Shift Of Emission Maximum Research Articles

Investigation on luminescence enhancement and decay characteristics of long afterglow nanophosphors for dark-vision display applications

Long afterglow SrAl2O4:Eu2+,Dy3+ nanophosphors were synthesized via a facile but effectual auto-combustion technique followed by post-annealing treatment at elevated temperatures. The influence of various fuels during synthesis and thereafter improvement in the luminescence decay characteristics under various illuminant irradiations of long afterglow nanophosphors have been reported. Extensive studies on structural, morphological and luminescent properties of the as-synthesized afterglow nanophosphors have been presented. Powder X-ray diffraction studies confirm the presence of high-purity, single-phase monoclinic nanophosphors. HRTEM investigations confirm the formation of nanophosphors of particle size less than 50nm. Photoluminescence emission is attributed to the characteristic d–f transition (4f65d1→4f7) of Eu2+ ions and was positioned at 512nm. As-synthesized nanophosphors exhibit considerable confinement effects resulting into blue shift in emission maxima as compared to their bulk counterparts. The mechanism underlined for long afterglow has been discussed using trapping–detrapping model. The nanophosphor being multifunctional finds many interesting applications including dark-vision display, energy storage, fingerprint detection, in vivo and in vitro biological staining, etc.

Interactions of amelogenin with phospholipids.

Amelogenin protein has the potential to interact with other enamel matrix proteins, mineral, and cell surfaces. We investigated the interactions of recombinant amelogenin rP172 with small unilamellar vesicles as model membranes, toward the goal of understanding the mechanisms of amelogenin-cell interactions during amelogenesis. Dynamic light scattering (DLS), fluorescence spectroscopy, circular dichroism (CD), and nuclear magnetic resonance (NMR) were used. In the presence of phospholipid vesicles, a blue shift in the Trp fluorescence emission maxima of rP172 was observed (∼334 nm) and the Trp residues of rP172 were inaccessible to the aqueous quencher acrylamide. DLS studies indicated complexation of rP172 and phospholipids, although the possibility of fusion of phospholipids following amelogenin addition cannot be ruled out. NMR and CD studies revealed a disorder-order transition of rP172 in a model membrane environment. Strong fluorescence resonance energy transfer from Trp in rP172 to DNS-bound-phospholipid was observed, and fluorescence polarization studies indicated that rP172 interacted with the hydrophobic core region of model membranes. Our data suggest that amelogenin has ability to interact with phospholipids and that such interactions may play key roles in enamel biomineralization as well as reported amelogenin signaling activities.

Optimising conditions for the growth of nanocrystalline ZnS thin films from acidic chemical baths

The growth of nanocrystalline zinc sulfide thin films onto glass substrates by chemical bath deposition has been optimized at acidic pH. Powder X-ray diffraction (p-XRD) confirms the deposition of sphalerite, the cubic phase of ZnS. The crystallite size calculated by Scherrer equation was found to be 4.0nm. Scanning Electron Microscopy (SEM) show clusters of spherical nanoparticles uniformly distributed over the surface of the glass substrates. Energy Dispersive X-ray (EDX) analysis of the deposited thin films show the zinc to sulfur ratio close to 1:1. The observed band gap (3.78eV) of the deposited thin films is higher than that reported for cubic phase of bulk ZnS (3.54eV) as expected due to nano-size crystallites. Binding energies calculated by X-ray Photoelectron Spectroscopy (XPS) confirm the material as ZnS and the photoluminescence measurements show the blue shift in emission maximum.

Estimation of ground and excited state dipole moments of synthesized coumarin derivative [N-(2-oxo-2H-chromen-4-yl)imino]triphenyl-phosphorane

Electronic absorption and fluorescence spectra of coumarin derivative [N-(2-oxo-2H-chromen-4-yl)imino] triphenyl phosphorane have been recorded at room temperature in wide range of solvents of different polarities. The absorption maximum remains almost unchanged with the increase in solvent polarity, whereas, a red shift in fluorescence emission maximum was observed. Synthesized compound [N-(2-oxo-2H-chromen-4-yl)imino] triphenyl phosphorane was characterized by 1H and 13C NMR, and FT-IR spectral studies. The ground and excited state dipole moments of molecule were obtained from Bakhshiev's and Bilot–Kawski's equations by means of the solvatochromic shift method. Very high value of dipole moment is observed for excited state as compared to ground state value and this is attributed to more polar excited state of the molecule. Numerical calculations are performed using B3LYP/6-31G+(d) and B3LYP/6-31G(d) level of theory for ground state in Gaussian 03. Studies in different solvents are also done using the CPCM method and UA0 radii with the same level of theory. A critical analysis between the values of dipole moment in gas phase and various solvents is also carried out for ground state.

