Excited-state properties of 6-methoxyflavone in the presence of halide ions in aqueous media.

The present work investigated the influence of different halides on the excited state dynamics of 6-methoxyflavone (6MF) in an aqueous solution with steady-state and time-resolved techniques. On successive addition of I-and Br-ions, the fluorescence of 6MF quenched significantly, whereas the respective ions do not change the maximum fluorescence band. Fluorescence of 6MF was quenched 66% by I-ions and 34% by Br-ions. In a pure aqueous medium, both the H-bonded: CT and protonated species of 6MF participate in the quenching of fluorescence. The quenching process was categorized by Stern-Volmer (S-V) and Lehrer equations. Quenching parameters such as KSV, KSV-Land kqwere higher for I-ions than Br-ions. The decrease in fluorescence intensity and a reduction in fluorescence lifetime suggested the dynamic nature of quenching by I-ions following the electron transfer mechanism. Fluorescence quenching of 6MF has also been observed in the acidic medium in the presence of different halides. Thus, the study reveals that 6MF is responsive towards I-ions in a wide range of pH, specifically in a purely aqueous environment (pH∼7), hence important for sensing/detection applications.

Selectively probing ferric ions in aqueous environments using protonated and neutral forms of 7-azaindole as a multiparametric chemosensor.

7-azaindole (7AI) dimer is a model molecule for DNA study and understanding the mutagenic behavior based on the excited-state proton transfer process in hydrogen-bonded networks. The neutral and protonated forms of 7AI monomer with significant fluorescence (FL) intensity fit the fluorescent sensor strategy to recognize selective metal ions. Out of several metal ions (Fe3+, Al3+, Fe2+, Pb2+, Ba2+, Ni2+, Zn2+, Mg2+, Ca2+, Cu2+, Hg2+ and Cd2+), the absorption, fluorescence and fluorescence lifetime of 7AI in the aqueous medium are selectively sensitive to the ferric (Fe3+) ions. The absolute value of absorption intensity increases linearly with concentration of a particular metal ions. FL intensity of both the forms of 7AI decreases gradually with Fe3+ ions and trails the linear Stern-Volmer relation. The formation of non-fluorescent complexes was confirmed with Benesi-Hildebrand and Job plots, along with FL and FL decays. The FL lifetime of the protonated form of 7AI, which is 0.83 ± 0.01 ns, is nearly constant with Fe3+ ions concentrations, confirming the static quenching mechanism. The limit of detection (LoD) of Fe3+ ions over the long range of 16-363 µM for the neutral and protonated forms of 7AI is 0.46 ± 0.02 and 0.49 ± 0.02 µM, respectively, estimated using FL spectra. Additionally, the linear plot of absorbance with Fe3+ ions of both the forms of 7AI can also act as a calibration curve with very close LoDs, as obtained by FL spectra. Thus, the multi-parameters-based probe for detecting the Fe3+ ions over long-range in real aqueous environments with operational, high sensitivity, fast response (< 5 s), and good selectivity (over 12 metal ions) is undoubtedly a superior approach over other methods.

Effect of halide ions on the fluorescence properties of 3-aminoquinoline in aqueous medium.

Fluorescence (FL) quenching of 3-aminoquinoline (3AQ) by halide ions Cl - Br - and I - has been explored in an aqueous acidic medium using the steady-state and time-domain FL measurement techniques. The halide ions showed no significant change in the absorption spectra of 3AQ in an aqueous acidic medium. The FL intensity was strongly quenched by I - ions and the order of FL quenching by halide ions was I - > Br - > Cl - . The decrease in FL lifetime along with the reduction in FL intensity of 3AQ suggested the dynamic nature of quenching. The obtained K SV values were 328 M - 1 for I - ions and 119 M - 1 for Br - ions and the k q values were ~ 1.66 × 10 10 M - 1 s - 1 and 6.02 × 10 9 M - 1 s - 1 , respectively. The observations suggested that the likely governing mechanism for FL quenching may be an electron transfer process and the involvement of the heavy atom effects.

Spectroscopic investigation on the interaction of direct yellow-27 with protein (BSA).

