biological fluids, selective detection of glycoproteins is still a challenging issue that needs to be addressed. In this study, molecularly imprinted colloidal array with multi-boronic acid sites for glycoprotein detection under physiological pH was proposed. Monodispersed glycoprotein imprinted particles (SiO 2 @PEI/MIPs) was first prepared based on surface imprinting strategy using horseradish peroxidase (HRP) as template, and polyethyleneimine (PEI) was used to increase the number of boronic acid groups. The binding experiment indicated that the SiO 2 @PEI/MIPs hold satisfactory adsorption capacity (1.41 μmol/g), rapid adsorption rate (40 min) and preferable selectivity toward HRP. Then the SiO 2 @PEI/MIPs was assembled into close-packed colloidal array to construct a label free optical sensor (denoted as GICA). Benefiting from the high ordered photonic crystal structure, binding of HRP onto the GICA could be directly readout from the changes in structure color and diffracted wavelength. The structure color of the GICA changed from bright blue to yellow with the diffraction wavelength red shifted 59 nm when the HRP concentration increased from 2.5 to 15 μmol/L. Importantly, the GICA was capable of detecting HRP from human serum samples. All those results indicated the potential of the GICA for naked-eye detection of glycoprotein.

研究领域: 生物化学 · 分析化学 · 材料科学
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Journal of Materials Chemistry B · 2021 ·Vol. 9 ·期 36 ·7557-7565 · IF 6.331

Boronic acid-functionalized spherical polymer brushes for efficient and selective enrichment of glycoproteins

Chen Hua,Kaimin Chen,Xuhong Guo

Glycoproteins are related to many biological activities and diseases, and thereby their efficient capture and enrichment for diagnostics and proteomics have emerged to exhibit great significance. However, the lack of materials with high binding capacity and selectivity is still a big obstacle for further application. Herein, we reported a facile and eco-friendly approach to fabricate spherical polymer brushes with multiple boronic acid groups. Specifically, the whole process can be divided into three steps, the polystyrene (PS) core was obtained by traditional emulsion polymerization, followed by immobilization of a home-made photoinitiator. Subsequently, boronic acid-functionalized polymer chains (PBA) were chemically grafted via photo-emulsion polymerization, leading to spherical polymer brushes (PS-PBA) with boronate affinity. The particle size, morphology, and composition of as-prepared spherical polymer brushes were systematically characterized. The characteristics of glycoproteins binding to the spherical polymer brushes under different conditions, including pH values and ionic strength, were also investigated. PS-PBA brushes possess fast binding speed (30 min) and high binding capacity for glycoprotein ovalbumin (OVA) (377.0 mg g−1) under physiological pH conditions at 25 °C, because the low steric hindrance of flexible polymeric PBA chains facilitates the interaction between boronic acid groups and glycoproteins. Moreover, the binding capacity of PS-PBA brushes for glycoprotein OVA was ∼6.7 times higher than that for non-glycoprotein bovine serum albumin (BSA), indicating the excellent selective adsorption. This study provided a facile and efficient approach for the fabrication of boronic acid-functionalized materials that will be useful in the enrichment and separation of glycoproteins for the diagnosis of diseases.

研究领域: 生物化学 · 材料科学 · 医学诊断
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Journal of Materials Chemistry B · 2017 ·Vol. 5 ·期 43 ·8525-8531 · IF 4.543

Aggregation-induced emission (AIE)-active fluorescent probes with multiple binding sites toward ATP sensing and live cell imaging

Hengchang Ma,Manyi Yang,Caili Zhang,Yucheng Ma,Yanfang Qin,Ziqiang Lei,Lu Chang,Lei Lei,Tao Wang,Yuan Yang

Aggregation-induced emission (AIE)-active compounds are attractive fluorescent materials for applications in chemical and biological sensing. The AIE effect of such materials amplifies changes in the fluorescence signal due to the physical state transformation from aggregation to disaggregation, which can be employed for detecting various analytes with high sensitivity. In particular, specific bio-active analyte recognition is not only very interesting but also challenging. In this paper, we report a set of novel AIE-active fluorescent probes containing pyridiniums and boric acid groups (TPA-PP, TPA-PPA-1, TPA-PPA-2, TPA-PPA-3), which has been developed for adenosine 5′-triphosphate (ATP) recognition. These probes with two types of interaction modes and multiple connection sites toward ATP molecules are able to selectively discriminate ATP among other bioactive anions with a significant enhancement in fluorescence emission. In particular, in the application of cell imaging, as the number of positive charges and boric acid group increased further, the probes could penetrate into cells, and then enter into the nucleus very specifically. These results clearly demonstrate that the newly developed sensors are suitable for specific tracing of different cell organelles with a height visualization and retention ability. Therefore, all of them are confirmed as promising alternatives for live cell imaging in the future.

