A Fluorescent Sensor Array Based on Heteroatomic Macrocyclic Fluorophores for the Detection of Polluting Species in Natural Water Samples

Abstract

The development of a novel all-solid-state optical sensor array based on heteroatomic macrocyclic fluorophores (diaza-crown ether, metallocorrole and pyridinophans) for the photographic analysis of liquid media, is presented. The sensitivity of the new optical system toward a number of different species (cations: Li+, K+, Na+, NH4+, Mg2+, Ca2+, Co2+, Cu2+, Zn2+, Cd2+, Pb2+ and anions: NO2-, NO3-, Cl−, Br−, HCO3-) was evaluated both in single selective sensor mode and in multisensory arrangement. The satisfactory PLS1 regression models between sensor array optical response and analyte concentration were obtained for Cd2+, Cu2+, Zn2+, and NO2- ions in all the range of tested concentrations. Among these species the highest attention was focused onto detection of cadmium and nitrite ions, for which the detection limits, DL, estimated by 3σ method were found 0.0013 mg/L and 0.21 mg/L respectively, and these values are lower than the corresponding WHO guideline values of 0.003 mg/L (Cd2+) and 2 mg/L (NO2-). The suitability of the developed sensors implemented with familiar devices for signal acquisition (Light Emitting Diode, LED, as light source and a digital camera as a signal detector), and chemometric methods for data treatment to perform fast and low-cost monitoring of species under interest, in real samples of environmental importance, is demonstrated.

Sensing Zn2+ in Aqueous Solution with a Fluorescent Scorpiand Macrocyclic Ligand Decorated with an Anthracene Bearing Tail

“…Scorpiand type aza-macrocyclic ligands, that is aza-macrocyclic ligands with coordinating tails [1], and their metal complexes have attracted considerable interest thanks to the numerous uses they have been tested for, including but not limited to various biomedical applications [2,3] (MRI contrast agents [4,5], radioisotopes complexation and radiolabelling [6][7][8][9], radiotherapy [10][11][12][13][14], chelation therapy [15][16][17], antiproliferative treatments [18][19][20][21], enzyme mimicking [22][23][24][25][26][27][28][29]), catalysis [30][31][32][33][34][35][36] and chemosensing [37][38][39][40][41][42][43].…”

“…As regards the latter, receptors that signal their interaction with substrate species through a modification of their fluorescence emission properties (fluorescent chemosensors) have aroused wide interest, in particular for their efficiency, in terms of sensitivity and response times, as well as for their relatively easy preparation and for their ability to detect a variety of chemical species [37][38][39][40][41][42][43][44][45][46][47][48][49][50].…”

Heavy Metal/Toxins Detection Using Electronic Tongues

“…Within this context, some researchers developed hybrid devices operating with both light and electricity, such as the light-addressable potentiometric sensor (LAPS) or the multiple light-addressable potentiometric sensor (MLAPS) that have been successfully applied in e-tongue systems [41,53,54,69,70]. Lvova et al [19] explored the fluorescent properties of macrocyclic fluorophore-modified PVC membranes to quantify the concentration of Cd 2+ , Zn 2+ , Pb 2+ , and Cu 2+ ions on fountains, rivers, and seawater of Rome and region. PCA and PLS multivariate analysis were performed to evaluate the precision of the proposed method.…”

“…The most traditional techniques for the detection of heavy metal ions are high performance liquid chromatography (HPLC) coupled with electrochemical-or UV-Vis-detectors, atomic absorption spectroscopy (AAS), inductively coupled plasma mass spectroscopy (ICP-MS), electrothermal atomic absorption spectrometry, flame atomic absorption spectrometry, wet chemical methods such as colorimetry, titrimetry, and gravimetry, and electrochemical techniques [19][20][21][22][23][24][25][26][27][28]. Despite the high accuracy and sensitivity reached in these methods, most of them require expensive, complex, and sophisticated equipment that needs trained staff, making them difficult to use in on-site measurements for portable and easy-to-use detection [19,26,29,30].In this context, electrochemical methods are preferable due to their high sensitivity, fast response, low power cost, simpler approach, and ease of adaptability in order to be integrated into portable, disposable devices for the in-situ multi-element analysis of heavy metals. Nanomaterials have been used as an interesting strategy to enhance the sensitivity of the sensors due to easy functionalization and high electrochemical activity enabled by the electron-transfer process derived from unique electronic, physical, and chemical properties [31].…”

Highly sensitive determination of heavy metals in water prior to and after remediation using Citrofortunella Microcarpa

“…The detrimental effects of heavy metals on human health necessitate the development of sensors and methods which are cost-effective, highly sensitive, thoroughly selective, and have the advantage of portability. The traditional methods of heavy metal detection are high-performance liquid chromatography (HPLC), coupled with electrochemical- or UV–Vis-detectors, atomic absorption spectroscopy (AAS), inductively coupled plasma mass spectroscopy (ICP-MS) electrothermal atomic absorption spectrometry, flame atomic absorption spectrometry, and wet chemical methods such as colorimetry, titrimetry, and gravimetry 12 – 24 . Most of these methods require expensive, state-of-the-art bulky equipment manned by trained staff which inhibits in situ measurements.…”