Direct yellow 27 (DY-27) interaction with bovine serum albumin (BSA) was investigated using multi-spectroscopic techniques to understand the toxicity mechanism. Fluorescence quenching of BSA by DY-27 was observed as a result of the formation of a BSA-DY27 complex with a binding constant of 1.19 × 105M-1and followed a static quenching mechanism with a quenching constant Ksvof 7.25 × 104M-1. The far UV circular dichroism spectra revealed the conformational changes in the secondary structure of BSA in the presence of DY-27. The calculated average lifetime of BSA is 6.04 ns and is nearly constant (5.99 ns) in the presence of dye and supports the proposed quenching mechanism. The change in free energy (ΔG) was calculated to be -28.96 kJ mol-1and confirmed the spontaneity of the binding process. Further, docking studies have been conducted to gain more insights into the interactions between DY-27 and serum albumin.

Surface plasmon resonance allied applications of silver nanoflowers synthesized from Breynia vitis-idaea leaf extract.

An environmentally friendly, green synthesis process has been adopted to synthesize silver nanoparticles (AgNPs) in an aqueous solution from a new remedial plant. Breynia vitis-idaea leaves act like natural capping and reducing agents. The resulting AgNPs were characterized and analyzed using different characterization techniques, such as UV-Vis spectroscopy, X-ray diffraction, zeta potential, transmission electron microscopy (TEM) and scanning electron microscopy (SEM). The UV-Vis absorption spectrum showed high stability and a surface plasmon resonance (SPR) peak around 430 nm. The effects of several processing variables, such as reaction time, temperature, concentration and pH, were analyzed. High temperature and alkaline pH intensify the ability to form flower-shaped AgNPs with enhanced properties. AgNPs were investigated for antibacterial activity against Gram-negative E. coli bacterial strains with a 10 mm zone of inhibition. These AgNPs showed dye degradation up to 88% when an aqueous crystal violet dye solution was mixed with AgNPs as the catalyst. Further, AgNPs alone were effectively used in the detection of hydrogen peroxide (H2O2) in an aqueous medium with a LOD (limit of detection) of 21 µM, limit of quantification (LOQ) of 64 µM and a decrease in absorption intensity up to 89%. Based on these results, these AgNPs were effectively used in numerous fields, such as biomedical, water purification, antibacterial and sensing of H2O2.

Solvatochromism and estimation of ground and excited state dipole moments of 6-aminoquinoline.

The spectral behaviour of 6AQ was investigated using fluorescence spectroscopy in several polar and non-polar solvents. Both the absorption and fluorescence spectra displayed solvatochromism. The Stokes shift increased significantly with increasing solvent polarity and signifies a more polar excited state with possible change in the excited state (ES) geometry. The involvement of π→π∗ transition was observed. The ground state (GS) and excited state (ES) dipole moments were determined by the solvatochromic shift method using Bilot-Kawaski, Lippert-Mataga, Kawski-Chamma-Viallet, and Reichardt equations. The experimental value of GS dipole moment matches closely with the theoretical value computed using DFT/B3LYP/6-311G(d,p). The ES dipole moment is higher than the GS dipole moment. Besides, the solvatochromic study reveals that the ES of 6AQ is more polarized than the GS due to intramolecular charge transfer (ICT), possibly aided by a change in the geometry of the molecule in the ES. The influence of the non-specific and specific interactions in the photophysical properties of the titled molecule was analyzed using the Catalan scale. The study shows that 6AQ has reasonable band-gap energy and good CIE chromaticity coordinate in the blue region close to the national television standard committee system (NTSC) for the ideal blue CIE coordinate. Therefore, future research into 6AQ as a source of light-emitting diodes and fluorescent sensors may have potential applications in the field of optoelectronics.

Structural, Electronic and NLO Properties of 6-aminoquinoline: A DFT/TD-DFT Study.

A computational study based on the DFT/TD-DFT approach was performed to explore various properties of 6-aminoquinoline (6AQ). The geometrical parameters, molecular orbitals (MOs), electronic spectra, electrostatic potential, molecular surface, reactivity parameters and thermodynamic properties of 6AQ were explored. The absorption and emission spectra of 6AQ in solvents have been estimated by TD-DFT coupled with the PCM model and correlated with the available experimental results. Depending on the solvents, the computed absorption maxima of 6AQ were noticed between 327 nm - 340 nm and ascribed to [Formula: see text] transition. The simulated emission maxima were obtained between 389 to 407 nm and ascribed to [Formula: see text] transition. On increasing the solvent polarity, both the emission and absorption maxima showed a bathochromic shift. The LUMO and HOMO were localized on the entire molecule. It was observed that the lowest excited state is possibly the [Formula: see text] charge-transfer (CT) state. The natural bonding orbital (NBO) study points out that ICT plays a significant role in stabilizing the molecular system. Moreover, the NLO (nonlinear optical) properties (polarizability, first-order hyperpolarizability and dipole moment) were computed using different hybrid functionals. The estimated values indicate that 6AQ can be considered a desirable molecule for further studies of the NLO applications.

