Xiqian Li

Highly Sensitive and Selective Sensing of Free Bilirubin Using Metal–Organic Frameworks-Based Energy Transfer Process

Free bilirubin, a key biomarker for jaundice, was detected with a newly designed fluorescent postsynthetically modified metal organic framework (MOF) (UIO-66-PSM) sensor. UiO-66-PSM was prepared based on the aldimine condensation reaction of UiO-66-NH2 with 2,3,4-trihydroxybenzaldehyde. The fluorescence of UIO-66-PSM could be effectively quenched by free bilirubin via a fluorescent resonant energy transfer process, thus achieving its recognition of free bilirubin. It was the first attempt to design a MOF-based fluorescent probe for sensing free bilirubin. The probe exhibited fast response time, low detection limit, wide linear range, and high selectivity toward free bilirubin. The sensing system enabled the monitor of free bilirubin in real human serum. Hence, the reported free bilirubin sensing platform has potential applications for clinical diagnosis of jaundice.

Preparation of a monolith functionalized with zinc oxide nanoparticles and its application in the enrichment of fluoroquinolone antibiotics

This study describes the enrichment ability of ZnO-modified methacrylic acid-co-ethylene dimethacrylate polymer monoliths as stationary phases for the simultaneous determination of antibiotics (ofloxacin, ciprofloxacin, enoxacin, and pefloxacin) combined with high-performance liquid chromatography. The prepared monolith was characterized by scanning electron microscopy, X-ray photoelectron spectroscopy, Fourier-transformed infrared spectroscopy, and thermogravimetric analysis. The polymer monolith microextraction method has been applied to the enrichment of fluoroquinolone antibiotics and satisfactory results were obtained in the analysis of water samples. Compared with the conventional methacrylic acid based monolith, the developed monolith exhibited a higher enrichment capacity because of the introduction of zinc oxide into the preparation process.

Development of Gd 3+ -immobilized glutathione-coated magnetic nanoparticles for highly selective enrichment of phosphopeptides

In this study, we designed a gadolinium-based immobilized metal ion affinity chromatography material for the selective enrichment of phosphopeptides. Gadolinium ion was immobilized on the surface of glutathione-coated magnetic nanoparticles through a facile and effective synthetic route. The adsorbent integrated the advantages of superparamagnetism of Fe3O4 core, good biological compatibility of glutathione, and strong interaction between gadolinium ion and phosphopeptides. It was employed to enrich phosphopeptides from standard protein digests coupled with MALDI-TOF MS. Results demonstrated that the adsorbent possessed high selectivity for phosphopeptides, good reusability and reproducibility. Moreover, the material provided selective enrichment of phosphopeptides from real samples including non-fat milk digests and human serum. The developed method exhibited high sensitivity (detection limit of 10 fmol), showing great potential in the detection of low-abundance phosphopeptides in biological samples.

Electrochemical sensing platform based on kelp-derived hierarchical meso-macroporous carbons

In this paper, kelp (Laminaria japonica), as a kind of abundant biomass, is used as the precursor for the preparation of kelp-derived hierarchical meso-macroporous carbons (K-dHMMCs) through the carbonization under nitrogen (N2) atmosphere at high temperature. The K-dHMMCs exhibits the unique structure with high specific surface area of 416.02 m2 g-1, large pore volume of 0.24 cm3 g-1, the hierarchical meso-macroporous size distribution centered at 2, 12 and 82 nm and high density of defective sites, enabling K-dHMMCs attractive for the electrocatalysis. Drop-casting K-dHMMCs on the glassy carbon (GC) surface allows the construction of K-dHMMCs based electrochemical sensing platform, which shows electrocatalytic activities towards many electroactive molecules, such as potassium ferricyanide, nicotinamide adenine dinucleotide (NADH), hydrogen peroxide (H2O2), dopamine (DA), uric acid (UA), ascorbic acid (AA), epinephrine (EP), l-tyrosine (Tyr) and acetaminophen (APAP). Especially, the K-dHMMCs modified GC (K-dHMMCs/GC) electrode exhibits higher sensitivity, wider linear range, and lower detection limit than both carbon nanotubes modified GC (CNTs/GC) and GC electrodes for H2O2 detection, which makes the K-dHMMCs/GC electrode to be able to determine the H2O2 levels in human urine sample and monitor the H2O2 released from human cancer cells. These results demonstrate that K-dHMMCs/GC possesses a great potential for conventional electrochemical sensing applications.

Highly selective enrichment of phosphopeptides by on-chip indium oxide functionalized magnetic nanoparticles coupled with MALDI-TOF MS

Selective and efficient preconcentration is indispensable for low concentration of phosphopeptides in phosphorylated protein‐related samples prior to MS‐based analysis. Herein, an on‐chip system coupled magnetic SPE with MALDI‐TOF MS was designed. A metal oxide affinity chromatography material, indium oxide, was coated on the surface of Fe3O4 magnetic nanoparticles to prepare the adsorbent, spatially confined with an applied magnetic field. The adsorbent exhibited high selectivity for phosphopeptides in tryptic digests of the mixture of β‐casein and BSA (1:1000) and the mixture of β‐casein, BSA, and ovalbumin (1:100:100). Thanking to the enrichment ability and specificity for phosphopeptides with the adsorbent, the on‐chip magnetic SPE‐MALDI‐TOF MS approach showed high sensitivity with a low detection limit of 4 fmol. In addition, the developed approach was used to analyze phosphopetides in non‐fat milk digests and human serum successfully.