Stimuli-sensitive breathing of Cucurbit[7]uril cavity: monitoring through the environment responsive fluorescence of 1'-hydroxy-2'-acetonaphthone (HAN).

In this work, we have focused on the supramolecular interactions of a water-soluble host Cucurbit[7]uril (CB[7]) with an excited state intramolecular proton transfer (ESIPT) probe 1'-hydroxy-2'-acetonaphthone (HAN) through steady-state and time-resolved fluorescence measurements. In water HAN is almost nonfluorescent in nature with a very low fluorescence quantum yield (Φ = 0.009). With gradual addition of CB[7] absorption maximum of HAN is red-shifted (292 cm(-1)) and hence confirming the formation of an inclusion complex in the ground state between HAN and CB[7]. Due to this complexation CB[7] offers a hydrophobic microenvironment to the HAN which is completely different from that of homogeneous water. Upon encapsulation into the nanocavity of CB[7], HAN exhibits a 20-fold increase in fluorescence intensity along with a 36 nm (1618 cm(-1)) hypsochromic shift in emission maxima. This hypsochromic shift is an indication about the modulation of excited state photophysical behavior of HAN due to the formation of HAN-CB[7] inclusion complex. Moreover, huge partition coefficient of HAN from water to CB[7] along with a∼ 12-fold increase in fluorescence lifetime confirm the favorable interaction between HAN and CB[7]. We have also observed the stimuli-sensitive (temperature and cationic stimuli) breathing of CB[7] cavity i.e., in the presence of different additives the portals of CB[7] open up to release HAN in water and take up the additives. Time-resolved anisotropy measurements further indicate about the probable location of HAN inside the CB[7]. The observation of a 1.7 ns component in the presence of CB[7] signifies the highly restricted rotational motion of HAN inside the cavity of CB[7] corroborates our finding.

Influence of Three Anionic Gemini Surfactants with Different Chain Lengths on the Optical Properties of a Cationic Polyfluorene

The effects of three sulfonate gemini surfactants with different hydrophobic chain lengths (8, 10, and 12 carbon atoms) on the optical properties of a fluorene-based conjugated cationic polymer poly{[9,9-bis(6'-N,N,N-trimethylammonium)hexyl]-fluorene-phenylene} bromide (PFP) dissolved in DMSO-water solutions (4% v/v) or water were investigated, respectively. When surfactants with PFP dissolved in DMSO-water solutions (4% v/v) are incubated, a decrease in photoluminescence (PL) intensity and a red shift of emission maxima are obtained at low surfactant concentrations. Intriguingly, two different Stern-Volmer constants (KSV1 and KSV2) are obtained and analyzed in detail for the first time. Further increase in the surfactant concentration enhanced PL intensity, and distinct blue shifts of both absorption and emission maxima are observed. Importantly, the turning point between the emission quenching and enhancement is closely related to the hydrophobic chain length: the longer the chain length, the earlier the turning point appears. Simulation studies provide strong evidence to explain these phenomena. Surface tension measurements show more insight on the interactions between PFP and surfactant. On the contrary, no emission quenching is obtained at low surfactant concentrations for PFP dissolved in water.

Elucidating the mode of action of urea on mammalian serum albumins and protective effect of sodium dodecyl sulfate

The effect of sodium dodecyl sulfate (SDS) on human, bovine, porcine, rabbit and sheep serum albumins were investigated at pH 3.5 by using various spectroscopic techniques like circular dichroism (CD), intrinsic fluorescence and dynamic light scattering (DLS). In the presence of 4.0mM SDS the secondary structure of all the albumins were not affected as measured by CD but fluorescence spectra revealed 8.0nm blue shift in emission maxima. We further checked the stability of albumins in the absence and presence of 4.0mM SDS by urea and temperature at pH 3.5. In the absence of SDS, urea starts unfolding both secondary as well as tertiary structural elements of the all the albumins at ∼2.0M urea but in the presence of 4.0mM SDS, urea was unable to unfold even up to 9.0M. The albumins were thermally less stable at pH 3.5 with decrease in Tm but in the presence of 4.0mM SDS, the Tm was increased. From this study, it was concluded that SDS is showing a protective effect against urea as well as thermal denaturation of albumins. This behavior may be due to electrostatic as well as the hydrophobic interaction of SDS with albumins. Further, we have proposed the mechanism of action of urea. It was found that urea interacted with proteins directly when proteins are in charged form. Indirect interaction may be taking place when the environment is more hydrophobic.

