Tri-armed Schiff base fluorescent sensor for the rapid recognition of Zn(II): application in live cell imaging, test strips and TLC.

Various metal ions exist in nature and human beings and play limitless vital roles in both the atmosphere and biology. A fundamental and useful aspect is the qualitative and quantitative assessment of Zn(II) at concentration levels as low as parts per billion (ppb). Thus, the design and development of novel fluorescent turn-on receptors have gained significant interest because of their potential for use in live cell imaging to detect biologically relevant metal ions with high selectivity and sensitivity. The present research illustrates the design and synthesis of a novel fluorescent sensor [(1,3,5-triazine-2,4,6-triyl)tris(hydrazine-2-yl-1-ylidene)tris(methaneylylidene)]tris(2,4-di-tert-butylphenol) (THDBP) for the selective and sensitive probing of Zn(II). The sensor exhibited a fluorescence turn-on mechanism upon treatment with Zn(II) ions at λemi. 503 nm in aq. acetonitrile. The formation of a 1 : 3 complex between THDBP and Zn(II) is confirmed from the Job plot and ESI-MS spectrum. The evaluated limit of detection (LOD) and association constant (Ka) of the sensor THDBP for Zn(II) were found to be 1.03 × 10-10 M and 2.33 × 108 M-1, respectively. Further research demonstrates the practical application of the sensor for the detection of Zn(II) ions in live cells. The sensing ability of the sensor THDBP was also explored through inexpensive test strips and TLC sheets.

A pyrene-induced PET-based chemosensor for biologically important Zn(II) ions: application in test strips and live cell imaging studies.

Cation and anion sensing is vital owing to their universal dispersion in ecosystems and biological functions. It has been shown that fluorescent receptors based on organic platforms are efficient for detecting a number of ions and have many advantages such as low cost, superior sensitivity and simplicity in installation. This study demonstrates the design and synthesis of a novel receptor (E)-3-[(3,5-di-tert-butyl-2-hydroxybenzylidene)amino]-2-(pyren-1-yl)-2,3-dihydroquinazolin-4(1H)-one (DTQ) for the rapid recognition of Zn(II) ions. DTQ exhibited a significant fluorometric "turn-on" characteristic towards Zn(II) at λmax 444 nm in aqueous acetonitrile by inhibiting the photo-induced electron transfer (PET) and -CN- process. The ESI-MS analysis and Job's plot experimental results confirmed stoichiometric 1 : 1 complex formation between DTQ and Zn(II). Fluorometric investigations revealed the detection limit and association constant of DTQ towards Zn(II), which were found to be 13.4 nM and 1.47 × 105 M-1, respectively. DTQ was employed to sense Zn(II) on low-cost test strips. The present research findings imply that DTQ can function as an effective sensor for Zn(II).

Design and Synthesis of Novel Fluorescent 2-(aryloxy)-3-(4,5-diaryl)-1H-imidazol-2-yl)quinolines: Solvatochromic, DFT, TD-DFT Studies, COX-1 and COX-2 Inhibition and Antioxidant Properties.

The present work focuses on the synthesis of novel heterocycles 2-(aryloxy)-3-(4,5-diaryl-1H-imidazol-2-yl)quinolines (6k-v) by an effective condensation reaction. These molecules exhibited fluorescent properties and hence for the proper understanding of their optical behavior and quantum yields, solvatochromic studies have been carried out. Further, frontier molecular orbitals, molecular electrostatic potential (MEP), and geometrical structure optimization have been investigated using the B3LYP/6-311G ++ (d, p) method. The energy gap between the HOMO, LUMO of the optical and energy band gap is determined by DFT and UV-visible spectra for TD-DFT studies are done. The screening of these compounds for in vitro COX-1 and COX-2 inhibition and DPPH free radical scavenging ability assays produced promising results. The binding interactions of these molecules against the COX-2 enzyme (PDB: 5IKR) were validated by docking studies.

Effect of Hydroxyl Group on Photo-Physical Properties and Dipole Moments of Fluorescent Dyes: An Experimental and Computational Approach.

