Modulation of fluorescence and phosphorescence of organoboron compounds from ortho-substituted phenolic Schiff bases by structural modification.

Light emission from organoboron compounds of Schiff bases is found to depend strongly on their chemical structure. Two of these compounds (OB1 and OB2), which contain a benzene ring between the Schiff base moieties, exhibit weak fluorescence in methanol, with marked viscosity dependence. Fluorescence lifetimes of these compounds are in picosecond timescale, as determined by femtosecond optical gating (FOG). A significant enhancement in fluorescence intensity and lifetime is observed at 77 K, indicating the operation of an activated nonradiative process. Using fluorescence lifetime imaging microscopy (FLIM), OB1 and OB2 are shown to be potential membrane probes. The third (OB3), which is devoid of this benzene ring, exhibits relatively stronger fluorescence with nanosecond lifetimes at room temperature. No viscosity dependence is observed in this case. The emission spectrum at 77 K is markedly more intense and exhibits an additional red shifted structured feature, which persists for a few seconds. Hence, OB3 seems to have greater promise not only as fluorescent probe but also for light harvesting. The marked improvement of the light emission properties of OB3 compared with OB1 and OB2 is likely to serve as a pointer for the design of Schiff base-derived organoboron luminophores with diverse potential applications.

Recombination dynamics and manybody effect of excitons in large-area monolayer MoS2capped with (111) NiO epitaxial layer.

CVD grown monolayer MoS2films on c-sapphire substrates are vacuum annealed and capped with (111) NiO epitaxial films using pulsed laser deposition technique. Time, energy and polarization resolved optical techniques are used to understand the effect of capping on the excitonic properties of the monolayer MoS2. It has been observed that trion contribution in the photoluminescence (PL) spectra increases after the capping, suggesting an enhancement of electron concentration in the conduction band. This has been attributed to the capping driven reduction of physisorbed air molecules from the sulphur vacancy (VS) sites. Note that the air molecules act as passivating agents for theVS-donors. Low temperature polarization resolved PL spectroscopy and ultrafast pump and probe transient absorption spectroscopy (TAS) show an increase of the biexcitonic population in the system after the encapsulation. The TAS study further reveals longer lifetime for both A and B excitons in capped samples implying a reduction of non-radiative recombination rate of the excitons after the capping. It has also been observed that in the capped samples,K/K'valleys are populated with trions under sufficiently high pump powers. This has been attributed to the lower non-radiative recombination rates of the high energy photoexcited carriers and the faster transfer of either electrons or holes from the high energy pockets to theK/K'valleys. The study further reveals different many-body effects in excitons and trions.

Noninvasive and Contactless Characterization of Electronic Properties at the Semiconductor/Dielectric Interface Using Optical Second-Harmonic Generation.

Optical second-harmonic generation (SHG) is a reliable technique for probing material surface and interface characteristics. Here, we have demonstrated a non-destructive, contactless SHG-based semiconductor/dielectric interface characterization method to measure the conduction band offset and quantitatively evaluate charge densities at the interface in oxide and at the oxide surface. This technique extracts the interface-trapped charge type (donor/acceptor) and qualitatively analyzes the process-induced variation in interface states (Dit), oxide, and oxide surface state density. These qualitative and quantitative analyses provide us with a glimpse into the band bending. The metrology method is validated through a detailed characterization of the Si/HfO2 interface. An optical setup has been developed to monitor the time-dependent second-harmonic generation (TDSHG) from the semiconductor/oxide interface. The temporal characteristics of TDSHG are explained with its relationship to the filling of Dit and spatio-temporal trapping of photoexcited charge in oxide and at the oxide surface. A numerical solver, based on plausible carrier dynamics, is used to model the experimental data and to extract the electronic properties at the Si/HfO2 interface.

Unique Metal-Ligand Interplay in Directing Discrete and Polymeric Derivatives of Isomeric Azole-Carboxylate. Varying Electronic Form, C-C Coupling, and Receptor Feature.

