Simultaneous discrimination of multiple enzymes in clinical diagnosis is significance and remains a great challenge. Herein, we reported a facile synthesis of three ternary transition metal sulfide (TTMS) nanoparticles , i.e. FeCo 2 S 4 , CuCo 2 S 4 and FeCu 2 S 4 , by using L -cysteine as sulphur source for oxidase discrimination. The CL emission from luminol oxidation by hydrogen peroxide (H 2 O 2 ) was greatly enhanced by TTMS, with the maximal three orders of magnitude CL signal amplification for FeCo 2 S 4 . Hence, an ultra-sensitive CL assay was developed for H 2 O 2 detection down to 0.5 pM. Because H 2 O 2 is generated via biocatalytic reaction between substrate and corresponding oxidase, thus, CL sensor arrays can be developed to discriminate different oxidases. The sensing principle is based on the fact that different substrates/oxidases produced different amounts of H 2 O 2 . For each substrate/oxidase couple, the sensor array produces a peculiar CL intensity pattern able to be distinguished via linear discriminant analysis. As a proof-of-concept study, four oxidases, i.e. glucose-, sarcosine-, choline- and cholesterol-oxidase, were selected to demonstrate the array’s discrimination performance and were identified successfully with an accuracy of 100%, and achieved the accurate discrimination of oxidases in serum samples. This work demonstrated the potential of the TTMS-based CL sensor array to discriminate multiple oxidases.
Efficient lipase-mediated research work was successfully exploited for synthesizing potential 6″- O -acyl-polydatin prodrugs in biomass-derived 2-methyltetrahydrofuran (2-MeTHF). The results of the enzyme recognitions of nine acyl donors evidently demonstrated that the position and number of the C C double bond in acyl chains profoundly influenced the behavior of the enzyme, which could be attributable to the resonance effect between the double bond and carbonyl group. Further investigations showed that introducing various acyl groups into the polydatin apparently enhanced its pH stability and 1-octanol-water partition coefficient (log P ). With regard to the human cervical cancer siHa cell apoptosis by a flow cytometry assay, the lipophilic 6″- O -sorboyl-polydatin exhibited improved apoptosis-inducing capability than the parent drug. The presence of the more lipophilic sorboyl chain in the acylated derivative could account for this.
Molecularly imprinted polymers against proteins are regarded as promising substitutes for natural antibodies, but have been frustrated with the problems including reduced interaction between functional monomers and protein template in the aqueous media required during their synthesis and restricted mass transfer across the resulting crosslinked polymer matrixes . For addressing these issues, herein we proposed a strategy for imprinting of a protein on the surface of nanoparticles using a metal chelating monomer. With lysozyme as a model protein template and Cu 2+ chelating N-(4-vinyl)-benzyl iminodiacetic acid as the coordination monomer along with other monomers, protein imprinted polymer nanoshells were formed over vinyl-modified silica nanoparticles via surface polymerization in high-dilution monomer solution. The feed concentration of the crosslinking monomer was optimized toward achieving the best imprinting effect. Compared with the related imprinted materials reported previously, the resultant core–shell imprinted particles showed greatly faster binding kinetics , elevated rebinding capacity and selectivity . More importantly, noticeably high binding affinity was achieved with an estimated dissociation constant of 4.1×10 −8 M which is comparable to that of conventional antibodies
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