In this work, structurally similar, (E)-N'-(2-hydroxybenzylidene)-3,5-di-tert-butyl-2-hydroxybenzohydrazide (A) and (E)-N'-(2-4-dihydroxybenzylidene)-3,5-di-tert-butyl-2-hydroxybenzohydrazide (A-OH) dyes dissolved in general solvents have been studied to explore photo-physical properties, employing solvatochromic shift method, thereby determining their dipole moments in the ground (µg) and excited (µe) states. The molecule A shows a bathochromic shift of fluorescence emission maxima in aprotic solvents whereas a hypsochromic shift in protic solvents. Interestingly, A-OH follows a hypsochromic shift in both protic and aprotic solvents with increasing solvent polarity. The effect of hydroxyl substituent on UV-Visible absorption, fluorescence emission, and dipole moment of the titled organic molecules was explained. Theoretical methods such as Bilot-Kawski method for determination of µg and µe and Bakshiev, Kawski-Chamma-Viallet, Lippert-Mataga equations for µe, and Reichardt method for the difference between µg and µe were employed. It is observed that µe is higher than that of µg for both the molecules, and interestingly, upon substituting an additional hydroxyl group the value of µg has increased while µe is decreased. The DFT calculations have been performed to support experimental results by employing DFT/B3LYP/6-311G + (d) and TD-DFT/B3LYP/6-311G + (d) method using Gaussian09 software. The electrophilic and nucleophilic sites on the molecules were studied with the help of MEP. The NBO analysis results show that the interaction N24 (σ) → C22-O23 (π*) is found to be stronger in both the molecules with energy 68.90 kJ/mol and the effect of hydroxyl group is also discussed on the basis of HOMO and LUMO.

Rotational Diffusion Dynamics of Fluorescein Derivatives in Binary Mixtures of Solvents: An Experimental and Computational Study.

With a view to understand the nature of solute solvent interactions, rotational reorientation times (τr) of three medium sized dipolar laser dyes viz., dichlorofluorescein (DCF), sodium fluorescein (SF) and kiton red (KR) in two binary mixtures namely, aqueous-DMSO and aqueous-1-propanol have been determined employing steady state fluorescence depolarization technique. The experimental results are analyzed in the light of SED hydrodynamic and of Gierer and Wirtz (GW) and Dote, Kivelson and Schwartz (DKS) quasihydrodynamic models. Rotational reorientation times (τr) are plotted as function of viscosity (η) on the binary solvent mixtures. An interesting hook shaped profile is observed in both the binary mixtures of solvents that is likely to shed light on solute-solvent interactions. Further, theoretical study has been carried out using Gaussian 09 software. The optimized geometry, HOMO-LUMO, energy gap and molecular electron potential map (MEPM) were extracted from DFT/B3LYP 6-311g(d) basis set. The hyper conjugation or intra-molecular delocalization was estimated from NBO analysis. Strong interactions were observed between nO33→σ*C31, πN38→σ*C12 and πO32→π*(C31- O33) with E(2) energies of 203.58, 121.89 and 39.92 kJ/mol for SF, KR and DCF.

Nanoparticle surface energy transfer (NSET) in ferroelectric liquid crystal-metallic-silver nanoparticle composites: Effect of dopant concentration on NSET parameters.

In the recent past, the resonance energy transfer studies using metallic nanoparticles has become a matter of quintessence in modern technology, which considerably extends its applications in probing specific biological and chemical processes. In the present study, metallic-silver nanoparticles of 2-4 nm (diameter) capped with hexanethiol ligand are developed and dispersed in ferroelectric liquid crystal (FLC). The morphology of nanoparticles was characterized using HR-TEM and SEM techniques. Furthermore, a systematic study of energy transfer between the host FLC material (as donors) and metallic-silver nanoparticles (as acceptors) has been explored employing steady state and time resolved fluorescence spectroscopic techniques. The nanoparticle based surface energy transfer (NSET) parameters viz., transfer efficiency, transfer rate, and proximity distance between donor and acceptor, have been determined for NSET couples (FLC material-metallic-silver nanoparticle) composites. It is observed that various NSET parameters and quenching efficiency follow a linear dependence on the concentration of metallic-silver nanoparticles in host FLC material. The nonradiative energy transfer and superquenching effect were analyzed with the help of Stern-Volmer plots. The impact of present study about superquenching effect of the silver nanoparticles can be used for sensing applications that require high degree sensitivity.

A combined solvatochromic shift and TDDFT study probing solute-solvent interactions of blue fluorescent Alexa Fluor 350 dye: Evaluation of ground and excited state dipole moments.