The synthesis and fluorescence properties of novel 1,8-naphthalimide derivatives

Three novel 1,8-naphthalimide derivatives containing indole and indoline were synthesized through Fischer indole synthesis, reduction, and alkylation. Two reference dyes with similar structures to the three novel dyes were also prepared. The absorption and fluorescence spectra of these dyes in a variety of solvents were investigated. In addition, fluorescence of these dyes in solid state was also measured. Intramolecular charge transfer was confirmed within the new dyes by virtue of shifts in emission maximum with increasing solvent polarity. Intermolecular close contacts and lateral intermolecular hydrogen bonding interactions between neighboring columns lead to fluorescence wavelength shift, short in the solution and long in the solid state.

Interaction of anticancer drug mitoxantrone with DNA hexamer sequence d-(CTCGAG)2 by absorption, fluorescence and circular dichroism spectroscopy

The interaction of mitoxantrone with d-(CTCGAG)2 has been studied by absorption, fluorescence and circular dichroism (CD) spectroscopy. The hypochromism and quenching of fluorescence showed that about four mitoxantrone molecules may be binding externally to DNA hexamer sequence at high drug to nucleic (D/N) acid duplex ratios (28.0–1.1). At lower D/N ratios (1.0–0.2), a red shift in absorption maxima at 610 and 660nm by 15 and 20nm, respectively and a red shift in emission maxima by 11nm accompanied by increase in absorbance and emission has been observed. The equilibrium constant for binding at low (1.0–0.2) and high (28.0–1.1) D/N ratios is 1.8×105M−1 and 1.38×106M−1, respectively. The CD spectra show change in intensity of bands accompanied by appearance of induced bands at 325nm and 650–700nm. The 251nm band shows blue shift at D/N ratio of 0.25 and 0.5. The binding isotherms show stoichiometry of 0.25 and 0.5 mitoxantrone molecules binding per duplex. The results suggest stacking of aromatic chromophore of mitoxantrone with terminal base pair of DNA strand forming a sandwiched structure of mitoxantrone between four and two duplex molecules. These investigations are relevant to the formation of ternary complex with topoisomerase enzyme and hence an understanding of anti tumor action of mitoxantrone.

Salicylaldehyde Phenylhydrazone: A New Highly Selective Fluorescent Lead (II) Probe

The fluorescence intensity of salicylaldehyde phenylhydrazone (L), in 1:1 (v/v) CH3OH:H2O was enhanced by ca. 100 times with a blue shift in emission maximum, on interaction with Pb(2+) ion. No enhancement in fluorescent intensity of L was observed on interaction with metal ions - Na(+), K(+), Ca(2+), Cu(2+), Ni(2+), Zn(2+), Cd(2+) and Hg(2+). This signal transduction was found to occur via photoinduced electron transfer (PET) mechanism. A 1:1 complexation between Pb(2+) and L with log β = 7.86 has been proved from fluorescent and UV/Visible spectroscopic data. The detection limit of Pb(2+) was calculated to be 6.3 × 10(-7) M.

Fluorescence emission properties of C60 nanoparticles

Fluorescence properties of C60 nanoparticles produced by sonication in pyridine have been systematically investigated. The fluorescence emission of C60 is dependent on the particle size. A red shift of emission maximum from 424 to 468nm originates from the average size increase caused by strong interaction among C60 molecules in nanoparticles. In addition, it is also confirmed that the emergence of broad fluorescence emission band in the 550–570nm region is ascribed to C60 nanoparticles aggregation.

Solvatochromatic shift of absorption and fluorescence spectra of 6-methoxyquinoline: Estimation of ground and excited state dipole moments

Electronic absorption and fluorescence spectra of protonated 6-methoxyquinoline (6MQ+) and neutral 6-methoxyquinoline (6MQ) have been recorded at room temperature in wide range of solvents of different polarities. The absorption maximum remains almost unchanged with the increase in solvent polarity, whereas a red shift in fluorescence emission maximum was observed. The ground-state dipole moment and the first excited singlet state dipole moment of 6MQ+ and 6MQ were obtained from Bakhshiev's and Bilot–Kawski's equations by means of solvatochromic shift method. High values of dipole moment are observed for excited state as compared to the corresponding ground state dipole moment values of 6MQ+ and 6MQ and this is attributed to the more polar excited states of 6MQ+ and 6MQ.