This article dealt with the ruthenium and osmium derivatives of isomeric 1H-indazole-3-carboxylic acid/2H-indazole-3-carboxylic acid (H2L1) and 1H-benzimidazole-2-carboxylic acid (H2L2) along with the π-acidic bpy (bpy = 2,2'-bipyridine) and pap (pap = 2-phenylazopyridine) co-ligands. It thus extended structurally authenticated monomeric ([(bpy)2RuII(HL1-)]ClO4 [1]ClO4, (pap)2RuII(L12-) 2, (bpy)2OsII(L12-) 3, (pap)2OsII(L12-) 4, (bpy)2RuII(L22-) 5, (bpy)2OsII(L22-) 8, and (pap)2OsII(L22-) 9) and dimeric ([(bpy)2RuII(µ-L22-)RuII(bpy)2](ClO4)2 [6](ClO4)2) complexes. It also described modified L2'2- (L2'2- = 2,2'-bisbenzimidazolate)-bridged [(pap)2RuII(µ-L2'2-)RuII(pap)2](ClO4)2 [7](ClO4)2, where L2'2- was developed selectively with the {Ru(pap)2} metal fragment via in situ intermolecular C-C coupling of the two units of decarboxylated benzimidazolate. Moreover, chemical oxidation (OsII to OsIII) of (bpy)2OsII(L12-) 3 (E0 = 0.11 V versus SCE) and (bpy)2OsII(L22-) 8 (E0 = 0.12 V versus SCE) by AgClO4 yielded unprecedented OsIII-AgI derived polymeric {[(bpy)2OsIII-L12--AgI(CH3CN)](ClO4)2}n {[10](ClO4)2}n and dimeric [(bpy)2OsIII-L22--AgI(CH3CN)](ClO4)2 [11](ClO4)2 complexes as a function of trans and cis orientations of the active N2 donor with special reference to the carboxylate O2 of L2-, respectively. Microscopic (FE-SEM, TEM-EDX, and AFM) and DLS experiments suggested a homogeneously dispersed hollow spherical shaped morphology of {[10](ClO4)2}n with an average particle size of 200-400 nm as well as its non-dissociative feature in the aprotic medium. Experimental (structure, spectroscopy, and electrochemistry) and theoretical (DFT/TD-DFT) explorations revealed a redox non-innocent feature of L2- in the present coordination situations and the selective anion sensing (X = F-, CN-, and OAc-) event of [1]ClO4 involving a free NH group at the backface of HL1-, which proceeded via the NH···X hydrogen bonding interaction.

Single-Particle Dynamics of ZnS Shelling Induced Replenishment of Carrier Diffusion for Individual Emission Centers in CuInS2 Quantum Dots.

Insights into blinking and photoactivation of aqueous copper indium sulfide (CIS) quantum dots have been obtained using fluorescence correlation spectroscopy (FCS) and fluorescence lifetime correlation spectroscopy (FLCS). An unusual excitation wavelength-dependence of photoactivation/photocorrosion is manifested in an increase in the initial correlation amplitude G(0) for λex = 532 nm, but a decrease for λex = 405 nm. This has been rationalized in terms of different contributions from surface-assisted recombination in the two cases. Blinking times obtained from the autocorrelation functions (ACFs) of the 100-200 ns lifetime component (core Cu-mediated recombination) are almost unaffected by shelling, but those from the ACF for the 10-30 ns lifetime (surface states) increase significantly. Absence of cross-correlation between the two recombinative states of bare CIS QDs and the emergence of an anticorrelation with the introduction of the ZnS shell are observed, indicating the diffusive nature of the two states for CIS-ZnS. The diffusion is inhibited in bare CIS QDs due to the preponderance of surface states.

Single particle level dynamics of photoactivation and suppression of Auger recombination in aqueous Cu-doped CdS quantum dots.

Cu-doped CdS quantum dots (QDs) have been synthesized in water using 3-mercaptopropionic acid (3-MPA) as the capping agent. They exhibit intense photoluminescence and excellent color tunability, unlike most of the QDs synthesized/dispersed in water so far. Complete characterization of these aqueous doped CdS QDs has been performed for the first time, along with a single particle level elucidation of their exciton dynamics using fluorescence correlation spectroscopy. Photoactivation via dim/dark to bright particle conversion is observed at higher excitation powers. Dispersive blinking kinetics in undoped QDs reflects the involvement of a broad distribution of trap states. A lesser extent of dispersity is observed for doped QDs, in which hole-capture by Cu-defect states predominates. Excitation fluence dependence of the blinking rate highlights the role of Auger recombination in undoped QDs, which is suppressed significantly upon doping, due to disruption of the electron-hole correlation.

Fluorescence monitoring of binding of a Zn (II) complex of a Schiff base with human serum albumin.

