Metal Ion Responsive Luminescent Bio-Templated Co-Assemblies: Label-Free Detection of Multi-Metal Ions in Aqueous Media.

Recently, anionic bio-templates have emerged as promising platforms for designing dynamic and stimuli-responsive chromophoric assemblies capable of light harvesting in aqueous media thereby mimicking natural photosynthesis. Here, we present multi-metal ion-responsive luminescent co-assemblies between cationic pyrene-imidazolium amphiphile and anionic bio-templates (ATP, heparin, and DNA) in aqueous media. The anionic bio-templates enhance Förster resonance energy transfer (FRET) in the co-assemblies, with pyrene serving as an excellent donor for generating tunable multi-luminescent materials with embedded acceptor dyes. However, a significant loss in energy transfer towards acceptor dyes was observed in the presence of various metal ions, attributed to excimeric emission quenching facilitated by electron transfer between the pyrene chromophore and metal ions. Interestingly, detailed studies revealed that only ATP-based co-assemblies exhibited quenching phenomena in the presence of metal ions, contrasting with heparin and ctDNA co-assemblies. Additionally, label-free detection of multi-metal ions in aqueous environments, such as Fe2+, Fe3+, and Cu2+ ions, was successfully achieved with lower detection limits of 0.01 µM (3 ppb), 0.12 µM (30 ppb), and 0.58 µM (150 ppb) respectively. These co-assemblies hold significant promise for practical applications in environmental and biomedical sensing, enabling sensitive monitoring of metal ion concentrations.

A carbon dots-MnO2 nanosheet-based turn-on pseudochemodosimeter as low-cost probe for selective detection of hazardous mercury ion contaminations in water.

Mercury is a highly hazardous element due to its profound toxicity and wide abundance in the environment. Despite the availability of various fluorimetric detection tools for Hg2+, including organic fluorophores and aptasensors, they often suffer from shortcomings like the utilization of expensive chemicals and toxic organic solvents, multi-step synthesis, sometimes with poor selectivity and low sensitivity. Whereas, biomass-derived fluorophores, such as carbon dots (CDs), present themselves as cost-effective and environmentally benign alternatives that exhibit comparable efficacy. Herein, we report a reaction-driven sensing assembly based on CDs, MnO2 nanosheets, and hydroquinone monothiocarbonate (HQTC) for the detection of Hg2+ ions, which relies on the formation of a CDs-MnO2 FRET-conjugate, resulting in the quenching of the intrinsic fluorescence of CDs. In a pseudochemodosimetric approach, the thiophilic nature of mercury was utilized for in-situ generation of the reducing species, hydroquinone from HQTC, resulting in the reduction of MnO2 nanosheets, the release of fluorescent CDs back to the solution. The low limit of detection (LOD) was achieved as 2 ppb (0.01 µM). The probe worked efficiently in real water samples like sea, river with good recovery of spiked Hg2+ and in some Indian ayurvedic medicines as well. Furthermore, solid-phase detection with sodium alginate beads demonstrated the ability of this cost-effective sensing assembly for onsite detection of Hg2+ ions.

A New Series of D1 -A-D2 -type ESIPT-TICT-AIE Active Orange-to-red Emissive Unsymmetrical Azines: Their All-throughout Mechanochemical Synthesis and Exploration of Photophysical Properties.

Azines are interesting compounds exhibiting aggregation-induced-emission (AIE) and twisted-intramolecular-charge-transfer (TICT) properties that have exciting prospects in chemosensing and bioimaging applications. They commonly have symmetrical structures and there is no report on red-emissive unsymmetrical azines. Herein, we report a novel class of orange-to-red emissive hydroxybenzothiazole(HBT)-based unsymmetrical azines (BTDPA) with triple photophysical characteristics of ESIPT-TICT-AIE. The dyes were synthesized by an all-throughout mechanochemical route in a sustainable way. They displayed D1 -A-D2 character and fluoresce strongly both in organic solvents due to ESIPT and in the solid state by AIE via TICT. The incorporation of different electron-withdrawing groups (EWGs) and electron-donating groups (EDGs) at either HBT or diphenyl-methylene moiety resulted in tunable fluorescence properties. The red-emissive character was achieved by keeping EDG both at HBT (-OMe) and the diphenyl-methylene moiety (-NMe2 ) (λem 680 nm). The dyes exhibited good quantum yields, large Stoke shifts (upto 293 nm) and were utilized in nitroaromatics and Cu2+ sensing.

A combination of a graphene quantum dots-cationic red dye donor-acceptor pair and cucurbit[7]uril as a supramolecular sensor for ultrasensitive detection of cancer biomarkers spermine and spermidine.

