Switching of photoinduced proton transfer from one six-membered hydrogen-bonded ring to other: a molecule of hydrazine and pH sensor.

The present study describes photophysical properties of 3-(benzo[d]oxazol-2-yl)-5-bromo-2-hydroxybenzaldehyde (HBOB) and (E)-2-(benzo[d]oxazol-2-yl)-4-bromo-6-(hydrazonomethyl)phenol (HBON) molecules with asymmetric two-way proton transfer sites. The purpose of this study is to know the direction of ESIPT out of the two-way proton transfer pathways in these molecules in both the solid and solution state. The steady state and time-resolved spectral behaviour of HBOB and HBON and a comparison of the spectral features with the two distinct control compounds 2-(benzo[d]oxazol-2-yl)-4-bromophenol (HBO) and (E)-4-bromo-2-(hydrazonomethyl)phenol (HBN) having single 6-membered hydrogen bonded network reveal that HBOB undergoes imine-amine photoisomerisation by proton transfer towards the oxazole side and HBON undergoes towards the hydrazone side with characteristic Stokes' shifted emission. Proton transfer forms with the red shifted emission of these molecules shows fast decay than the locally excited state. In the solid state, extremely high fluorescence intensity was observed, following a similar type of ESIPT pattern. Calculated ground (S0) and excited state (S1) energy barriers for the PT process obtained using density functional theory (DFT) and time-dependent density functional theory (TD-DFT) corroborate the unidirectional excited state intramolecular proton transfer (ESIPT) process for HBOB and HBON, and the theoretical spectral features validate our experimental absorption and emission spectra well. Interestingly, the unique unidirectional ESIPT behaviour of HBOB was utilised to detect hydrazine both in solution and solid phases. On the other hand, HBON was found to be a good fluorescence pH sensor with a ratiometric color change from yellow to green in acidic and basic media.

Dual-Channel Imine-Amine Photoisomerization in a Benzoimidazole and Benzothiazole Coupled System: Photophysics and Applications.

A molecule, namely 2-(1H-benzo[d]imidazol-2-yl)-6-(benzo[d]thiazol-2-yl)-4-bromophenol (BIBTB), having a two-way proton transfer unit of thiazole and imidazole moieties was synthesized and characterized by NMR, electrospray ionization mass spectrometry (ESI-MS), and single-crystal diffraction studies. Steady state and time-resolved spectral studies of BIBTB support excited state intramolecular proton transfer (ESIPT), causing imine-amine tautomerization through a two-way 6-membered H-bonded ring, where the N atoms of benzothiazole and the benzoimidazole unit are involved as proton acceptor sites. Interestingly, in a nonpolar and moderately polar solvent, photoisomerization in BIBTB is found to be favored toward the thiazole ring, whereas in a highly polar solvent, it is favored toward the imidazole ring. A spectral comparison of BIBTB with judicially designed molecules 2-(benzo[d]thiazol-2-yl)-4-bromophenol (HBT) and 2-(1H-benzo[d]imidazol-2-yl)-4-bromophenol (BIB) supports these inferences. Theoretical calculation using the Density Functional Theory (DFT) at CAM-B3LYP/6-311+G(d,p) level supports the existence of two low-energy 6-membered hydrogen-bonded planar conformers in the ground state in the gas phase and in solvents of different dielectrics. The potential energy curves (PECs) calculated along the proton transfer (PT) coordinate are found to have a high energy barrier in the ground state and to be barrierless or have a low energy barrier in the excited state for both the forms. The calculated vertical excitation and the emission energy from the relaxed excited and PT states show good correlation with the experimental spectral data. Aggregation of BIBTB in water with red shifted emission was established from X-ray single-crystal structure analysis, solid state emission, and Dynamic Light Scattering (DLS) measurement. The molecule BIBTB also acts as a fluorescence probe for sensing the explosive picric acid in the subnano scale and can be used to determine the proportion of water in dimethyl sulfoxide (DMSO) solvent.

Investigating the Photophysical Aspects of a Naphthalene-Based Excited-State Proton Transfer Dye 1-(1H-Benzo[d]imidazol-2-yl)naphthalen-2-ol: pH-Dependent Modulation of Photodynamics.

