Exploring Various Photochemical Processes in Optical Sensing of Pesticides by Luminescent Nanomaterials: A Concise Discussion on Challenges and Recent Advancements.

Food safety is a burning global issue in this present era. The prevalence of harmful food additives and contaminants in everyday food is a significant cause for concern as they can adversely affect human health. More particularly, among the different food contaminants, the use of excessive pesticides in agricultural products is severely hazardous. So, the optical detection of residual pesticides is an effective strategy to counter the hazardous effect and ensure food safety. In this perspective, nanomaterials have played a leading role in defending the open threat against food safety instigated by the reckless use of pesticides. Now, nanomaterial-based optical detection of pesticides has reached full pace and needs an inclusive discussion. This Review covers the advancement of photoprocess-based optical detection of pesticides categorically using nanomaterials. Here, we have thoroughly dissected the photoprocesses (aggregation and aggregation-induced emission (AIE), charge transfer and intramolecular charge transfer (ICT), electron transfer and photoinduced electron transfer (PET), fluorescence resonance energy transfer (FRET), hydrogen bonding, and inner filter effect) and categorically demarcated their significant role in the optical detection of pesticides by luminescent nanomaterials over the last few years.

Selective Luminescence Turn-On-Based Sensing of Phosphate in the Presence of Other Interfering Anions Using a Heterobimetallic (3d-4d) MOF with an Acidic Pocket.

A luminescent metal-organic framework with the molecular formula [YMn1.5(C7N1H3O5)3(H2O)6]·11H2O, 1 {where C7N1H3O5 = chelidamate}, was synthesized by a hydrothermal method by employing chelidamic acid as an organic ligand and Y(III) and Mn(II) as metal ions. A two-dimensional heterobimetallic structure with phenolic hydroxyl-functionalized pockets was revealed by single-crystal X-ray diffraction analysis of compound 1. PXRD, TGA, IR, BET analysis, and UV-vis spectroscopy were used for the thorough characterization of compound 1. Upon excitation at 280 nm, compound 1 shows bright blue emission, which was utilized for the selective and sensitive turn-on detection of the PO43- ion. Based on Bronsted-Lowry acid-base interactions, the photoluminescence of compound 1 was enhanced in the presence of very low concentrations of the aforementioned anion. The mechanism behind the detection of the phosphate ion has been explored in detail. It was seen that the PO43- anion entered the hydroxyl-functionalized pockets of compound 1 and stabilized the aromatic portion of compound 1 via molecular-level interactions through acid-base interactions. These molecular-level interactions are responsible for the enhancement of the photoluminescence intensity of compound 1 after the incorporation of phosphate ions by reducing the nonradiative transitions. These phenomena were also confirmed by time-correlated single photon counting (TCSPC) measurement, which shows that the excited-state lifetime increased with the increase in addition of phosphate anions. The calculated limit of detection (LOD) of 1 was 19.55 ppb for phosphate (PO43-), which was significantly lesser than the recommended level for the PO43-anion toward the human body. The luminescence enhancement coefficient, KSV, value was also much higher than those of other reported metal-organic frameworks.

Response of a Zn(II)-based metal-organic coordination polymer towards trivalent metal ions (Al3+, Fe3+ and Cr3+) probed by spectroscopic methods.

A new zinc-based two-dimensional coordination polymer, [Zn(5-AIP)(Ald-4)]·H2O (5-AIP = 5-amino isophthalate, Ald-4 = aldrithiol-4), 1, has been synthesized at room temperature by the layer diffusion technique. Single-crystal X-ray diffraction analysis of 1 showed a two-dimensional bilayer structure. An aqueous suspension of 1 upon excitation at 300 nm displayed an intense blue emission at 403 nm. The luminescence spectra were interestingly responsive and selective to Al3+, Cr3+ and Fe3+ ions even in the presence of other interfering ions. The calculated detection limits for Al3+, Cr3+ and Fe3+ were 0.35 µM ([triple bond, length as m-dash]8.43 ppb), 0.46 µM ([triple bond, length as m-dash]22.6 ppb) and 0.30 µM ([triple bond, length as m-dash]15.85 ppb), respectively. Notably, with the cumulative addition of Al3+ ions, the luminescence intensity at 403 nm decreased steadily with a gradual red shift up to 427 nm. Afterward, this red shifted peak showed a turn-on effect upon further addition of Al3+ ions. On the other hand, for Cr3+ and Fe3+ ions, there was only drastic luminescence quenching and a large red shift up to 434 nm. This indicated the formation of a complex between 1 and these metal ions, which was also supported by the UV-Visible absorption spectra of 1 that showed the appearance of a new band at 280 nm in the presence of these three metal ions. The FTIR spectra revealed that these ions interacted with the carboxylate oxygen atom of 5-AIP and the nitrogen atom of the Ald-4 ligand in the structure. The luminescence lifetime decay analysis manifested that a charge-transfer type complex was formed between 1 and Cr3+ and Fe3+ ions that resulted in huge luminescence quenching due to the efficient charge transfer involving the vacant d-orbitals, whereas for Al3+ ions having no vacant d-orbital, turn-on of luminescence occurred because of the increased rigidity of 1 upon complexation.