Thermally stable strongly fluorescent multi-stimuli responsive carbazole zwitterionic fluorophores: Alkyl chain length dependent thermofluorochromism and latent fingerprinting.

Carbazole-picoline based π-conjugated zwitterionic fluorophores, (E)-3-(4-(4-(9H-carbazol-9-yl)styryl)pyridin-1-ium-1-yl)propane-1-sulfonate (Cz-PS) and (E)-4-(4-(4-(9H-carbazol-9-yl)styryl)pyridin-1-ium-1-yl)butane-1-sulfonate (Cz-BS) were synthesized and investigated the stimuli-responsive solid-state fluorescence properties. Cz-PS and Cz-BS displayed enhanced fluorescence in the solid-state (555 and 542 nm) with the quantum yield (Φf) of 32.9 and 28.5 %, respectively. Thermogravimetric analysis (TGA) indicated good thermal stability up to 300 °C for both Cz-PS and Cz-BS. Single crystal structural analysis of Cz-BS confirmed twisted molecular conformation and supramolecular interactions induced network structure, which lead to increase of solid-state fluorescence. Cz-BS showed mechanical stimuli-induced reversible/self-reversible fluorescence switching between two fluorescence states whereas Cz-PS did not show mechanofluorochromism. But both Cz-PS and Cz-BS showed acid/base dependent on-off reversible fluorescence switching in solution as well as solid-state. Further, both compounds also displayed reversible thermofluorochromism by heating and cooling. The yellow fluorescence of Cz-PS and Cz-BS was transformed to orange upon heating at 110 °C and cooling reversed the fluorescence to initial state. The good thermal stability and enhanced solid-state fluorescence of Cz-PS and Cz-BS were utilized for latent fingerprinting (LFP) application on various solid substrate. Particularly, LFP images of Cz-BS showed finger marks with well-defined features. Thus, integrating zwitterionic functionality produced strong solid-state fluorescence with multi-functional applications.

Water sensitive fluorescence tuning of V-shaped ESIPT fluorophores: Substituent effect and trace amount water sensing in DMSO.

Highly sensitive nature of excited state intramolecular proton transfer (ESIPT) functionality in organic fluorophores made them potential candidates for developing environmental sensors and bioimaging applications. Herein, we report the synthesis of V-shaped Dapsone based Schiff base ESIPT derivatives (1-3) and water sensitive wide fluorescence tuning from blue to red in DMSO. Solid-state structural analysis confirmed the V-shaped molecular structure with intramolecular H-bonding and substituent dependent molecular packing in the crystal lattice. 1 showed strong solid-state fluorescence (λmax = 554 nm, Φf = 21.2 %) whereas methoxy substitution (2 and 3) produced tunable but significantly reduced fluorescence (λmax = 547 (2) and 615 nm (3), Φf = 2.1 (2) and 6.5 % (3)). Interestingly, aggregation induced emission (AIE) studies in DMSO-water mixture revealed water sensitive fluorescence tuning. The trace amount of water (less than 1 %) in DMSO converted the non-emissive 1-3 into highly emissive state due to keto tautomer formation. Further increasing water percentage produced deprotonated state of 1-3 in DMSO and enhanced the fluorescence intensity with red shifting of emission peak. At higher water fraction, 1-3 in DMSO produced aggregates and red shifted the emission with reduction of fluorescence intensity. The concentration dependent fluorescence study revealed the very low detection limit of water in DMSO. The limit of detection (LOD) of 1, 2 and 3 were 0.14, 1.04 and 0.65 % of water in DMSO. Hence, simple Schiff bases of 1-3 showed water concentration dependent keto isomer, deprotonated and aggregated state tunable fluorescence in DMSO. Further, scanning electron microscopic (SEM) studies of 1-3 showed water concentration controlled self-assembly and tunable fluorescence.

Bio-functionalized silver nanoparticles for selective colorimetric sensing of toxic metal ions and antimicrobial studies.

Hibiscus Sabdariffa (Gongura) plant extracts (leaves (HL) and stem (HS)) were used for the first time in the green synthesis of bio-functionalized silver nanoparticles (AgNPs). The bio-functionality of AgNPs has been successfully utilized for selective colorimetric sensing of potentially health and environmentally hazardous Hg(2+), Cd(2+) and Pb(2+) metal ions at ppm level in aqueous solution. Importantly, clearly distinguishable colour for all three metal ions was observed. The influence of extract preparation condition and pH were also explored on the formation of AgNPs. Both selectivity and sensitivity differed for AgNPs synthesized from different parts of the plant. Direct correlation between the stability of green synthesized AgNPs at different pH and its antibacterial effects has been established. The selective colorimetric sensing of toxic metal ions and antimicrobial effect of green synthesized AgNPs demonstrated the multifunctional applications of green nanotechnology.