Inorganic–Organic Hybrid Tongue-Mimic for Time-Resolved Luminescent Noninvasive Pattern and Chiral Recognition of Thiols in Biofluids toward Healthcare Monitoring

Abstract

In this work, manganese(II)-doped zinc/germanium oxide nanoparticles (Mn@ZGNPs) have been hydrothermally synthesized to equip with appealing time-resolved luminescence (TRL). Interestingly, we reveal that they can be readily quenched ("turn off") via a facile surface coating with bioinspired polydopamine (PDA) polymerized from dopamine (DA), resulting from PDA-triggered TRL resonance energy transfer (TRL-RET). By integrated with the thiol-induced inhibition of PDA formation, an ingenious inorganic-organic hybrid tongue-mimic sensor array is thus unveiled for noninvasive pattern recognition of thiols in biofluids in a TRL-RET-reversed "turn on" format toward healthcare monitoring. The sensing principle is based on the new finding that there are differential inhibitions from thiols against the polymerization of DA with various concentrations. Furthermore, density function theory (DFT) studies excellently prove our sensing principle and experimental results, reinforcing the power of the presented system. More importantly, chiral recognition of varied concentrations and mixtures of cysteine enantiomers using our platform are also been demonstrated, promising its practical usage. This is a novel concept of inorganic-organic hybrid-based pattern and chiral recognition platform for TRL background-free sensing and would sprout more novel relevant strategies toward broader applications.

Direct Determination of Redox Statuses in Biological Thiols and Disulfides with Noncovalent Interactions of Poly(ionic liquid)s

“…56−64 However, among them, only a few studies can enable a simultaneous discrimination of Cys, Hcys, and GSH. 60,63,64 More seriously, an added oxidized form of these biothiols would unquestionably impede sensor arrays for full and direct discrimination of redox identity just considering the low affinity of S−S group towards metals and the similarity in disulfides such as Cyss and Hcyss. Thus, currently no work attempts to address such a significant but neglected issue.…”

“…The structural similarity among these biothiols, particularly for Cys and Hcys which differ by a single methylene unit, poses considerable difficulties to design highly specific probes for simultaneously distinguishing one thiol species from another. Unlike a lock and key-based sensing strategy, differential sensing or sensor array technologies using cross-responsive sensing elements make it relatively easier to tackle such an intractable problem. − Recently, several groups constructed sensor arrays for the discrimination of biothiols mainly on the basis of interactions between thiols and metal ions/gold nanoparticles. − However, among them, only a few studies can enable a simultaneous discrimination of Cys, Hcys, and GSH. ,, More seriously, an added oxidized form of these biothiols would unquestionably impede sensor arrays for full and direct discrimination of redox identity just considering the low affinity of S–S group towards metals and the similarity in disulfides such as Cyss and Hcyss. Thus, currently no work attempts to address such a significant but neglected issue.…”

A Surface Mediated Supramolecular Chiral Phenomenon for Recognition of l- and d-Cysteine

“…Various methods have been used for the chiral recognition of enantiomers, in particular, optical methods, such as colorimetry [4,5,6,7], spectrofluorimetry [8,9,10,11] and circular dichroism (CD) spectroscopy [12,13,14,15,16,17,18] have received great interest due to their apparent advantages over other methods by virtue of their high sensitivity and the convenience in operation. CD spectroscopy is generally utilized to analyze the molecular chirality, which is sensitive to the conformational changes of the chiral molecules.…”

Engineering Ratiometric Persistent Luminous Sensor Arrays for Biothiols Identification

“…With the impressive discrimination power among very similar analytes, array-based optical sensors termed as “chemical noses“ have received more and more attention, which combines the reponses of cross-reactive sensor elements (receptors) to generate a unique pattern for each target analyte. − To improve the sensitivity and discrimination ability of array-based optical sensing, novel nanomaterials involving ratiometric/colometric, ,, lanthanide-derived, − or multiparameters luminous receptors have been developed for thiols detection in recent years. Notably, persistent luminescence (PersL) refers to a particular optical phenomenon whereby luminescence remains after ceasing excitation. , More importantly, the groundbreaking demonstration of PersL nanoparticles represented by zinc galletes (ZGO) were introduced by Scherman’s group in which PersL materials emitting luminescence as a highly promising contrast agent enabled long-term optical imaging in vivo.…”