Herein we report, the effect of solvents on absorption and fluorescence spectra of Alexa Fluor-350 labelled fluorescent dye examined both experimentally and computationally. The steady state absorption and fluorescence measurements are carried out in a series of solvents to explore their solvatochromism and to determine its dipole moments. To this end, different empirical solvatochromic models like Bilot-Kawaski, Lippert-Mataga, Bakhshiev, Kawaski-Chamma-Viallet and Reichardt models are assessed against Alexa Fluor 350 dye to determine the singlet excited and ground state dipole moments. Computational studies were carried out to optimize ground and excited geometries using density functional theory (DFT) and time dependent density functional theory (TD-DFT), respectively, in vacuum. Additionally, this study encompasses estimation of the electronic transition energies from the ground to first excited state of dye employing TD-DFT. Further, TD-DFT has been combined with integral equation formalism of the polarizable continuum model (IEF-PCM) to calculate various solute-solvent interaction potentials which are then compared with experimental values. The highest occupied molecular orbital energy (HOMO), lowest unoccupied molecular orbital energy (LUMO), the energy gap, chemical hardness (η), softness (σ), electronegativity (χ) and chemical potential (µ) were estimated. Mulliken atomic charge, natural population analysis (NPA) and molecular electrostatic potential (MEP) map are correlated using density functional theory. The experimentally obtained ground and excited state dipole moments are compared with the ones obtained from computational and the results are discussed. NBO analysis is carried out to investigate the intramolecular charge transfer interactions and stabilization energy within the studied molecule.

Synthesis, Photophysical and Computational Study of Novel Coumarin-based Organic Dyes.

A series of novel coumarin pyrazoline moieties combined with tetrazoles, 3-(1-phenyl-4-(1H-tetrazol-5-yl)-1H-pyrazol-3-yl)-2H-chromen-2-one, 6-chloro-3-(1-phenyl-4-(1H-tetrazol-5-yl)-1H-pyrazol-3-yl)-2H-chromen-2-one, 6-bromo-3-(1-phenyl-4-(1H-tetrazol-5-yl)-1H-pyrazol-3-yl)-2H-chromen-2-one and 6-bromo-3-(1-(4-bromophenyl)-4-(1H-tetrazol-5-yl)-1H pyrazol-3-yl)-2H-chromen-2-one7(a-d), were designed and synthesized. Single crystal X-ray diffraction and their interactions were studied by Hirshfeld surface analysis. Thermal stabilities and electrochemical properties of these compounds were examined from differential scanning calorimetry (DSC), thermogravimetric (TGA) and cyclic voltammetric (CV) studies. Their spectroscopic properties were analyzed in various alcohols and general solvents by UV-Vis absorption, fluorescence and time-resolved spectroscopy. In addition, the ground and excited state electronic properties were investigated using density functional theory (DFT). The calculated highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) and energy band gap (Eg ) values have revealed the effect of substitution of halogens. The substitution has equally affected the ground and excited states of 7(a-d) compounds. The solvatochromism on absorption, fluorescence spectra and fluorescence lifetimes of these compounds was investigated. All these results showed the chromen-2-one of pyrazoline tetrazole derivatives could play an important role in photonic and electronic devices.

Steady State and Time Resolved Spectroscopic Study of CdSe and CdSe/ZnS QDs:FRET Approach.

This article highlights some physical studies on the relaxation dynamics and Förster resonance energy transfer (FRET) of semiconductor quantum dots (QDs) to proximal dye molecule and the way these phenomena change with core to core-shell QD is discussed. Efforts to understand the optical and carrier relaxation dynamics of CdSe and CdSe/ZnS QDs are made by using absorption, steady-state fluorescence and time-resolved fluorescence (TCSPC) techniques. Steady-state as well as time-resolved fluorescence measurements were employed to evaluate the QD PL quenching induced by the proximal Rhodamine 101 dye molecule and to examine the influence of deep trap states on energy transfer efficiency. The FRET parameters such as spectral overlap, Förster distance, intermolecular distance for each donor-acceptor pair are determined and variation of these parameters from core to core-shell QD is discussed.

Rotational Diffusion of a New Large Non Polar Dye Molecule in Alkanes.

Rotational reorientation times of a newly synthesized 2,5-bis(phenylethynyl)1,4-bis(dodecyloxy) benzene (DDPE) are experimentally determined in series of n-alkanes by employing steady state and time resolved fluorescence depolarization technique with a view to understand rotational dynamics of large non-polar solute molecule in non-polar solvents and few general solvents of different sizes and varying viscosity. It is observed that rotational reorientation times vary linearly as function of viscosity. The hydrodynamic stick condition describes the experimental results at low viscosities while the results tend to deviate significantly from it at higher viscosities. This is attributed to the possibility of long chains in solvents hosting a variety of chain defects (end-gauche, double-gauche, all-trans, kink, etc.) thereby reducing the effective length of the molecule, leading to a slightly reduced friction. The experimental results are compared with the predictions of Stokes-Einstein-Debye (SED) hydrodynamic theory as well as the quasi-hydrodynamic theories of Gierer-Wirtz (GW) and Dote-Kivelson-Shwartz (DKS). The predictions from these theories underestimate τr in the solvents employed in the study.