Zn (II) complexes of Schiff bases have potential applications in biomedical sciences as imaging agents, cancer therapeutics and diagnostics. Thus, it is important to understand their interaction with carrier proteins, like serum albumins. The present paper focuses on the binding interactions between Human serum albumin (HSA) and Znsalampy, making use of fluorescence spectroscopic techniques at ensemble as well as at single molecular level. An idea about the binding constant is obtained from the quenching of the single Trp (Tryptophan) residue of HSA by Znsalampy. Fluorescence correlation spectroscopy (FCS) has also been used to monitor the protein-ligand binding. The location of Znsalampy in its complex with HSA is determined by competitive binding experiments and molecular docking calculations. The binding constant obtained from the Znsalampy-HSA interaction falls in the ideal range for biological applications and the location is found to be in the proximity of Sudlow's site I. The esterase activity of HSA is retained in the presence of the Znsalampy. Hence, it is concluded that this Znsalampy may be a potential probe and biomarker in biomedical applications.

Interplay of conformational relaxation and hydrogen bond dynamics in the excited states of fluorescent Schiff base anions.

Time resolved fluorescence spectroscopic investigation of four Schiff base anions has established that their excited state dynamics is governed by several solvent properties: polarity, viscosity and hydrogen bond donating ability. With viscous protic solvents like glycerol, fluorescence lifetimes of anions have been found to be markedly longer than those in ethanol, implying that conformational relaxation of molecules plays a key role in their nonradiative relaxation. Surprisingly, the lifetimes in less viscous aprotic solvents, like acetonitrile, are found to be even longer. The only plausible rationalization of this observation is in the light of hydrogen bond-assisted nonradiative phenomena that are operative in protic solvents. This contention draws support from a time evolution of the emission in the red end of the spectrum in low to moderately hydrogen bond donating protic solvents, with regard to an absence of such a rise time in aprotic solvents and strongly hydrogen bond donating solvents, viz., 2,2,2-trifluoroethanol. Rudimentary quantum chemical calculations provide a preliminary idea about the nature of excited state hydrogen bond redistribution involved in the process.

Microscopic Insights into the Mechanism of White Light Generation by Disruptive Interaction between Human Serum Albumin Amyloid Fibrils and Surfactant-AIEgen Nanorods.

Dimethyl-2,5-bis[4-(methoxyphenyl)amino] terephthalate (DBMPT) exhibits aggregation-induced enhancement of emission with Tween 40 and formation of nanorods with strong orange fluorescence. These nanorods disrupt fibrils of human serum albumin and lead to partial refolding of the protein, as monitored by circular dichroism and thioflavin T (ThT) fluorescence. The resultant milieu emits white light, the mechanism of which is explored in this study. It is established that direct excitation of the acceptor plays a significant role, even though Förster resonance energy transfer (FRET) is found to be operative to some extent. A decrease in the fluorescence intensity and lifetime of ThT with progressive addition of DBMPT, which is often used as the sole indicator of FRET, is ascribed to the disruption of the fibrils by the nanorods.

Exciton Dynamics in Colloidal CdS Quantum Dots with Intense and Stokes Shifted Photoluminescence in a Single Decay Channel.

CdS quantum dots (QDs), synthesized by a sol-gel method, exhibit significantly Stokes shifted bright photoluminescence (PL), predominantly from the trap states. Surprisingly, the PL decay at the emission maximum is single-exponential. This is an unusual observation for as-prepared QDs and indicates a narrow distribution in the nature of trap states. A closer look reveals an additional fast component for the decays at shorter emission wavelengths, presumably due to the band edge emission, which remains elusive in the steady-state spectra. Indeed, a significantly narrower and blue-shifted emission band is observed in the decay-associated spectra. The contribution of this component to the steady-state PL intensity is shown to be overwhelmed by that of the significantly stronger trap emission. Exciton dynamics in the quantum dots is elucidated using transient absorption spectra, in which the stimulated emission is observed even at low pump power.

Photoluminescent Silica Nanostructures and Nanohybrids.

The complicated photophysics of wide variety of defects existing in silica (SiO2 ) layer of nanometer thickness determines widespread photoluminescence bands of Si/SiO2 based system as well as SiO2 nanoparticles (NPs) for their applications in photovoltaic and optoelectronic devices. This review attempts to summarize different photophysical processes in pure SiO2 NPs. Moreover, these NPs also act as scaffolds for various guest molecules to perform their specific functions. Guest fluorophore molecules when trapped inside pores of SiO2 NPs exhibit a different photodynamics than free state, which opens up several important applications of hybrid SiO2 NPs in artificial photosynthesis, sensing, biology and optical fiber.

3-aminoquinoline: a turn-on fluorescent probe for preferential solvation in binary solvent mixtures.

