The development of sensitive and
selective tools for the detection
and quantification of biomarkers is important in the diagnosis and
treatment of clinical diseases. Spermine (SP) and spermidine (SPD)
act as biomarkers for early-stage diagnosis of cancer in humans as
their increased levels in urine are indicative of abnormal biological
processes associated with this fatal disease. In this study, we introduced
a strategy for solid-supported amplification of the effective aggregation-induced-emission
(AIE) effect of a water-soluble tetraphenylethylene (TPE)-based probe
in developing a supramolecular sensing platform for the rapid, sensitive,
and selective detection of SP and SPD in water. The nonemissive TPE
derivative (TPEHP) forms a less emissive conjugate with hydroxyl cucurbit[6]uril
(CB[6]OH) in water, which undergoes several-fold enhancement of effective
emission upon electrostatic interaction with the solid surface of
hydroxyapatite nanoparticles (HAp NPs), dispersed in the aqueous media.
The corresponding three-component supramolecular assembly disrupts
by the intrusion of SP and SPD in the CB[6] portal because of the
stronger binding ability with CB[6], resulting in a turn-off fluorescence
sensor for SP and SPD with enhanced sensitivity. The assembly–disassembly-based
sensing mechanism was thoroughly demonstrated by carrying out isothermal
titration calorimetry (ITC), spectroscopic, and microscopic experiments.
The sensing system showed low limits of detection (LODs) of 1.4 ×
10–8 and 3.6 × 10–8 M for
SP and SPD, respectively, which are well below the required range
for the early diagnosis of cancer. Besides, a good linear relationship
was obtained for both SP and SPD. Nominal interference from various
metal ions, anions, common chemicals, amino acids, and other biogenic
amines makes this sensing platform suitable for the real-time, low-level
measurement of spermine (and spermidine) in human urinary and blood
samples.
Two sulfonate functionalized tetraphenylethylene (TPE) derivatives were synthesized and used as probes for the detection and imaging of Gram-positive bacteria (e.g. Staphylococcus aureus).
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