研究领域: 生物化学 · 分析化学 · 细胞生物学
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Analytical Methods · 2023 ·Vol. 15 ·期 21 ·2677-2684 · IF 3.1

One-step preparation of boronic acid-rich hydrothermal spheres for N-glycopeptide analysis from preeclampsia serum

Shuwen Hua,Baichun Wang,Jiayi Wang,Bing He,Chuan-Fan Ding,Yongyao Wu,Yinghua Yan,Rongrong Xuan

In this study, we developed a green, one-step hydrothermal carbonization (HTC) method that used water as the sole solvent to create boronic acid group-rich carbonaceous spheres (BCS). When the abundant boronic acid groups on the carbonaceous spheres react with the hydroxyl groups on the glycans in an alkaline environment, the glycopeptides are specifically captured. The results showed that BCS had excellent detection limits (0.1 fmol μL−1), selectivity (1 : 1000), and stability (10 cycles). In addition, the BCS also demonstrated excellent glycopeptide enrichment capabilities in complex biological samples; 219 glycopeptides attributed to 167 glycoproteins and 235 glycopeptides related to 166 glycoproteins in PE patient and normal pregnancy control serum were identified by nano LC-MS/MS, respectively. In addition, the molecular function of heparin binding and biological process of complement activation, positive regulation of immune response, and positive regulation of tumor necrosis factor production were significantly different between PE patients and healthy pregnant women according to gene ontology analysis, indicating that these may be associated with the development of PE.

CAS / MDL: 1066-33-7 76-05-1
研究领域: 分析化学 · 医学 · 生物信息学
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Nanoscale · 2020 ·Vol. 12 ·期 46 ·23748-23755 · IF 6.895

A novel fluorescent covalent organic framework containing boric acid groups for selective capture and sensing of cis-diol molecules

Zhaosen Chang,Ying Liang,Shunli Wang,Lu Qiu,Yan Lu,Lijuan Feng,Zhuyin Sui,Qi Chen

Owing to specific formation of five-membered or six-membered cyclic esters between boric acid groups and cis-diol molecules, boric acid bearing fluorescent materials can not only selectively capture but also specifically identify cis-diol substances. In this work, a novel covalent organic framework containing boric acid groups (COF-BA) was prepared through post-modification via the aza-Diels–Alder cycloaddition reaction. COF-BA with good stability, a permanent pore structure, a high specific surface area (606 m2 g−1) and a uniform pore size (2.59 nm) exhibited unique selectivity toward the cis-diol guest molecule 1,2-dihydroxyanthracene-9,10-dione (1,2-Doa) with a high adsorption capacity of 177.95 mg g−1. However, as for the isomers of 1,2-Doa (1,4-dihydroxyanthracene-9,10-dione and 2,6-dihydroxyanthracene-9,10-dione), the corresponding uptake capacities are distinctively decreased to 40.86 mg g−1 and 3.05 mg g−1, respectively. It is worth noting that the COF-BA can be recovered and recycled. Moreover, because the formation of the quinoline enhanced the conjugation effect of the COF skeleton, it was unexpectedly found that COF-BA possessed an intrinsic fluorescence property and could be used as an optical sensor for 1,2-Doa.