3-Aminoquinoline (3AQ) has been used as a fluorescent probe for preferential solvation in hexane-ethanol solvent mixtures. Results of the present experiment have been put into context by comparison with prior observations with 5-aminoquinoline (5AQ) as the probe. 3AQ exhibits a relatively small change of dipole moment (Δµ= 2.2 D) upon photoexcitation, compared to 5AQ (Δµ= 6.1D), which might appear to be a hindrance in the way of its use as a solvation probe. Indeed, the values of parameters like spectral shifts are smaller for the present experiment with 3AQ. At the smallest concentration of alcohol used, its local mole fraction around the probe is significantly lower than in the previous experiments with 5AQ. However, these apparent disadvantages are outweighed by the significant increase in fluorescence intensity and lifetime observed with increasing concentration of ethanol in the solvent mixture, as opposed to the drastic fluorescence quenching that occurs for 5AQ. This is a marked advantage in the use of 3AQ in studies like the present one. The local mole fraction of ethanol and preferential solvation index experienced by 3AQ are in line with those reported for 5AQ. The disadvantage of the smaller magnitude of Δµpersists in the time resolved fluorescence experiments, for solvent mixtures with very low ethanol content. Negligible wavelength dependence of fluorescence transients of 3AQ is observed forxp= 0.002,. However, this effect is outweighed at higher alcohol concentrations, for which nanosecond dynamics of preferential solvation is observed.

Ultraslow Biological Water-Like Dynamics in Waterless Liquid Protein.

Fluorescence correlation spectroscopy and time-dependent fluorescence Stokes shift have been employed to elucidate dynamics in different time scales, ranging from picoseconds to nanoseconds, for human serum albumin, in its native and cationized forms as well as in the self-assembled complex of the cationized protein with the polymer surfactant (PS) glycolic acid ethoxylate lauryl ether. The effect of crowding in this complex, especially in the waterless condition, is of prime importance in this context. Excellent correlation of the dynamics with the structures, obtained by circular dichroism and Fourier transform infrared spectroscopy, has been observed. Slow solvation, associated classically with biological water, has been observed in these systems, even in the waterless condition. This apparently intriguing observation has been rationalized by the relaxation of segments of the protein and the PS in the microenvironment of the fluorescent probe.

Conformational and Solvation Dynamics of an Amyloidogenic Intrinsically Disordered Domain of a Melanosomal Protein.

The conformational plasticity of intrinsically disordered proteins (IDPs) allows them to adopt a range of conformational states that can be important for their biological functions. The driving force for the conformational preference of an IDP emanates from an intricate interplay between chain-chain and chain-solvent interactions. Using ultrafast femtosecond and picosecond time-resolved fluorescence measurements, we characterized the conformational and solvation dynamics around the N- and C-terminal segments of a disordered repeat domain of a melanosomal protein Pmel17 that forms functional amyloid responsible for melanin biosynthesis. Our time-resolved fluorescence anisotropy results revealed slight compaction and slower rotational dynamics around the amyloidogenic C-terminal segment when compared to the proline-rich N-terminal segment of the repeat domain. The compaction of the C-terminal region was also associated with the restrained mobility of hydration water as indicated by our solvation dynamics measurements. Our findings indicate that sequence-dependent chain-solvent interactions govern both the conformational and solvation dynamics that are crucial in directing the conversion of a highly dynamic IDP into an ordered amyloid assembly. Such an interplay of amino acid composition-dependent conformational and solvation dynamics might have important physicochemical consequences in specific water-protein, ion-protein, and protein-protein interactions involved in amyloid formation and phase transitions.

Recent Advances in Small Molecule-Based Intracellular pH Probes.

Intracellular pH plays an important role in many biological and pathological processes. Small-molecule based pH probes are found to be the most effective for pH sensing because of ease of preparation, high sensitivity, and quick response. They have many advantages such as small perturbation to the functions of the target, functional adaptability, cellular component-specific localization, etc. The present review highlights the flurry of recent activity in the development of such probes. The probes are categorized based on the type of fluorophore used like quinoline, coumarin, BODIPY, rhodamine, indolium, naphthalimide, etc., and their analytical performance is discussed.

L-cysteine functionalized graphene quantum dots for sub-ppb detection of As (III).