Rapid optical sensor for recognition of explosive 2,4,6-TNP traces in water through fluorescent ZnSe quantum dots.

In this report, blue fluorescent zinc selenide quantum dots (ZnSe QDs) were synthesized using 3-mercaptopropionic acid through a direct aqueous route at a lower temperature of 70 °C. The photoluminescence (PL) characteristics of ZnSe QDs have been employed to recognize nitroaromatic compounds, i.e., traces of 2,4,6-TNP (picric acid) in water. The sensing of nitroaromatic compounds was performed via fluorescence techniques. The PL band of ZnSe QDs observed at 490 nm is selectively quenched with an increasing concentration of picric acid in DI water and river water. For the proposed sensing probe, the Stern-Volmer (S-V) plot shows linearity over the range of 2.0 µM-0.25 mM with the detection limit of 12.4 × 10-6 M without any interference effect of other nitroaromatic compounds. The plausible mechanism of PL quenching is considered as the inner filter effect, based on absorption, PL and PL lifetimes.

Reinvestigation of the photophysics of 3-aminobenzoic acid in neat and mixed binary solvents.

The present study elucidates the reinvestigation of the photophysical behavior of 3-aminobenzoic acid (3ABA) in solvents of different polarities using the steady-state spectroscopic techniques. Kamlet-Taft and Catalan solvatochromic models have been used to analyze the solvatochromic changes in neat solvents. The hydrogen bond donating ability of the solvent was found to be the main parameter affecting the spectral behavior of 3ABA. The solvatochromic characteristics of 3ABA have also been examined in binary solvent mixtures viz. acetonitrile (ACN)-methanol (MeOH) and benzene (BEN)-MeOH using the concept of preferential solvation. The preferential solvation of 3ABA shows unusual behavior for BEN-MeOH binary mixture and described unnoticed sigmoidal behavior in the ground state and synergistic impact in the excited state. Besides, the 3ABA was studied theoretically by quantum chemical calculations using (HF) Hartree-Fock and (DFT/B3LYP) density functional theories and its electronic absorption bands have been assigned by time-dependent density functional theory (TD-DFT). The effect of solvents on 3ABA was considered using a IEF-PCM-TDDFT (integral equation formalism of the polarizable continuum model- TDDFT) method. Thus, the theoretical results were found to be closer to the experimental results.

Flavones Fluorescence-Based Dual Response Chemosensor for Metal Ions in Aqueous Media and Fluorescence Recovery.

Responsiveness of sensing materials 3-hydroxyflavone (3HF) towards metal ions in aqueous medium has been explored following photoexcitation. 3HF exhibited both colorimetric and fluorescence (FL) turn-off response towards Cu2+ and Fe2+ with high sensitivity and selectivity. Meanwhile, the distinct colour change and the rapid quenching of FL intensity provide naked-eye detection. On successive addition of Cu2+and Fe2+ ions, FL of 3HF was "turned off," whereas there is no change in wavelength of FL bands. Quenching efficiencies for Cu2+and Fe2+ ions are 88% and 49%, respectively. The detection limit of the sensor towards Cu2+ and Fe2+ was 1.54 µM and 1.98 µM, respectively. The binding strategy between 3HF and metal ions (Cu2+, Fe2+) and the nature of quenching have been explored with the Benesi-Hildebrand and Stern-Volmer plots, respectively. The FL of 3HF significantly quenched in the presence of Cu2+ ions, and then recovered upon addition of HCl, providing the possibility of constructing a sensitive Cu2+-HCl off-on fluorescent probe. Moreover, the proposed simple, quick response and visual test strip-based chemosensor could be used for the detection of Fe2+ and Cu2+ ions.

Luminescence properties and exciton dynamics of core-multi-shell semiconductor quantum dots leading to QLEDs.

