1.
Experimental and theoretical validations of a one-pot sequential sensing of Hg2+ and biothiols by a 3D Cu-based zwitterionic metal-organic framework.
Chen, HL, Li, RT, Wu, KY, Hu, PP, Zhang, Z, Huang, NH, Zhang, WH, Chen, JX
Talanta. 2020;:120596
Abstract
A zwitterionic three-dimensional (3D) metal-organic framework (MOF) of {[Cu(Cdcbp)(bipy)]·4H2O}n (1) has been synthesized and characterized (H3CdcbpBr = 3-carboxyl-(3,5-dicarboxybenzyl)-pyridinium bromide; bipy = 4,4'-bipyridine). MOF 1 exhibits a variety of structural traits, such as ligand conjugated, positively charged pyridinium center, and Cu(II) cations that collectively enable its efficient hybridization with the flexible, negatively charged, single-stranded, and thymine-rich (T-rich) DNA. The T-rich DNA is labeled with carboxyfluorescein (FAM) fluorescent probe (characterized as P-DNA), but the resultant MOF 1 - P-DNA hybrid (characterized as P-DNA@1) is non-emissive (off-state) because of the fluorescent quenching by MOF 1. The P-DNA@1 hybrid functions as an effective and selective sensor for Hg2+ due to the formation of rigid hairpin-like T-Hg2+-T double-stranded DNA (ds-DNA@Hg2+) which is subsequently ejected by MOF 1, triggering a recovery of the P-DNA fluorescence (on-state). Subsequent addition of biothiols further sequestrates Hg2+ from the ds-DNA@Hg2+ duplex driven by the stronger Hg-S coordination, thus release the P-DNA and, in turn, resorbed by MOF 1 to regain the initial hybrid (off-state). P-DNA@1 hybrid thus detects Hg2+ and biothiols sequentially via a fluorescence "off-on-off" mechanism. The limits of detection (LOD) for Hg2+, biothiols, including cysteine (Cys), glutathione (GSH) and homocysteine (Hcy) are 3.0, 14.2, 15.1 and 8.0 nM, respectively, with the detection time of 60 min for Hg2+, and instantaneous detection for all the three biothiols. The detection mechanism is further confirmed by circular dichroism (CD), fluorescence anisotropy (FA), binding constant and molecular simulation. This sequential detection of Hg2+ and biothiols counter-proofs the presence of each other and may shed light to the occurrence of related diseases, such as neurodegenerative disorders of Parkinson's disease (PD), and Alzheimer's disease (AD).
2.
Quantitative/qualitative analysis of adhesive-dentin interface in the presence of 10-methacryloyloxydecyl dihydrogen phosphate.
Zhou, J, Wurihan, , Shibata, Y, Tanaka, R, Zhang, Z, Zheng, K, Li, Q, Ikeda, S, Gao, P, Miyazaki, T
Journal of the mechanical behavior of biomedical materials. 2019;:71-78
Abstract
Dental adhesive provides effective retention of filling materials via adhesive-dentin hybridization. The use of co-monomers, such as 10-methacryloyloxydecyl dihydrogen phosphate (10-MDP), is thought to be crucial for hybridization owing to their ionic-binding to calcium and co-polymerization in the polymerizable adhesives. Optimal hybridization partly depends on the mechanical properties of polymerized adhesives, which are likely to be proportional to the degree of conversion ratio. This study assessed the correlation between polymerization quality and mechanical properties at the adhesive-dentin interfaces in the presence or absence of 10-MDP. In situ Raman microspectroscopy and nanoindentation tests were used concurrently to quantify the degree of conversion ratio and dynamic mechanical properties across the adhesive-dentin interfaces. Despite the excellent diffusion and apparent higher degree of co-polymerization, 10-MDP reduced the elastic modulus of the interface. The higher viscoelastic properties of the adhesive are suggestive of poor polymerization, namely polymerization linearity related to the long carboxyl chain of 10-MDP. Such reduced mechanical integrity of hybridization could also be associated with the inhibition of nano-layering between 10-MDP and mineralized tissue in the presence of hydroxyethyl methacrylate (HEMA). This potential drawback of HEMA necessitates further qualitative/quantitative characterization of adhesive-dentin hybridization using a HEMA-free/low concentration experimental 10-MDP monomer, which theoretically possesses superior chemical bonding potential to the current HEMA-rich protocol.