Here, we report functionalized graphene quantum dots (GQDs) for the optical detection of arsenic at room temperature. GQDs with the fluorescence of three fundamental colors (red, green, and blue) were synthesized and functionally capped with L-cysteine (L-cys) to impart selectively towards As (III) by exploiting the affinity of L-cys towards arsenite. The optical characterization of GQDs was carried out using UV-vis absorption spectroscopy, Fourier transform infrared spectroscopy, and fluorescence spectrometry, and the structural characterizations were performed using transmission electron microscopy. The fluorescence results showed instantaneous quenching in intensity when the GQDs came in contact with As (III) for all test concentrations over a range from 0.025 to 25 ppb, which covers the permissible limit of arsenic in drinking water. The experimental results suggested excellent sensitivity and selectivity towards As (III).

The Role of Hydrogen Bonding in the Preferential Solvation of 5-Aminoquinoline in Binary Solvent Mixtures.

5-Aminoquinoline (5AQ) has been used as a fluorescent probe of preferential solvation (PS) in binary solvent mixtures in which the nonpolar component is diethyl ether and the polar component is protic (methanol) or aprotic (acetonitrile). Hence, the roles of solvent polarity and solute-solvent hydrogen bonding have been delineated. Positive deviations of spectral shifts from a linear dependence on the concentration of the polar component, signifying PS, are markedly more pronounced in case of the protic solvent. Solvation dynamics on a nanosecond time scale mark the formation of the solvation shell around the fluorescent probe. Time-resolved area-normalized emission spectra indicate the occurrence of the continuous solvation of the excited state when the polar component is acetonitrile. In contrast, two distinct states were observed when the polar component was methanol, the second state being the hydrogen bonded one. Translational diffusion is the rate-determining step for formation of the solvation shell. The time constant associated with it has been estimated from rise times observed in fluorescence transients monitored at the red end of the fluorescence spectra and also from the time evolution of the spectral width of time-resolved emission spectra.

From fluorogens to fluorophores by elucidation and suppression of ultrafast excited state processes of a Schiff base.

Strategies have been explored for developing strongly fluorescent species out of a weakly fluorescent Schiff base, 2-(((pyridin-2-ylmethyl)imino)methyl)phenol (salampy). The locally excited enolic state of salampy undergoes an intramolecular proton transfer with a time constant of ca. 200 fs. The emissive cis keto state thus formed decays completely within 50 ps. Its fast decay and miniscule fluorescence quantum yield are attributed to efficient non-radiative channels associated with conformational relaxation. The anionic form, salampy-, has a significantly longer fluorescence lifetime of 800 ps. Its emissive state evolves in tens of picoseconds, from the locally excited state, by solvent and conformational relaxation. Both the neutral and anionic forms have a fluorescence lifetime of about 6 ns at 77 K, a temperature at which all activated nonradiative channels are blocked. This lifetime is similar to that obtained at room temperature, upon rigidification of the anion by complexation with Zn2+. Two such complexes have been studied. The first is binuclear, with acetate bridge between the two Zn2+ ions. The second, with ClO4- as the counterion, is mononuclear with two salampy ligands ligating the metal ion. Unlike a previous report on a different Schiff base, in which the ligands are π-stacked in its dimeric Zn2+ complex, no additional nonradiative deactivation pathway opens up in the Zn complexes of salampy, which are devoid of such stacking. The complex of salampy with Al3+ has an even longer fluorescence lifetime of 9 ns, indicating a greater degree of rigidification and consequent suppression of nonradiative processes.

Intense photoluminescence from Cu-doped CdSe nanotetrapods triggered by ultrafast hole capture.

Brightly photoluminescent Cu-doped CdSe nanotetrapods (NTPs) have been prepared by a modified hot injection method. Their photoluminescence (PL) has a quantum yield of 38% and decays slowly over a few microseconds, while the PL in undoped NTPs has a rather small quantum yield of 1.7% and decays predominantly in tens of picoseconds, with a minor component in the nanosecond time regime. PL spectra of doped NTPs are significantly Stokes shifted compared to the band edge (BE). Efficient PL quenching by a hole scavenger confirms the oxidation state of +I for the dopant ion and establishes hole capture by this ion to be the primary event that leads to the Stokes shifted PL. A fast decay of the photoinduced absorption band, along with a similar decay in PL, observed in a femtosecond optical gating experiment, yields a time constant of about a picosecond for the hole capture from the valence band (VB) by Cu+. The remarkably long PL lifetime in the doped NTPs is ascribed to the decrease in the overlap between the wavefunctions of the photogenerated electrons and the captured hole. Hot carrier relaxation processes, triggered by excitation at energies greater than the band gap, leave their signature in a rise time of few hundreds of femtoseconds, in the ground state bleach recovery kinetics. Hence, a complete picture of exciton dynamics in the doped NTPs has been obtained using ultrafast spectroscopic techniques working in tandem.