In this study, we grew CdSe core quantum dots (QDs) along with CdSe/ZnS/ZnS and CdSe/CdS/CdS core-multi-shell semiconductor QDs via successive ionic layer adsorption and reaction. The effects of the shell layers on the optical properties and exciton dynamics of the QDs were examined using steady-state and time-resolved measurements together with transient absorption (TA). The photoluminescence (PL) intensity and quantum yield (QY) of the synthesized QDs were enhanced by shell growth. The QY of the QDs increased from 23% to 41% with shell growth due to the decrease in nonradiative recombination sites, which was attributed to surface passivation by the shell layer. The average PL lifetime decreased with shell growth. This effect might be related to the reduction of electron and hole densities on the QD surfaces. The TA spectra show bleaching and photoinduced absorption, corresponding to the state-filling effect and trap states, respectively. The findings are essential for understanding the growth and applications of core-multi-shell QDs.

Wavefunction Engineering of Type-I/Type-II Excitons of CdSe/CdS Core-Shell Quantum Dots.

Nanostructured semiconductors have the unique shape/size-dependent band gap tunability, which has various applications. The quantum confinement effect allows controlling the spatial distribution of the charge carriers in the core-shell quantum dots (QDs). Upon increasing shell thickness (e.g., from 0.25-3.25 nm) of core-shell QDs, the radial distribution function (RDF) of hole shifts towards the shell suggesting the confinement region switched from Type-I to Type-II excitons. As a result, there is a jump in the transition energy towards the higher side (blue shift). However, an intermediate state appeared as pseudo Type II excitons, in which holes are co-localized in the shell as well core whereas electrons are confined in core only, resulting in a dual absorption band (excitation energy), carried out by the analysis of the overlap percentage using the Hartree-Fock method. The findings are a close approximation to the experimental evidences. Thus, the understanding of the motion of e-h in core-shell QDs is essential for photovoltaic, LEDs, etc.

A2B corroles: Fluorescence signaling systems for sensing fluoride ions.

Four free base corroles, 1-4, A2B, (where A = nitrophenyl, and B = pentafluorophenyl, 2, 6-difluoro, 3, 4, 5-trifluoro and 4-carboxymethylphenyl group) have been synthesized, characterized and demonstrated as excellent chemosensor for the detection of fluoride ions selectively in toluene solution. The reported corroles shows highest quantum yield in free base form of porphyrinoid systems so far. All these corrole, 1-4, have the excellent ability to sense fluoride ion. Cumulative effect of static and dynamic factors is responsible for the quenching of fluorescence which indicates the detection of fluoride ion in solution.

Tunable single and double emission semiconductor nanocrystal quantum dots: a multianalyte sensor.

We have prepared stable colloidal CdTe and CdTe/ZnS core-shell quantum dots (QDs) using hot injection chemical route. The developed CdTe QDs emit tunable single and dual photoluminescence (PL) bands, originating from the direct band edge and the surface state of QDs, as evident by the steady-state and time-resolved spectroscopy. The developed CdTe and CdTe/ZnS QDs act as optical sensors for the detection of metal ions (e.g., Fe2+ and Pb2+) in the feed water. The PL quenching in the presence of analytes has been examined by both the steady-state and time-resolved PL spectroscopy. The linear Stern-Volmer (S-V) plots obtained for PL intensity and lifetime as a function of metal ion concentration demonstrates the diffusion-mediated collisional quenching as a dominant mechanism together with the possibility of fluorescence resonance energy transfer. Thus, the prepared core and core-shell QDs which cover a broad spectral range of white light with high quantum yield (QY) are highly sensitive to the detection of metal ions in feed water and are also important for biological applications (Ratnesh and Mehata 2017 Spectrochim. Acta A: Mol. Biomol. Spectro. 179 201-10).

Medicinal Plant Leaf Extract and Pure Flavonoid Mediated Green Synthesis of Silver Nanoparticles and their Enhanced Antibacterial Property.

The rewards of using plants and plant metabolites over other biological methods for nanoparticle synthesis have fascinated researchers to investigate mechanisms of metal ions uptake and bio-reduction by plants. Here, green chemistry were employed for the synthesis of silver nanoparticles (AgNPs) using leaf extracts of Ocimum Sanctum (Tulsi) and its derivative quercetin (flavonoid present in Tulsi) separately as precursors to investigate the role of biomolecules present in Tulsi in the formation of AgNPs from cationic silver under different physicochemical conditions such as pH, temperature, reaction time and reactants concentration. The size, shape, morphology, and stability of resultant AgNPs were investigated by optical spectroscopy (absorption, photoluminescence (PL), PL-lifetime and Fourier transform infrared), X-ray diffraction (XRD) analysis, and transmission electron microscopy (TEM). The enhanced antibacterial activity of AgNPs against E-Coli gram-negative bacterial strains was analyzed based on the zone of inhibition and minimal inhibitory concentration (MIC) indices. The results of different characterization techniques showed that AgNPs synthesized using both leaf extract and neat quercetin separately followed the same optical, morphological, and antibacterial characteristics, demonstrating that biomolecules (quercetin) present in Tulsi are mainly responsible for the reduction of metal ions to metal nanoparticles.