The steady state and time-resolved photophysical behavior of a proton transfer dye 1-(1H-benzo[d]imidazol-2-yl)naphthalen-2-ol (H-BINO) was investigated. The excited state intramolecular proton transfer (ESIPT) reaction in H-BINO is predominant in nonpolar solutions (toluene and DCM) with a lifetime of ∼1.0 ns. However, in polar media (DMF and MeOH), the excited state photodynamics is characterized by a complex equilibrium of emission from the locally excited state (0.1-2.3 ns), the phototautomer (0.5-1.2 ns), and the anionic emission (2.1-5.4 ns). In the solid state, emission from the various aggregated states dictates the photobehavior. Interestingly, the photodynamics in aqueous solution changes starkly as a function of pH with the anionic (2.1 ns) and phototautomeric (0.5-1.0 ns) emissions guiding the photodynamics as the pH of the medium increases. Optimized structural parameters at the proton donor and acceptor sites for the enol and keto forms and the calculated potential energy curve along the proton transfer coordinate at the density functional theory (DFT) level with the B3LYP/6-311G++(d,p) theory support a favorable and barrierless ESIPT process. The current results will surely boost the ongoing research on small molecule emissive materials.

Interrogating the nature of aggregates formed in a model azine based ESIPT coupled AIE active probe: stark differences in photodynamics in the solid state and aggregates in water.

A novel Schiff base 4-bromo-2-((E)-((E)-(1-(naphthalen-2-yl)ethylidene)hydrazono)methyl)phenol (BNHMP) was synthesized and characterized by NMR, ESI-MS, FTIR and single crystal X-ray diffraction studies. In the solution phase, BNHMP shows prominent emission from the keto-form, a consequence of excited state intramolecular proton transfer (ESIPT). The quantum yield and excited state lifetime decrease in polar solvent THF compared to relatively non-polar solvent DCM. Interestingly, in aqueous solution (pH 7.0), the quantum yield along with the excited state lifetime undergoes tremendous increment. Dynamic light scattering experiments and FESEM reveal the formation of aggregates in water as reflected by the increased hydrodynamic radius of BNHMP in water. Hence, aqueous phase studies revealed BNHMP to be an AIE active probe. On the other hand, BNHMP shows huge emission intensity in the solid state. Interestingly, the emission decay behavior of BNHMP changes upon excitation, as BNHMP shows very broad absorption in the solid state. Upon excitation at 360 nm, a triexponential decay pattern is found, which changes to a biexponential one upon excitation at 450 nm. Meticulous analysis of the fluorescence lifetimes led to the assignment of J and H aggregates coexisting in the solid state with the former dominating the photodynamics. A judicious comparison of the lifetime behavior in the solid state to that in water leads to the conclusion that BNHMP undergoes AIE by the formation of J and H aggregates to an equal extent, a phenomenon starkly different from the solid-state scenario. The current results hold significance as this is among a few reports where such comprehensive spectrodynamic dissection has been performed for an ESIPT-AIE active Schiff base in solution as well as in the solid phase, thereby giving a holistic vision of the nature and fate of aggregation occurring in such azine based systems and subsequently advancing the understanding of such systems in terms of their photo behavior.

Structural isomerism induces pH dependent AIE-coupled ESIPT: an in-depth spectroscopic exploration with application in amine vapor sensing.

A novel excited state intramolecular proton transfer probe 3-(benzo[d]thiazol-2-yl)-4-hydroxy-5-methoxybenzaldehyde (3BTHMB) was synthesized and characterized using NMR, ESIMS and single crystal diffraction studies. The steady state and time resolved studies using the time correlated single photon counting (TCSPC) technique revealed that 3BTHMB shows ESIPT reaction with a time constant of 0.10-0.15 ns and longer local emission and anion emissions of time constants 0.5-2.0 ns and 3.0-4.0 ns, respectively, that co-exist in polar solution. In a polar protic solution like methanol, the ESIPT process is damped. Interestingly, 3BTHMB shows aggregation induced emission (AIE) solely in an acidic environment, evidenced by the enhanced quantum yield of emission (∼35%) in acidic solution as well as a long lifetime component of 7.4 ns that corresponds to the lifetime in the solid state. The AIE phenomenon was explored using the DLS technique where enhancement of the hydrodynamic radius in an acidic medium was observed. The judicious positioning of the formyl group in 3BTHMB gives the mentioned probe to show AIE in an acidic medium, as opposed to its previously reported structural isomer BTHMB, which showed no AIE phenomenon as well as its parent molecule 2-(benzo[d]thiazol-2-yl)-6-methoxyphenol (TMP), which showed AIE in neutral pH. The AIE property of 3BTHMB was exploited by successful and rapid detection of amine vapor in the solid state, qualitative ratiometric detection of aqueous pH, by observing the colour change under UV light in acidic (yellow-green) and basic to neutral (blue) medium. The above results pave the way for multiutility fluorescent probes for environmental purposes along with a deep understanding of the underlying photophysical processes which bestow the probes with such outstanding utilities.