Immobilization of β-Cyclodextrin-Conjugated Lactoferrin onto Polymer Monolith for Enrichment of Ga in Metabolic Residues of Ga-Based Anticancer Drugs

Biological-material-functionalized porous monoliths were prepared with lactoferrin and β-cyclodextrin via a click reaction. With the monolith as an extraction medium, a method combined with ICP-MS was developed for the determination of total gallium originating from metabolic residues of orally bioavailable gallium complexes with tris(8-quinolinolato)gallium (GaQ3) as a representative. The method exhibited favorable adsorption behaviors for gallium with high selectivity, low detection limit (2 ng L-1), and an enrichment factor of 29-fold with the sample throughput of 30 min-1. The developed approach was validated by the analysis of gallium from GaQ3 metabolic residues in a human cell line. Additionally, the practical applicability of this method was evaluated by the determination of gallium in human blood and urine samples from cancer patients. Results illustrated that the prepared monolith had potential in Ga-based anticancer drug analysis in complex biological samples.

Multilayer Cucurbit[6]uril-Based Magnetic Nanoparticles Prepared by Host-Guest Interaction: Remarkable Adsorbent for Low Density Lipoprotein Removal from Plasma

Efficient removal of low density lipoprotein (LDL) is a key challenge due to its high level in plasma as a primary risk factor in the pathogenesis of atherosclerotic cardiovascular disease. In this work, a facile synthesis strategy based on host-guest interactions was developed to prepare multilayer cucurbit[6]uril-based magnetic nanoparticles, MNPs-(HA-DAH5 /HA-CB[6]5 ). The compound was employed as a blood purification material for the removal of LDL from plasma because it had good blood compatibility and could be easily separated with an external magnet. The efficient removal of LDL was attributed to the electrostatic interactions between the positive charged apoB-100 domain of LDL and the negative charged adsorbent. Moreover, the prepared material exhibited high recyclability and could release LDL in physiological saline for recyclable use. MNPs-(HA-DAH5 /HA-CB[6]5 ) offered promising perspectives and broad applications in extracorporeal treatment for the removal of LDL.

Cost-effective synthesis of three-dimensional nitrogen-doped nanostructured carbons with hierarchical architectures from the biomass of sea-tangle for the amperometric determination of ascorbic acid

In this work, the three-dimensional nitrogen-doped nanostructured carbons with hierarchical architectures (3D-NNCsHAs) with high density of defective sites, high surface area and pluralities of pore size distributions was prepared through the pyrolysis of sea-tangle (Laminaria japonica), an inexpensive, eco-friendly and abundant precursor. Benefitting from their structural uniqueness, a selective and sensitive ascorbic acid (AA) sensor based on 3D-NNCsHAs was developed. Compared to the glassy carbon electrode (GCE) and the carbon nanotubes modified GCE (CNTs/GCE), the 3D-NNCsHAs modified GCE (3D-NNCsHAs/GCE) presents higher performance towards the electrocatalysis and detection of AA, such as lower detection limit (1 μM), wider linear range (10-4410 μM) and lower electrooxidation peak potential (-0.02 V vs. Ag/AgCl). In addition, 3D-NNCsHAs/GCE also exhibits high anti-interference and anti-fouling abilities for AA detection. Particularly, the fabricated 3D-NNCsHAs/GCE is able to determine AA in real samples and the results acquired are satisfactory. Therefore, the 3D-NNCsHAs can be considered as a kind of novel electrode nanomaterial for the fabrication of selective and sensitive AA sensor for the extensive practical applications ranging from food analysis, to pharmaceutical industry and clinical test.

A magnetic hydrazine-functionalized dendrimer embedded with TiO 2 as a novel affinity probe for the selective enrichment of low-abundance phosphopeptides from biological samples

Dendrimers exhibit tunable terminal functionality and bio-friendly nature, making them of being promising materials for applications in the field of separation and enrichment. In this work, we prepared magnetic hydrazide-functionalized poly-amidoamine (PAMAM) dendrimer embedded with TiO2 for the enrichment of phosphopeptides. The novel affinity probe possessed superparamagnetism, realizing its rapid separation from sample solution. Electrostatic attraction and hydrogen bonding existed between PAMAM and phosphopeptides while Lewis acid-base interaction was originated between TiO2 and the targets. The combined synergistic strength of multiple binding interactions contributed to the highly selective enrichment of phosphopeptides. The specificity for the capture of phosphopeptides was reflected in quantities as low as 1:1000 mass ratio of phosphopeptides to non-phosphopeptides. The detection limit of β-casein digests was low to 0.4 fmol, indicating the high sensitivity of the developed method. Fifteen and four phosphopeptides could be selectively captured from non-fat milk digests and human serum samples, which further confirmed the great potential of the affinity probe in the extraction of low-abundance phosphopeptides from real complex biological samples.

Design of pH-Responsive Polymer Monolith Based on Cyclodextrin Vesicle for Capture and Release of Myoglobin

β-Cyclodextrin vesicles (CDVs) were first introduced into the polymer monolith to prepare a pH-responsive adsorption material and used for capture and release of a cardiac biomarker, myoglobin (Myo). SH-CDV was decorated with adamantane-modified SH-octapeptide to enhance the encapsulation and release rates of Myo. Afterward, SH-CDV was introduced into the polymer monolith via click reaction to produce a pH-responsive monolith. Combining with the mass spectrometry detection, the CDV-based pH-responsive monolith was used for the enrichment of Myo glycopeptides from the mixture of glycopeptides and nonglycoprotein (bovine serum albumin) tryptsin digests reach up to 1:10 000. A limit of detection of 0.1 fmol was obtained for Myo glycopeptides in the blood sample, indicating the high sensitivity of the method. The prepared CDV-based hybrid monolith demonstrated itself to be a promising material for capture of glycoproteins in complex samples, which provides an efficient strategy for the identification and discovery of biomarkers of acute myocardial infarction.