CAS / MDL: 95-50-1
研究领域: 材料科学 · 化学
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POLYMERS FOR ADVANCED TECHNOLOGIES · 2021 ·Vol. 32 ·期 6 ·2339-2351 · IF 3.665

Polyhedral oligomeric silsesquioxane hybrided with DOPO and phenylboronic acid for flame-retarded epoxy resin

Zeng Birong,Zhou Ruirui,Zheng Xianghong,Ye Jianyu,Chen Jinmei,Xu Yiting,Yuan Conghui,Dai Lizong

A new polyhedral oligomeric silsesquioxane (POSS) derivate bearing phenylboronic acid group and 6H-dibenzo[c,e][1,2]oxaphosphinine-6-oxide (DOPO) unit was synthesized and applied in flame retardant epoxy resin (EP). Compared to pure EP, EP/POSS-DOPO-(phenylboronic acid) composites had good transparency and better thermal stability. Micro-scale combustion calorimetry results showed that the addition of POSS-DOPO-(phenylboronic acid) hybrid could greatly reduce the PHRR and THR of EP/POSS-DOPO-(phenylboronic acid) composite. Simultaneously, the UL-94 of EP composite with 7% POSS-DOPO-(phenylboronic acid) achieved V-0 grade and the LOI value increased from 19.4% (neat EP) to 28.6%. Raman spectra results suggested that POSS-DOPO-(phenylboronic acid) hybrid enhanced the formation of residual char with graphitic structure during combustion. Besides, SEM characterization showed that the char of EP/POSS-DOPO-(phenylboronic acid) composite was much more continuous and compact in comparison with that of control samples. Moreover, the mechanical and dielectric properties of EP/POSS-DOPO-(phenylboronic acid) composites have been greatly improved for a better application.

CAS / MDL: 87199-17-5
研究领域: 材料科学 · 化学工程
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Journal of Materials Chemistry B · 2019 ·Vol. 7 ·期 18 ·3027-3033 · IF 5.047

Nanoscaled luminescent terbium metal–organic frameworks for measuring and scavenging reactive oxygen species in living cells

Huaping Li,Xuanyu Cao,Xinyu Fei,Shiming Zhang,Yuezhong Xian

A luminescent terbium metal–organic framework (Tb-MOF) was prepared using Tb3+ as metal ions and a boronic acid ligand (3,5-dicarboxybenzeneboronic acid) as linkers, which was successfully employed for the detection and scavenging of reactive oxygen species (ROS) in living cells. After the formation of the Tb-MOF, the luminescence of Tb3+ is sensitized by the organic linkers. In addition, the functionalization of boronic acid groups in the channels of MOFs also enhances the luminescence of Tb3+ ions through the antenna effect by adjusting the energy level of the ligand. In addition, the free boronic acid groups act as active sites and react with ROS due to a rapid nucleophilic addition reaction, which leads to the luminescence quenching of Tb-MOF. On the basis of these findings, the boronic acid-functionalized Tb-MOF can be used as an excellent ROS scavenger and a nanoprobe for highly selective and sensitive detection of ROS in living cells.

研究领域: 生物化学 · 材料科学 · 医学检测
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ANALYTICAL CHEMISTRY · 2013 · IF 5.695

Facile Synthesis of Boronate-Decorated Polyethyleneimine-Grafted Hybrid Magnetic Nanoparticles for the Highly Selective Enrichment of Modified Nucleosides and Ribosylated Metabolites

Hua Li,Yuanhong Shan,Lizhen Qiao,Abo Dou,Xianzhe Shi,Guowang Xu

Ribosylated metabolites, especially modified nucleosides, have been extensively evaluated as cancer-related biomarkers. Boronate adsorbents are considered to be promising materials for extracting them from complex matrices. However, the enrichment of ribosylated metabolites in low abundance is still a challenge due to the limited capacity and selectivity of the existing boronate adsorbents. In this study, a novel type of magnetic nanoparticles named Fe3O4@SiO2@PEI-FPBA was synthesized by grafting polyethyleneimine (PEI) onto the surface of Fe3O4@SiO2 before modification by boronate groups. The high density of the amino groups on the PEI chains supplied a large number of binding sites for boronate groups. Thus, the adsorption capacity (1.34 ± 0.024 mg/g) of the nanoparticles, which is 6- to 7-fold higher than that of analogous materials, was greatly improved. The unreacted secondary amines and tertiary amines of the PEI enhanced the aqueous solubility of the nanoparticles, which could efficiently reduce nonspecific adsorption. The nanoparticles were able to capture 1,2 cis-diol nucleosides from 1000-fold interferences. Moreover, the flexible chains of PEI were favorable for effective enrichment and quick equilibration (<2 min). Finally, 60 ribose conjugates were enriched from human urine using the nanoparticles. Among them, 43 were identified to be nucleosides and other ribosylated metabolites. Nine low abundance modified nucleosides were detected for the first time. In conclusion, Fe3O4@SiO2@PEI-FPBA is an attractive candidate material for the highly selective enrichment of 1,2-cis-diol compounds.