Fluorescence detection of Al3+ ion in aqueous medium and live cell imaging by ESIPT probe (E)-N'-(5-bromo-2-hydroxybenzylidene)-4-hydroxybenzohydrazide.

The molecule (E)-N'-(5-bromo-2-hydroxybenzylidene)-4-hydroxybenzohydrazide (BHHB) has been synthesized and its photophysical properties have been investigated by using steady state absorption, emission and time resolved emission spectroscopy. The molecule shows excited state intramolecular proton transfer (ESIPT) process with characteristics large Stoke shifted emission. Fluorescence enhancement of BHHB only in presence of Al3+ ion is used as selective aluminium ion sensor in the sub-nano molar scale in aqueous solution. BHHB-Al3+ ion complex can penetrate through live Hepatocellular Carcinoma (HepG2) cell membranes and is capable for imaging of nucleus of live cells by fluorescence confocal microscopy.

Proton transfer inhibited charge transfer in a coumarinyl chalcone: Hassle free detection of chloroform vapor in alcohol medium and in neat solution.

The photophysical aspects of a synthesized coumarinyl chalcone derivative 3-((2E, 4E)-5-(4-(dimethylamino) phenyl) penta-2, 4-dienoyl)-4-hydroxy-2H-chromen-2-one (DPPHC) were explored. DPPHC shows excited state intramolecular proton transfer (ESIPT) suppressed excited state intramolecular charge transfer (ESICT) as evidenced from steady state and time resolved spectroscopic analysis. Interestingly, DPPHC behaves as a strong red emitter solely in chloroform and dichloromethane semi-polar solvents exclusively. Using this property, on-spot detection of these two solvents was achieved in paper strips coated with DPPHC as well as in spiked alcohol samples by emission ratiometry change.

Effect of temperature and salts on niosome-bound anti-cancer drug along with disruptive influence of cyclodextrins.

Encapsulation of a persuasive anticancer drug (Sanguinarine, SGR) within microheterogeneous environment of niosome has been investigated. Utilizing steady-state and time-resolved spectroscopic methods the effects of extrinsically added salts and temperature on the photophysical properties of niosome-bound bio-active drug have been explored thoroughly. The prototropic (alkanolamine⇌ iminium) equilibrium of SGR is found to be preferentially favored toward the neutral form inside the hydrophobic interior of niosome. With addition of salts and increment of temperature the reverse tendency of stabilization of the cationic species is observed which can be explained on the basis of degree of water penetration of water molecules to the hydration layer of niosome. Furthermore, drug sequestration has been investigated via disruption of niosome applying cyclodextrins (CDs). Exploration of the effect of CDs (ß-CD and γ-CD) on the niosome aids to have knowledge of the effect of CDs on cell membrane. In addition, the differential rotational relaxation behavior of SGR at various environmental circumstances has been observed to substantiate with other experimental results.

Sphingomyelin-induced structural modification of native human hemoglobin and its chemically and thermally disrupted secondary structure: A photophysical exploration.