The effect of lysozyme amyloid fibrils on cytochrome c–lipid interactions

Protein polymerization into ordered fibrillar structures (amyloid fibrils) is currently associated with a range of pathological conditions. Recent studies clearly indicate that amyloid cytotoxicity is provoked by a continuum of cross-β-sheet aggregates including mature fibrils. In view of the possible diversity of cytotoxicity mechanisms, the present study addressed the question of whether protein conversion into amyloid fibrils can modify its competitive membrane adsorption behavior. Using a combination of resonance energy transfer, dynamic light scattering and fluorescence quenching techniques, the competitive binding of either monomeric or polymerized lysozyme, and cytochrome c to the model lipid membranes composed of phosphatidylcholine mixtures with varying proportions of phosphatidylglycerol, phosphatidylserine or cardiolipin has been studied. The ability of fibrillar lysozyme to induce dissociation of cytochrome c from the membrane binding sites proved to be markedly stronger than that of its monomeric counterpart, with desorption process displaying cooperativity features upon increasing the charge of lipid bilayer. The decreased efficiency of tryptophan fluorescence quenching by acrylamide and short-wavelength shift of emission maximum observed upon membrane binding of lysozyme fibrils were rationalized in terms of fluorophore transfer into interfacial bilayer region. It is hypothesized that electrostatic interactions play predominant role in determining the lipid-associating and competitive abilities of fibrillar lysozyme.

A ratiometric fluorescent probe for assessing mitochondrial phospholipid peroxidation within living cells

Mitochondrial oxidative damage contributes to a wide range of pathologies, and lipid peroxidation of the mitochondrial inner membrane is a major component of this disruption. However, despite its importance, there are no methods to assess mitochondrial lipid peroxidation within cells specifically. To address this unmet need we have developed a ratiometric, fluorescent, mitochondria-targeted lipid peroxidation probe, MitoPerOx. This compound is derived from the C11-BODIPY581/591 probe, which contains a boron dipyromethane difluoride (BODIPY) fluorophore conjugated via a dienyl link to a phenyl group. In response to lipid peroxidation the fluorescence emission maximum shifts from ∼590 to ∼520nm. To target this probe to the matrix-facing surface of the mitochondrial inner membrane we attached a triphenylphosphonium lipophilic cation, which leads to its selective uptake into mitochondria in cells, driven by the mitochondrial membrane potential. Here we report on the development and characterization of MitoPerOx. We found that MitoPerOx was taken up very rapidly into mitochondria within cells, where it responded to changes in mitochondrial lipid peroxidation that could be measured by fluorimetry, confocal microscopy, and epifluorescence live cell imaging. Importantly, the peroxidation-sensitive change in fluorescence at 520nm relative to that at 590nm enabled the use of the probe as a ratiometric fluorescent probe, greatly facilitating assessment of mitochondrial lipid peroxidation in cells.

Ground and excited state dipole moments of quinine sulfate dication: Solvatochromic shift of absorption and fluorescence spectra

Electronic absorption and fluorescence spectra of quinine sulfate dication (QSD) have been recorded at room temperature in a wide range of solvents of different polarities. The absorption maximum remains almost unchanged with the increase in solvent polarity, whereas a red shift in fluorescence emission maximum was observed. The ground-state dipole moment of QSD was obtained from quantum mechanical calculations and the first excited singlet state dipole moment of QSD was obtained from Bakhshiev's and Bilot–Kawski's equations by means of solvatochromic shift method. Very high value of dipole moment is observed for excited state as compared to the corresponding ground state value and this is attributed to the more polar excited state of QSD. Compared to the dipole moment of quinine sulfate, both the ground and excited state dipole moments of QSD are lower.