UV laser radiation alters the embryonic protein profile of adrenal-kidney-gonadal complex and gonadal differentiation in the lizard, Calotes Versicolor.

PURPOSE: To examine the impact of ultraviolet (UV) laser radiation on the embryos of Calotes versicolor in terms of its effects on the protein profile of the adrenal-kidney-gonadal complex (AKG), sex determination and differentiation, embryonic development and hatching synchrony. MATERIALS AND METHODS: The eggs of C. versicolor, during thermo-sensitive period (TSP), were exposed to third harmonic laser pulses at 355 nm from a Q-switched Nd:YAG laser for 180 sec. Subsequent to the exposure they were incubated at the male-producing temperature (MPT) of 25.5 ± 0.5°C. The AKG of hatchlings was subjected to protein analysis by sodium dodecyl sulphate-polyacrylamide gel electrophoresis (SDS-PAGE) and to histology. RESULTS: The UV laser radiation altered the expression of the protein banding pattern in the AKG complex of hatchlings and it also affected the gonadal sex differentiation. SDS-PAGE of AKG of one-day-old hatchlings revealed a total of nine protein bands in the control group whereas UV laser irradiated hatchlings expressed a total of seven protein bands only one of which had the same Rf as a control band. The UV laser treated hatchlings have an ovotestes kind of gonad exhibiting a tendency towards femaleness instead of the typical testes. CONCLUSIONS: It is inferred that 355 nm UV laser radiation during TSP induces changes in the expression of proteins as well as their secretions. UV laser radiation had an impact on the gonadal differentiation pathway but no morphological anomalies were noticed.

Rotational diffusion of coumarins: a dielectric friction study.

The rotational diffusion of three probes: coumarin 522B (C522B), coumarin 307 (C307) and coumarin 138 (C138) with nearly identical size was studied at room temperature employing steady-state and time-resolved fluorescence anisotropy techniques in series of alcohols and alkanes. Experimental observations indicate faster rotation of C138 compared to the other two dyes in alcohols and a faster rotation of C522B than C307 in alkanes. The dielectric friction theories of Nee-Zwanzig (NZ) and van der Zwan-Hynes (ZH) were employed to estimate the friction experienced by the probes in alcohols, in addition to the mechanical friction calculated using Stokes-Einstein-Debye (SED) hydrodynamic with slip boundary condition and Dote-Kivelson-Schwartz (DKS) quasihydrodynamic theories. The observed reorientation times for the three probes do not follow the trend predicted by dielectric friction theories of NZ and ZH. The dipole moments determined from solvatochromic techniques were found to be different for the three probes.

Triacontanol and jasmonic acid differentially modulate the lipid organization as evidenced by the fluorescent probe behavior and 31P nuclear magnetic resonance shifts in model membranes.

Fluorescence resonance energy transfer (FRET), time-resolved fluorescence and anisotropy decays were determined in large unilamellar vesicles (LUVs) of egg phosphatidylcholine with the FRET pair N-(7-nitrobenz-2-oxa-1,3-diazol-4-yl)-1,2-dipalmitoyl-sn-glycero-3-phospho-ethanolamine as donor and lissamine rhodamine B 1,2-dipalmitoyl-sn-glycero-3-phosphoethanolamine as acceptor, using 2-ps pulses from a Ti:sapphire laser on LUVs with incorporated plant growth regulators: triacontanol (TRIA) and jasmonic acid (JA). FRET efficiency, energy transfer rate, rotation correlation time, microviscosity, and diffusion coefficient of lateral diffusion of lipids were calculated from these results. It was observed that TRIA and JA differentially modulated all parameters studied. The effect of JA in such modulations was always partially reversed by TRIA. Also, the generalized polarization of laurdan fluorescence indicated that JA enhances the degree of hydration in lipid bilayers to a larger extent than does TRIA. Solid-state (31)P magic-angle spinning nuclear magnetic resonance spectra of LUVs showed two chemical shifts, at 0.009 and -11.988 ppm, at low temperatures (20 degrees C), while at increasing temperatures (20-60 degrees C) only one (at -11.988 ppm) was prominent and the other (0.009 ppm) gradually became obscure. However, LUVs with TRIA exhibited only one of the shifts at 0.353 ppm even at lower temperatures and JA did not affect the chemical shifts.