Sphingomyelin-induced structural modification of Human Hemoglobin (Hb) has been investigated in its native and unfolded conformers that are partially denatured in presence of ∼ 4 M urea, completely denatured in ∼ 8 M urea and thermally disrupted (at ∼ 65 °C) state. The absorption studies unveil ground state complexation between Hb and SM. From steady-state fluorescence and quenching studies alteration of the micro-environments around Trp residues of Hb in above mentioned different cases has been determined. Moreover, lesser exposure of Trp residues to SM in thermally disrupted Hb can be accounted for the exceptionally interesting outcomes in other experiments. The alterations in the time-resolved decay profiles of native Hb, partially and totally chemically denatured as well as thermally disrupted Hb with gradual addition of SM also affirm the amendment of the proteinous micro-environment surrounding Trp residues in a view of FRET between Trp residues and heme group. Wavelength-sensitive emission spectral studies reveal that the protein shows red edge effect in its different conformations in presence and absence of SM. Interestingly, the wavelength-responsive time-resolved study at a constant excitation wavelength demonstrates that with addition of lipid the increment of the average fluorescence lifetime signifies a considerable modulation of solvation dynamics of the fluorescent Trp residues in their excited state being greatest in case of thermally disrupted Hb. Nevertheless, the loss of α-helicity of Hb at its various conformers with addition of SM has been portrayed thoroughly by means of far-UV CD spectral studies in a view of disruption of secondary structure of the protein.

How is the interaction of a chloride channel blocker with phospholipids influenced by divalent metal ions? Effect of unsaturation on the lipid side chain.

The present study reveals the effect of various divalent ions (Ca2+, Mg2+and Zn2+) on the binding interaction of a prospective chloride channel blocker, 9-methylanthroate (9MA), with liposome membranes, namely, dimyristoylphosphatidylcholine (DMPC) and 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine (POPC). The liposome membranes DMPC and POPC differ in the unsaturation of the side-chain. The drug (9MA) is found to experience a greater degree of partitioning into the POPC lipid bilayer (containing unsaturated side-chain) in comparison to DMPC (containing saturated side-chain). The stronger 9MA-POPC binding interaction is found to be only nominally perturbed by the presence of metal salts. On the contrary, the 9MA-DMPC binding interaction is found to be significantly perturbed by the presence of metal salts and is manifested on the environment-responsive spectroscopic properties of the drug. The steady-state and picosecond-resolved fluorescence spectroscopic results reveal the effect of metal ions on DMPC bilayer to follow the trend Ca2+ < Mg2+ < Zn2+. This is also quantified by evaluating the partition coefficient of the drug into DMPC lipid in the presence of various divalent ions which is found to follow the same sequence. The degree of penetration of these cations has been rationalized on the basis of adsorption of cations on DMPC headgroup region resulting in dehydration of the headgroup along with shrinking of it.

Imine-Amine Tautomerism vs Keto-Enol Tautomerism: Acceptor Basicity Dominates Over Acceptor Electronegativity in the ESIPT Process through a Six-Membered Intramolecular H-Bonded Network.

Photophysical properties of a synthesized asymmetric two-way proton transfer molecule 3-(benzo[d]thiazol-2-yl)-2-hydroxy-5-methoxybenzaldehyde (BTHMB) were studied in detail. BTHMB could undergo excited-state intramolecular proton transfer (ESIPT) involving a 6-membered H-bonded network toward either the N or the O atom present in the molecule as proton acceptors. From tedious spectroscopic dissection, however, it was established that ESIPT was driven exclusively toward the N center over the O center in the solid state as well as in the solution phase. The aforementioned deduction was based on spectral comparison with judicially designed molecules 2-hydroxy-5-methoxybenzaldehyde (HMB) and 2-(benzo[d]thiazol-2-yl)-4-methoxyphenol (BTMP). In solution, the coexistence of the anionic and neutral forms of BTHMB in basic solvents dimethylsulfoxide (DMSO) and dimethylformamide (DMF) enables BTHMB to behave as a white light emitter. Thus, apart from establishment of directionality of ESIPT in double ESIPT probes, the current work deserves special merit as BTHMB can be considered as a standard in future designs involving red light and solvent-specific white light emitters.

Photophysical Properties of an Azine-Linked Pyrene-Cinnamaldehyde Hybrid: Evidence of Solvent-Dependent Charge-Transfer-Coupled Excimer Emission.

