Highly Enhanced Electrochemiluminescence Luminophore Generated by Zeolitic Imidazole Framework-8-Linked Porphyrin and Its Application for Thrombin Detection

Abstract

Novel and distinct enhancement in electrochemiluminescence (ECL) signals of advanced organic luminophores are of importance for expanding their applications in early diagnosis. This work reported the construction of an ultrasensitive label-free ECL aptasensor for thrombin (TB) detection by grafting zinc proto-porphyrin IX (ZnP) onto an aminated zeolitic imidazole framework-8 (defined as ZnP-NH-ZIF-8 for clarity) as the luminophore. The structure and optical properties of the resulting ZnP-NH-ZIF-8 were carefully characterized. For that, there appeared to be weak ECL radiation for ZnP in dichloromethane (DCM) containing tetra-n-butylammonium perchlorate (TBAP) because of the as-formed singlet-state oxygen via the “reduction–oxidation” route. More notably, the ECL signals display 153-times enhancement for ZnP-NH-ZIF-8, thanks to the excellent catalytic kinetics for the oxygen reduction reaction (ORR). By virtue of the specific interactions of the TB aptamer (TBA) with the TB protein and the highly efficient catalysis of the ZnP-NH-ZIF-8 for ORR, the as-prepared aptasensor showed a wider linear range (0.1 fM∼1 pM) and a lower detection limit (ca. 58.6 aM). This work provides some useful guidelines for synthesis of an advanced organic luminophore with largely boosted ECL signals in ultrasensitive analysis and clinical diagnosis.

Metal–Organic‐Framework‐Supported Molecular Electrocatalysis for the Oxygen Reduction Reaction

“… [23–25] Attaching molecular catalysts on nanomaterials through covalent bonds can solve this problem and lead to boosted electrocatalysis, but connecting molecules and supports is challenging from a synthetic point of view (Figure 1 b). [26–33] …”

“…[23][24][25] Attaching molecular catalysts on nanomaterials through covalent bonds can solve this problem and lead to boosted electrocatalysis, but connecting molecules and supports is challenging from a synthetic point of view (Figure 1 b). [26][27][28][29][30][31][32][33] We herein report MOF-supported Co porphyrins as catalysts for oxygen electrocatalysis. Co porphyrins are active and robust for electrocatalytic ORR, which is a significant process in many new energy conversion technologies, including fuel cells and metal-air batteries.…”

A sensitive electrochemiluminescent sensor chip based on the ssDNA‐Ru(II) complex and aptamer for the determination of thrombin

“…[2][3][4] The currently available TB detection methods include high performance liquid chromatography (HPLC), [5,6] fluorescence spectra, [7][8][9] surface plasmon resonance (SPR), [10][11][12][13][14] electrochemistry, [15][16][17] and electrochemiluminescence (ECL). [18][19][20][21][22][23][24][25] Among these methods, ECL is the method widely used in various bioanalyses due to its simplicity, high sensitivity, wide dynamic range, and low background interference. [26] An aptamer is a single-stranded or double-stranded oligonucleotide fragment obtained from artificially constructed random singlestranded oligonucleotide (ssDNA or ssRNA) libraries through ligand index enrichment phylogenetic evolution technology.…”

“…[ 2–4 ] The currently available TB detection methods include high performance liquid chromatography (HPLC), [ 5,6 ] fluorescence spectra, [ 7–9 ] surface plasmon resonance (SPR), [ 10–14 ] electrochemistry, [ 15–17 ] and electrochemiluminescence (ECL). [ 18–25 ] Among these methods, ECL is the method widely used in various bioanalyses due to its simplicity, high sensitivity, wide dynamic range, and low background interference. [ 26 ]…”

A Sensitive Signal‐off Electrochemical Aptasensor for Thrombin Detection using PB−Au@MoS2 Nanomaterial as Both Platform and Signal Reporter

“…Thus, it is extremely significant to detect TB for early diagnosis and prognosis judgment. Up to now, various techniques have been reported for the determination of TB, for example, electrochemiluminescence [8], chemiluminescence [9], surface enhanced Raman spectroscopy [10], fluorescence [11, 12] and electrochemical method [13–15]. Among these, special attention has been paid on the electrochemical strategy due to its relatively cheap equipment, simple operation, rapid response and high sensitivity [15, 16].…”