Spermine detection via metal-mediated ethynylarene ‘turn-on’ fluorescence signaling

Abstract

A dicarboxylated ethynylarene was shown to behave as a fluorescent chemosensor for millimolar concentrations of polyamines when mixed with Cd(II), Pb(II) or Zn(II) ions at micromolar concentrations. A bathochromic shift and intensification of fluorescence emission was observed with increasing amounts of metal ion in the presence of aqueous polyamines buffered at pH = 7.6. Such perturbations manifested as ‘turn-on’ signals from a ratiometric comparison of emission intensities at 390 nm versus 340 nm. Using Pb(II) as the metal mediator, spermine was selectively detected as a 40-fold signal enhancement relative to spermidine, putrescine, cadaverine and several other non-biogenic diamines. Evaluation of additional triamine and tetraamine analytes showed the influence that amine group quantity and spacing had on signal generation. By increasing the ratio of Pb(II) relative to ethynylarene, the detection limit for spermine was successfully lowered to a 25 micromolar level. Noncovalent association between ethynylarene, metal ion and polyamine are believed to promote the observed spectroscopic changes. This study exploits the subtle impact that polyamine structural identity has on transition metal chelation to define a new approach towards polyamine chemosensor development.

MOF sensors for food safety: ultralow detection of putrescine and cadaverine in protein rich foods

“…It is noteworthy that only a handful of fluorescent sensors have been reported to date for the sensing of biogenic amines. [10][11][12][13][14][15][16][17] Most of these sensors comprise purely organic materials. [10][11][12][13][14] Porous materials such as metal organic frameworks (MOFs) possessing a high surface area, permanent porosity, and good thermal and chemical stability with tuneable properties are known for various applications.…”

“…[10][11][12][13][14][15][16][17] Most of these sensors comprise purely organic materials. [10][11][12][13][14] Porous materials such as metal organic frameworks (MOFs) possessing a high surface area, permanent porosity, and good thermal and chemical stability with tuneable properties are known for various applications. [18][19][20][21][22] Due to their unique properties and advantage of pre-selecting suitable building blocks, MOFs have been used for designing fluorescent sensors for detection of nitro explosives, volatile organic compounds, heavy metal ions, amines, drugs, etc.…”

Solid-Supported Amplification of Aggregation Emission: A Tetraphenylethylene–Cucurbit[6]uril@Hydroxyapatite-Based Supramolecular Sensing Assembly for the Detection of Spermine and Spermidine in Human Urine and Blood

“…Spermine (SP) and spermidine (SPD) are the most ubiquitous among biogenic polyamines (PAs) and they are important regulators of various cellular processes including cell growth, proliferation, homeostasis, and even protein biosynthesis. − They are also involved in metabolic regulation, regeneration of intestinal mucosa, and wound healing, especially at low concentrations. − However, elevated levels of these amines are responsible for aging and symptomatic of anomalous biological progressions concomitant with cancer. − Spermine/spermidine is investigated as a biochemical marker for the timely diagnosis of cancer. ,, The presence of spermine and spermidine is also measured as an indicator of the quality of food, as their concentration surges due to fermentation or decomposition, which leads to health issues. , In addition, at higher concentrations, these PAs cause food spoilage and food poisoning. , Thus, the development of selective and sensitive detection tools for these biogenic polyamines is of great importance for the early diagnosis of diseases as well as the maintenance of food hygiene. Encouraged by these facts, a variety of chemosensors for spermine and spermidine have been developed based on fluorimetry, mainly adopting various supramolecular approaches. − This includes dye-embedded micelles, , sol–gel films, , conjugated polymers, − and other supramolecular approaches. , A close look at most of these reports suggests that selectivity of these polyamines is based on analyte-induced self-assembly of the reporting units to amplify the sensing response. However, they suffer from one or more limitations such as interference from other polyamines, susceptibility to external stimuli (e.g., light, heat), and also not well explored under physiological condition.…”

Simple fluorescence optosensing probe for spermine based on ciprofloxacin-Tb3+ complexation

“…In contrast, fluorescence methods have become a popular method due to the versatility, sensitivity, low detection, and visual capacities [31][32][33]. For example, Fletcher and Bruck [34] reported an SP sensor based on "turn-on" fluorescence of dicarboxylated ethynylarene by mixing Pb(II) cations with SP. However, the preparation procedure of dicarboxylated ethynylarene was too complicated to adapt for practical applications.…”