We report the photophysical properties of a synthetic asymmetric azine-based compound (17Z,18E)-4'-((E)-3-phenylallylidene)-1'-(dimethylamino)-1-((pyren-8-yl)methylene)hydrazine (PYNC). The molecule PYNC shows an appreciable red shift in the emission maximum in a wide range of solvents. In water, PYNC shows the characteristic feature of excimer formation exclusively. However, in all other solvents, the excimer band is present alongside the charge transfer emission band. The assignment of charge transfer and excimer bands has been established by various steady-state emission spectral data. PYNC, owing to this novel excimer-coupled charge transfer phenomenon, can be a potential probe for studying various supramolecular assemblies of biological interest.

Evaluating the merit of a diethylamino coumarin-derived thiosemicarbazone as an intramolecular charge transfer probe: efficient Zn(ii) mediated emission swing from green to yellow.

We report the synthesis and photophysical properties of a coumarin based probe (1E)-1-(1-(7-(diethylamino)-2-oxo-2H-chromen-3-yl) ethylidene) thiosemicarbazide (DIDOT). DIDOT shows a polarity dependent change in the emission maxima in the solution phase. This is explained by the increased dipole moment in the excited state by an intramolecular charge transfer (ICT) process. DIDOT can successfully detect Zn(ii) in aqueous methanol by a shift in the charge transfer emission maxima from approximately 506 to approximately 535 nm. This shift led to a change in the color of the emission from green to yellow under UV-light. The mechanism of Zn(ii) detection has been delineated using electrospray ionization-mass spectrometry (ESI-MS), Fourier-transform infrared spectroscopy (FTIR) and fluorescence time resolved studies coupled with theoretical calculations. The increment in the charge transfer in the Zn(ii) complex of DIDOT over the bare receptor as a consequence of conformational locking was determined to be the underlying cause of the cation detection phenomenon. The limit of detection and binding constant values of DIDOT towards Zn(ii) were approximately 3 × 10-8 M and 2.35 × 105 M-1 respectively. Finally, the practical utility of DIDOT has been demonstrated by successful detection and quantification of Zn(ii) in spiked water samples.

Comparative Photophysical Study of Differently Substituted Cinnamaldehyde-Based Chalcones: From Intramolecular Charge Transfer to Fluorogenic Solvent Selectivity.

We synthesized three cinnamaldehyde-based chalcone derivatives, (2E,4E)-1-(2-hydroxyphenyl)-5-phenylpenta-2,4-dien-1-one (HPD), (2E,4E)-5-(4-(dimethylamino)phenyl)-1-phenylpenta-2,4-dien-1-one (DPPD), and (2E,4E)-5-(4-(dimethylamino)phenyl)-1-(2-hydroxyphenyl)penta-2,4-dien-1-one (DPHPD). The molecule HPD was totally nonfluorescent. Exclusion of a phenolic -OH moiety from HPD along with the introduction of a dimethylamino moiety in DPPD resulted in excellent excited-state charge-transfer properties in the solution phase. Interestingly, introduction of phenolic -OH and dimethylamino moieties in DPHPD resulted in solvent selectivity in the excited state. DPHDP behaved as a strong fluorophore only in carbonyl- or thiocarbonyl-containing solvents, such as dimethylsulfoxide (DMSO), dimethylformamide (DMF) and dimethylacetamide (DMAC) and showed a prominent red color under UV light. However, no emission was observed in similar carbonylated solvents, such as acetone or formamide, or in viscous medium, such as glycerol. The difference in solvent response was probed by various spectroscopic techniques and analyzed using the crystal structure of the three chalcones along with theoretical calculations. The practical utility of DPHPD was explored by detecting the percentage of water in DMSO solvent.

Unsaturation of the phospholipid side-chain influences its interaction with cyclodextrins: A spectroscopic exploration using a phenazinium dye.

