Chanjiao Ma

Determination of tetracycline in milk by using nucleotide/lanthanide coordination polymer-based ternary complex

The meta-organic coordination polymers have been emerged as fascinating nanomaterials because of their tunable nature. In this work, we employed lanthanide coordination polymer self-assembled from adenosine monophosphate (AMP) and europium ion (Eu(3+)) as receptor reagent and citrate (Cit) as ancillary ligand to construct a fluorescent sensor for the detection of tetracycline (Tc) in milk. The co-coordination of Cit and Tc with Eu(3+) on the surface of the coordination polymer AMP/Eu leads to the formation of ternary complex which emitted strong fluorescence due to the removal of coordinated water molecules and an intramolecular energy transfer from Tc to Eu(3+). The fluorescent intensity of Eu(3+) displayed a good linear response to Tc concentrations in the range of 0.1-20 μM with a detection limit of 60 nM. This method was successfully applied to determine the levels of Tc in milk, which is the first application of coordination polymer as a fluorescent sensor in real sample. Compared with other Eu(3+)-based fluorescent methods for Tc detection, the presented method allows simple, direct analysis of Tc without requiring special reaction media or complicated prepreparation processes. This straightforward strategy could be extended to the preparation of other lanthanide coordination polymer-based fluorescent probes for applications in biosensing, imaging, drug delivery, and so on.

A sensitive fluorescent assay for thiamine based on metal-organic frameworks with intrinsic peroxidase-like activity

Metal-organic frameworks (MOFs) with tunable structures and properties have recently been emerged as very interesting functional materials. However, the catalytic properties of MOFs as enzymatic mimics remain to be further investigated. In this work, we for the first time demonstrated the peroxidase-like activity of copper-based MOFs (HKUST-1) by employing thiamine (TH) as a peroxidase substrate. In the presence of H2O2, HKUST-1 can catalyze efficiently the conversion of non-fluorescent TH to strong fluorescent thiochrome. The catalytic activity of HKUST-1 is highly dependent on the temperature, pH and H2O2 concentrations. As a peroxidase mimic, HKUST-1 not only has the features of low cost, high stability and easy preparation, but also follows Michaelis-Menten behaviors and shows stronger affinity to TH than horseradish peroxidase (HRP). Based on the peroxidase-like activity of HKUST-1, a simple and sensitive fluorescent method for TH detection has been developed. As low as 1 μM TH can be detected with a linear range from 4 to 700 μM. The detection limit for TH is about 50 fold lower than that of HRP-based fluorescent assay. The proposed method was successfully applied to detect TH in tablets and urine samples and showed a satisfactory result. We believed that the present work could improve the understanding of catalytic behaviors of MOFs as enzymatic mimics and find out a wider application in bioanalysis.

Terbium-Based Coordination Polymer Nanoparticles for Detection of Ciprofloxacin in Tablets and Biological Fluids

The metal-organic coordination polymers with tunable structures and properties have been rapidly emerging as very important functional materials. In this work, we prepared terbium (Tb(3+))-based coordination polymer nanoparticles (CPNPs) by employing adenine (Ad) as bridging ligands. The CPNPs was further used as a receptor reagent for ciprofloxacin (CF) detection in aqueous solution. Addition of CF induces a typical emission of Tb(3+) due to the formation of Ad/Tb-CF complex and the sensitization of CF. The fluorescent intensity of Tb(3+) was enhanced linearly with increasing the CF concentration from 60 nM to 14 μM. The detection limit for CF in aqueous solution is 60 nM. The Ad/Tb CPNPs was successfully applied to detect CF in tablet and urine samples and showed a satisfactory result. Compared with other methods, the proposed method is advantageous because that it provides a very simple strategy for CF detection, which does not require complicated sample pretreatment processes or special reaction media. The proposed strategy could be contributed to expand the potential applications of lanthanide coordination polymers in biological and environmental fields.

Lanthanide based dual-emission fluorescent probe for detection of mercury (II) in milk

It is highly desirable to develop a simple and sensitive method for Hg(2+) detection because of the dangerous nature of Hg(2+). In this work, we prepared a dual-emission fluorescent probe for Hg(2+) detection by combining two lanthanide chelates with different emission wavelengths. Green-emitting terbium (Tb(3+)) chelates as reference signals were embedded into SiO2 nanoparticles and red-emitting europium (Eu(3+)) chelates as response units were covalently linked to the surface of silica shell. Upon the addition of Hg(2+), the fluorescence of Eu(3+) chelates can be selectively quenched, while the fluorescence of Tb(3+) chelates remained unchanged. As a kind of Hg(2+) nanosensor, the dual-emission fluorescent probe exhibited excellent selectivity to Hg(2+) and high sensitivity up to 7.07 nM detection limit. The Hg(2+) levels in drinking water and milk samples were determined by using the dual-emission fluorescent probe with satisfied recovery. Additionally, our probe has a long enough fluorescence lifetime, which can avoid the interference from autofluorescence of the biological samples. We envision that the proposed probe could find great potential applications for ultrasensitive time-resolved fluorometric assays and biomedical imaging in the future.

Luminescence detection of cysteine based on Ag⁺-mediated conformational change of terbium ion-promoted G-quadruplex.

In this work, we developed a simple and sensitive method for the detection of cysteine (Cys) by employing terbium ion (Tb(3+))-promoted G-qudraplex (G4/Tb) as a luminescent probe, which is based on Ag(+)-mediated conformational change of G4/Tb. Due to Ag(+) is able to compete with Tb(3+) to bind guanine at G4, the presence of Ag(+) can lead to the formation of G4/Tb-Ag(+) complex and disrupt the structure of G4/Tb. Meanwhile, the binding of Ag(+) with G4/Tb will also cause the alteration of the excited state of G4 and more efficient energy transfer from G4 to Tb(3+), enhancing the luminescence of G4/Tb. However, upon the addition of Cys, Ag(+) will be released from G4/Tb-Ag(+) complex because of the high affinity of Cys to Ag(+). This results in the re-formation of the conformation of G4/Tb and the decrease of the luminescence of G4/Tb. So, Ag(+)-enhanced luminescence of G4/Tb is associated with its conformational transformation. As a luminescent probe for Cys, G4/Tb not only shows excellent selectivity and sensitivity with a detection limit of 20 nM, but also possesses the features of simple preparation, easy reproducibility, and eliminating the interferences from background fluorescence. We envision that the presented strategy might provide new insight into the biosensing applications of lanthanide complex.

Surfactant-mediated morphology and fluorescent properties of amino acids-based lanthanide coordination polymers

In this study, the effects of surfactants with different characteristics on the morphology and fluorescent properties of biomolecule-based lanthanide coordination polymers were investigated using Phe/Tb CPs (Phe = phenylalanine) as a model. In the presence of surfactants, significant changes in the morphologies of Phe/Tb CP can be observed, which are highly dependent on the charged characteristics and alkyl chain length of the surfactants. Compared with the anionic SDS, CTAB carrying positive charge and PVP with a super-long alkyl chain are favorable for the formation of monodispersed Phe/Tb CPs that are smaller in size and more uniform. This is due to the fact that the binding ability and steric effect of SDS to growing Phe/Tb are weaker than that of CTAB and PVP. Moreover, a significant increase in the fluorescent intensity and emission lifetime of Phe/Tb CPs were also found after the addition of surfactants, which indicate the influence of surfactants on the fluorescent properties of Phe/Tb CPs. We believe that the present study may be helpful for the rational design and preparation of functional fluorescent biomolecule-based LnCPs for biomedical applications.