Investigation of biocompatible and protein sensitive highly luminescent quantum dots/nanocrystals of CdSe, CdSe/ZnS and CdSe/CdS.

The size and shape dependent semiconductor quantum dots (0D nanoparticles) with color tunability demonstrating significant influence in a biological system and considered as ideal probes. Here, a non-coordinated colloidal approach was used for the synthesis of CdSe, CdSe/ZnS and CdSe/CdS core-shell quantum dots (QDs) of 3-4nm. The synthesized nanocrystals show a high crystallinity, examined by X-ray diffraction (XRD) and high-resolution electron microscopy (HRTEM). The core-shell semiconductor QDs exhibit stronger photoluminescence (PL) as compared to the core QDs. The strong PL with small full-width half maximum (FWHM) indicates that the prepared QDs have a nearly uniform size distribution and well dispersibility. The quantum yield (QY) of core-shell QDs increases due to the surface passivation. Further, the PL of BSA is quenched strongly by the presence of core-shell QDs and follows the well-known Stern-Volmer (S-V) relation, whereas the PL lifetime does not follow the S-V relation, demonstrating that the observed quenching is predominantly static in nature. Among CdSe core, CdSe/ZnS and CdSe/CdS core-shell QDs, the CdSe/ZnS QDs shows the least cytotoxicity and most biocompatibility. Thus, the prepared core-shell QDs are biocompatible and exhibit strong sensing ability.

Probing Charge-Transfer and Short-Lived Triplet States of a Biosensitive Molecule, 2,6-ANS: Transient Absorption and Time-Resolved Spectroscopy.

We report the existence of a short-lived triplet electronic state of 2,6-ANS (2-anilinonaphthalene-6-sulfonic acid), which, together with nonplanar (NP) and planar [charge-transfer (CT)] states, is produced following photoexcitation; these results are based on nanosecond transient absorption and time-resolved decays. The short-lived triplet state has a lifetime of ∼126 ns and is observed via triplet-triplet (T-T) transitions after exciting 2,6-ANS with a pump laser pulse of 355 nm (probe wavelength range of 360-500 nm). Moreover, the CT state, which is very close to the NP state produced from the locally excited state/NP state, emits active fluorescence with a lifetime of ∼11 ns. The solvent plays a major role in the rotation of the phenylamino group during the conversion of the NP state to the CT state, and vice versa. Intersystem crossing occurs from the CT state. Thus, investigating the triplet state together with the CT/NP states of 2,6-ANS, a commonly used probe for sensing proteins and other biomolecules, is highly relevant and helps reveal its photoexcitation dynamics.

Synthesis, characterization and fluorescence turn-on behavior of new porphyrin analogue: meta-benziporphodimethenes.

New fluorescence switch-on meso-substituted free base meta-benziporphodimethenes were synthesized, characterized via acid catalyzed condensation reaction and metallated with Zn(2+). Their photophysical properties were also studied. The fluorescence spectra analysis demonstrates substituent's independent behaviour on emitting λmax. The average Stokes shift of 33nm was observed. Crystal structure of 8 was obtained and gave expected perturbed geometry.

Experimental and theoretical study of hydroxyquinolines: hydroxyl group position dependent dipole moment and charge-separation in the photoexcited state leading to fluorescence.

Optical absorption and fluorescence (FL) spectra of 2-, 6-, 7-, 8-hydroxyquinolines (2-,6-,7- and 8-HQs) have been measured at room temperature in the wide range of solvents of different polarities, dielectric constant and refractive index. The ground state dipole moment (µ g) and excited state dipole moment (µ e) of 2-, 6-, 7- and 8-HQs were obtained using solvatochromic shift (SS) methods and microscopic solvent polarity parameters (MSPP). Change in the dipole moment (Δµ) between the ground and photo-excited states was estimated from SS and MSPP methods. DFT and TDDFT based theoretical calculations were performed for the ground and excited states dipole moments, and for vertical transitions. A significant enhancement in the excited state dipole moment was observed following photo-excitation. The large value of Δµ clearly indicates to the charge-separation in the photo-excited states, which in turn depends on the position of the hydroxyl group in the ring.