In a unique approach, the combination of a donor-acceptor pair of hydroxy graphene quantum dots (GQDs-OH) and a red-emissive donor-two-acceptor (D-2-A) type dye with pyridinium units (BPBP) and the well-known host cucurbit[7]uril (CB[7]) has been exploited as a supramolecular sensing assembly for the detection of cancer biomarkers spermine and spermidine in aqueous media at the sub-ppb level based on the affinity-driven exchange of guests from the CB[7] portal. In the binary conjugate, green fluorescent GQDs-OH transfers energy to trigger the emission of the dye BPBP and itself remains in the turn-off state. CB[7] withdraws the dye from the surface of GQDs-OH by strong host-guest interactions with its portal, making GQDs-OH fluoresce again to produce a ratiometric response. In the presence of spermine (SP) or spermidine (SPD), their strong affinity with CB[7] forces the ejection of the fluorophore to settle on the GQDs-OH surface, and the strong green emission of GQDs-OH turns off to device a supramolecular sensor for the detection of SP/SPD. The DFT studies revealed interesting excited-state charge-transfer conjugate formation between BPBP and GQDs leading to turn-on emission of the dye, and further supported the stronger binding modes of BPBP-CB[7], indicating the retrieval of the emission of GQDs. The assembly-disassembly based sensing mechanism was also established by Job's plot analysis, particle size analysis, zeta potential, time-resolved spectroscopy, ITC studies, microscopic studies, etc. The supramolecular sensing assembly is highly selective to SP and SPD, and showed nominal interference from other biogenic amines, amino acids, various metal ions, and anions. The limits of detection (LODs) were 0.1 ppb and 0.9 ppb for spermine and spermidine, respectively. The potential for the real-world application of this sensing assembly was demonstrated by spiking SP and SPD in human urine and blood serum with a high %recovery.

A coumarin coupled tetraphenylethylene based multi-targeted AIEgen for cyanide ion and nitro explosive detection, and cellular imaging.

A coumarin coupled tetraphenylethylene based AIEgen (TPE-Lac) with an intense greenish-yellow emission has been synthesized and utilized for multipurpose sensing and imaging applications. TPE-Lac acts as a sensitive sensor for the detection of cyanide ions (CN-) with an immediate turn-off response in the presence of many other interfering cations and anions. The limit of detection (LOD) was as low as 33 nM, which is well below the permissible limit set by the World Health Organization (WHO). Cyanide detection in the solid phase was successfully demonstrated by drop-casting the solution of the TPE-Lac probe on TLC plates and measuring and analysing the fluorescence response by ImageJ analysis. TPE-Lac was further employed in the detection of explosive nitroaromatics in solution and solid phases. Also, TPE-Lac was found suitable as an imaging agent and could easily percolate into live H520 cells giving bright fluorescence from the intra-cellular region. Easy and cost-effective synthesis, fast response and low LODs are some of the advantages of this AIEgen over available molecular probes for the same purpose.

Phthalimide conjugation turns the AIE-active tetraphenylethylene unit non-emissive: its use in turn-on sensing of hydrazine in solution and the solid- and vapour-phase.

Hydrazine is a vital precursor used in several pharmaceuticals and pesticide industries and upon exposure can cause severe health hazards. Herein, a new AIEgen, tetraphenylethylene phthalimide (TPE-PMI), is synthesized in a one-step solvent-free mechanochemical approach exploiting the simple condensation between TPE-NH2 and phthalic anhydride and used for the selective and sensitive detection of hydrazine. TPE-PMI with an AIE-active TPE-moiety is non-emissive in the solid phase by design. Hydrazine performs the cleavage of TPE-PMI in a typical "Gabriel synthesis" pathway to release AIE-active TPE-NH2 in an aqueous solution to emit blue fluorescence. A gradual rise in fluorescence intensity at 462 nm was due to the increasing hydrazine concentration and TPE-PMI showed a linear relationship with hydrazine in the concentration range from 0.2 to 3 µM. The selectivity study confirmed that the probe is inert to amines, amino acids, metal anions, anions and even common oxidants and reductants. The detection limit is 6.4 ppb which is lower than the US Environmental Protection Agency standard (10 ppb). The practical utilities of TPE-PMI were successfully demonstrated through quantitative detection of hydrazine vapour on solid platforms like paper strips and TLC plates. Furthermore, on-site detection of hydrazine in the solid phase was demonstrated by spiking the soil samples with measured quantities of hydrazine and quantitation through image analysis. This cost-effective sensing tool was successfully utilized in in vitro detection of hydrazine in live HeLa cells.