The interaction of a cationic photosensitizer Safranin-O with liposome membranes having similar surface charge (negative) but differing in the presence of saturation on the lipid side-chain has been studied. To this end, dimyristoyl-l-R-phosphatidylglycerol (DMPG) and 1,2-dioleoyl-sn-glycero-3-phospho-(1'-rac-glycerol) (DOPG) phospholipids were employed to prepare small unilamellar vesicles. The dye is found to bind in the headgroup region of both the liposome membranes with significantly higher affinity to DOPG lipid containing unsaturated side chain. The effects of various cyclodextrins (CDs) on the stability of the probe-bound liposome membranes have also been investigated using steady-state and picosecond-resolved fluorescence as well as dynamic light scattering techniques. The modulations of the fluorescence properties of the lipid-bound dye were exploited to rationalize the membrane destabilization following interaction with the cyclodextrins. Experimental results reveal the selective interaction of DMPG membrane with CDs leading to rupture of the integrated structure of the liposome units accompanying release of the bound probe to the bulk aqueous phase. On the contrary, no discernible interaction of the CDs was observed with DOPG liposome membrane. Our results also show the differential extents of interaction of various CDs (α-CD, ß-CD, methyl-ß-CD, and γ-CD) with DMPG leading to varying degrees of release of the bound-dye molecule.

Host sensitized lanthanide photoluminescence from post-synthetically modified semiconductor nanoparticles depends on reactant identity.

This work investigates the photoluminescence characteristics where cadmium selenide (CdSe) and zinc sulfide (ZnS) nanoparticles are treated post-synthetically by the trivalent lanthanide cations (Ln3+) [Ln = Pr, Nd, Sm, Eu, Tb, Dy, Ho, Er, Tm, Yb] separately to form either CdSe/Ln or ZnS/Ln nanoparticles. Host sensitized Ln3+ emission was found to be present only in CdSe/Eu, CdSe/Tb, ZnS/Eu, ZnS/Tb and ZnS/Yb nanoparticles. In all the cases tuning of emission of the nanoparticles has been observed, irrespective of the presence or absence of host sensitization. The elemental compositions of CdSe and ZnS nanoparticles upon post-synthetic treatment show a remarkable difference. Incorporation of lanthanides in the nanoparticles is evident with significant alteration in the anionic content, and complete cation exchange of either Cd2+ or Zn2+ by Ln3+ has not been detected; as evaluated from energy dispersive X-ray spectroscopy. Further evaluation on this comes from considering thermodynamic parameters of inter cation interaction. In cases where the host sensitized Ln3+ emission have been observed, luminescence lifetime measurements reveal significant protection of Ln3+ in the nanoparticles. Noticeable difference in photophysical properties for a given Ln3+ has been realized in the two hosts. The photophysical observations have been rationalized using (i) charge trapping mediated host sensitized dopant emission, (ii) autoionization of excited electrons, and (iii) environment induced photoluminescence quenching. The post-synthetic modification discussed in the present work provides an easy and less synthetically demanding room temperature based protocol to avail lanthanide incorporated (doped) semiconductor nanoparticles that can potentially use the unique emission properties of the lanthanide cations.

CHEF-Affected Fluorogenic Nanomolar Detection of Al3+ by an Anthranilic Acid-Naphthalene Hybrid: Cell Imaging and Crystal Structure.

We report the synthesis of a novel hydrazine-bridged anthranilic acid-naphthalene conjugate (E)-2-(benzamido)-N'-((2-hydroxynaphthalen-1-yl) methylene) benzohydrazide (BBHAN) and its crystal structure. BBHAN can detect Al3+ by a sharp increment in fluorescence intensity (∼40 times) in aqueous methanolic medium. The limit of detection of BBHAN towards Al3+ is 1.68 × 10-9 M, and the former undergoes a 2:1 binding with Al3+ with a high binding constant of ∼1.15 × 1011 M2-. BBHAN detects Al3+ by the well-known mechanism of chelation-enhanced fluorescence (CHEF), established by fluorescence time-resolved measurement. The mode of interaction between BBHAN and Al3+ has been explored by 1H NMR and electrospray ionization mass spectrometry techniques. Paper strips coated with BBHAN can detect Al3+ under UV light observed through the naked eye. Lastly, BBHAN can detect Al3+ in MDA-MB-468 cells.

Interaction of a cationic amphiphile with monomeric and polymeric electrolytes: From morphological transition to associative phase separation.