研究领域: 分析化学 · 生物医学
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ADVANCED FUNCTIONAL MATERIALS · 2015 ·Vol. 25 ·期 25 ·3847-3854 · IF 11.805

Metal–Organic Frameworks with Boronic Acid Suspended and Their Implication for cis-Diol Moieties Binding

Xiangyang Zhu,Jinlou Gu,Junying Zhu,Yongsheng Li,Liming Zhao,Jianlin Shi

Introduction of accessible boronic acid functionality into metal–organic frameworks (MOFs) might to endow them with desired properties for potential applications in recognition and isolation of cis -diol containing biomolecules (CDBs). However, no investigation is found to address this topic until now. Herein, Cr-based MOFs of MIL-100 (MIL stands for Materials from Institut Lavoisier) integrated with different pendent boronic acid group (MIL-100-B) are reported. This new functional material is successfully prepared using a simple metal–ligand–fragment coassembly (MLFC) strategy with isostructure to the parent MIL-100 as verified by X-ray diffraction characterization. The integration and content tunability of the boronic acid group in the framework are confirmed by X-ray photoelectron spectroscopy and 11 B NMR. Transmission electron microscopy reveals that MIL-100-B can evolve into well-defined morphology and nanoscale size at optimized boronic acid incorporating level. The obtained MOFs exhibit comparable surface areas and pore volumes with parent MIL-100 and present exceptional chemical stability in a wide pH range. The inherent boronic acid components in MIL-100-B can effectively serve as the recognition units for the cis -diol moieties and consequently enhance the capture capabilities for CDBs. The exceptional chemical stability, high porosity, and good reusability as well as the intrinsic cis -diol moieties recognition function prefigure great potential of the current MIL-100-B in CDBs purification, sensing, and separation applications.

研究领域: 材料科学 · 生物化学
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MACROMOLECULAR CHEMISTRY AND PHYSICS · 2021 ·Vol. 222 ·期 17 ·2100145 · IF 2.527

Preparation of P(EGDMA-co-VPBA) Adsorbent and Its Application in the Separation of Steviol Glycosides

Qiaoge Fu,Nana Chen,Guanyu Wang,Ruili Guo

The poly (ethylene glycol dimethacrylate- co -vinylphenylboronic acid) P(EGDMA- co -VPBA) adsorbents are prepared via reversible addition-fragmentation chain transfer (RAFT) precipitation polymerization with 4-vinylphenylboronic acid (VPBA) as the functional monomer, and used for selective adsorption of steviol glycosides (SGs). The boron content and pore structure of the P(EGDMA- co -VPBA) adsorbent are adjusted by changing the polymerization conditions. The adsorption results show that the pore structure of the P(EGDMA- co -VPBA) affects the adsorption capacity to SGs, the presence of boric acid functional groups shows favorable adsorption selectivity for stevioside (STV), and the adsorption selectivity is proportional to the content of boric acid in P(EGDMA- co -VPBA) adsorbents. The adsorption performance of P(EGDMA- co -VPBA) toward SGs is the best when the ratio of monomer to cross-linker is 1:50 and the solvent is acetonitrile. In the SG solution (6.0 mg mL −1 , C STV / C RA = 1:1), the adsorption capacities and adsorption selectivity ( α STV/RA ) of P(EGDMA- co -VPBA) to SGs are 113.20 mg g –1 and 4.99, respectively. The adsorption kinetics and isotherm data obey pseudo-second-order kinetic model and Langmuir isotherm model, respectively. The boric acid copolymers with VPBA as the monomer prepared by the one-step method can become a promising material for efficient separation and purification of SGs.

CAS / MDL: 97-90-5
研究领域: 化学工程 · 食品科学
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