The discrete effects of a series of structurally divergent monomeric viz. Sodium Chloride (NaCl), Tetra-butyl Ammonium Chloride (TBAC) and Sodium Benzoate (NaBz) and polymeric viz. Sodium Polystyrene Sulfonate (NaPSS) electrolytes towards the morphological and/or aggregation properties of Octadecyl-trimethyl Ammonium Bromide (OTAB) micelles have been quantified spectroscopically by means of the modulations of the absorption and emission spectral properties of an extrinsic anthracene-based probe 9-methyl anthroate (9-MA) within the concerned media. Further corroboration of the spectroscopic results was acquired from the non-invasive dynamic light scattering technique. The qualitatively similar mode of action of all the monomeric salts has been explained on the basis of the archetypal Israelachvili model whereas the corresponding extent of the morphological transition of the micelles, which is found to follow the order NaBz > NaCl > TBAC, has been explained invoking the co-sphere overlap model. Conversely, to explain the aggregation behaviour of the micelles in the presence of the polymeric electrolyte, a two-step model has been formulated. According to this model, at the low concentration regime, the polymeric salt is found to only neutralize the surface charge of the micelles inducing micellar growth; whereas further increment in the concentration of the polymer assists the hydrophobic association between the micelles leading to the formation of larger aggregates, eventually causing a phase separation.

Binding interaction of phenazinium-based cationic photosensitizers with human hemoglobin: Exploring the effects of pH and chemical structure.

The present study demonstrates a spectroscopic study on the interaction of two phenazinium-based cationic photosensitizers, namely, phenosafranin (PSF) and safranin-O (SO) with human hemoglobin (Hb) with particular emphasis on exploring the effects of pH and chemical structures of the dye molecules on the binding phenomenon. The protein (Hb) undergoes complex conformational transitions depending on the medium pH. The dye molecules exhibit a prominent fluorescence quenching following interaction with Hb under various experimental conditions (pH 3.5, 7.4, and 9.0). Our combined steady-state and time-resolved spectroscopic results provide persuasive evidence for static quenching mechanism showing that the dye:Hb interaction proceeds through ground-state complex formation. The meticulous investigations on the pH-dependence of the interaction of the dye molecules with the protein reveal a relatively strong binding of PSF as well as SO with Hb at physiological pH and alkaline pH, while the binding is weaker at acidic pH at which Hb predominantly exists as monomeric units. The binding constant for PSF:Hb interaction is K(PSF:Hb) = (1.09 ±â€¯0.06) × 106 M-1 and that of SO:Hb interaction is K(SO:Hb) = (1.34 ±â€¯0.07) × 105 M-1 at pH 7.4. However, at pH 3.5, the binding constant values are K(PSF:Hb) = (3.58 ±â€¯0.18) × 104 M-1 and K(SO:Hb) = (4.29 ±â€¯0.22) × 104 M-1 and at pH 9.0, the values are K(PSF:Hb) = (8.08 ±â€¯0.40) × 104 M-1 and K(SO:Hb) = (5.07 ±â€¯0.25) × 104 M-1. This depicts a much stronger binding interaction of the dyes with the native Hb at pH 7.4 compared to those at pH 3.5 and 9.0. Our results also unveil the effect of chemical structures of the dyes on the interaction phenomenon in the sense that the binding constant of PSF with Hb is found to be higher than that of SO at pH 7.4 and pH 9.0. The present study also focuses on exploring such important aspects of the interaction phenomena as the effect of binding of the dyes on the protein conformation by circular dichroism spectroscopy and probable binding location of the dyes within the protein scaffolds via micropolarity measurements and molecular docking simulation.

Employing a hydrazine linked asymmetric double naphthalene hybrid for efficient naked eye detection of F-: Crystal structure with real application for F.

An asymmetric hydrazide, (12E, 13E)-2-((naphthalen-1-yl) methylene)-1-(1-(2-hydroxynaphthalen-6-yl) ethylidene) hydrazine (abbreviated as AH) is synthesized and characterized by standard techniques and crystal structure of AH has been obtained. The naked eye detection of F- in aqueous acetonitrile (acetonitrile: water=7:3/v:v) by AH has been investigated by UV-Visible titration and in presence of other anions, the limit of detection being 1.31×10-6(M). The mechanism of F- sensing has been explored by 1H NMR titration. AH undergoes hydrogen bonding with F- followed by deprotonation. The practical utility of AH has been explored by successful test kit response and color change in toothpaste solution.