Microwave-Assisted Green Synthesis of Small Gold Nanoparticles Using Aqueous Garlic (Allium sativum) Extract: Their Application as Antibiotic Carriers

ABSTRACT This article establishes a rapid, microwave-assisted green synthetic method for the production of gold nanoparticles (AuNPs) using garlic extract as a reducing and stabilizing agent and seeks their application as antibiotic carriers. The appearance, crystalline nature, size, and shape of nanoparticles are understood by different physical techniques like UV-vis spectroscopy, transmission electron microscopy, and X-ray diffraction. The AuNPs of size varying from 1.8 ± 0.85 nm to 23.2 ± 4.1 nm were synthesized successfully by varying the power of microwave irradiation. Further, AuNPs (of size 23.2 ± 4.1 nm) were functionalized with ciprofloxacin (cfH), a broad-spectrum antibiotic. A red shift in absorption and emission maxima with decreased intensity suggested successful binding of cfH to AuNPs. AuNPs-conjugated cfH (cfH@AuNPs) were found to have better antibacterial activities in terms of zone of inhibition compared to free cfH against the tested bacterial strains.

Abstracts of the 17th International Symposium on Bioluminescence and Chemiluminescence ‐ (ISBC 2012)

WARNING : The light-emitting molecular structures responsible for the chemiluminescence and fluorescence phenomena are not necessarily the same!

Luminescent Di‐ and Polynuclear Organometallic Gold(I)–Metal (Au2, {Au2Ag}n and {Au2Cu}n) Compounds Containing Bidentate Phosphanes as Active Antimicrobial Agents

The reaction of new dinuclear gold(I) organometallic complexes containing mesityl ligands and bridging bidentate phosphanes [Au(2)(mes)(2)(μ-LL)] (LL=dppe: 1,2-bis(diphenylphosphano)ethane 1a, and water-soluble dppy: 1,2-bis(di-3-pyridylphosphano)ethane 1b) with Ag(+) and Cu(+) lead to the formation of a family of heterometallic clusters with mesityl bridging ligands of the general formula [Au(2)M(μ-mes)(2) (μ-LL)][A] (M=Ag, A=ClO(4)(-), LL=dppe 2a, dppy 2b; M=Ag, A=SO(3)CF(3)(-), LL=dppe 3a, dppy 3b; M=Cu, A=PF(6)(-), LL=dppe 4a, dppy 4b). The new compounds were characterized by different spectroscopic techniques and mass spectrometry The crystal structures of [Au(2)(mes)(2)(μ-dppy)] (1b) and [Au(2)Ag(μ-mes)(2)(μ-dppe)][SO(3)CF(3)] (3a) were determined by a single-crystal X-ray diffraction study. 3a in solid state is not a cyclic trinuclear Au(2)Ag derivative but it gives an open polymeric structure instead, with the {Au(2)(μ-dppe)} fragments "linked" by {Ag(μ-mes)(2)} units. The very short distances of 2.7559(6) Å (Au-Ag) and 2.9229(8) Å (Au-Au) are indicative of gold-silver (metallophilic) and aurophilic interactions. A systematic study of their luminescence properties revealed that all compounds are brightly luminescent in solid state, at room temperature (RT) and at 77 K, or in frozen DMSO solutions with lifetimes in the microsecond range and probably due to the self-aggregation of [Au(2)M(μ-mes)(2)(μ-LL)](+) units (M=Ag or Cu; LL=dppe or dppy) into an extended chain structure, through Au-Au and/or Au-M metallophilic interactions, as that observed for 3a. In solid state the heterometallic Au(2)M complexes with dppe (2a-4a) show a shift of emission maxima (from ca. 430 to the range of 520-540 nm) as compared to the parent dinuclear organometallic product 1a while the complexes with dppy (2b-4b) display a more moderate shift (505 for 1b to a max of 563 nm for 4b). More importantly, compound [Au(2)Ag(μ-mes)(2)(μ-dppy)]ClO(4) (2b) resulted luminescent in diluted DMSO solution at room temperature. Previously reported compound [Au(2)Cl(2)(μ-LL)] (LL dppy 5b) was also studied for comparative purposes. The antimicrobial activity of 1-5 and Ag[A] (A=ClO(4)(-), SO(3)CF(3)(-)) against gram-positive and gram-negative bacteria and yeast was evaluated. Most tested compounds displayed moderate to high antibacterial activity while heteronuclear Au(2)M derivatives with dppe (2a-4a) were the more active (minimum inhibitory concentration 10 to 1 μg mL(-1)). Compounds containing silver were ten times more active to gram-negative bacteria than the parent dinuclear compound 1a or silver salts. Au(2)Ag compounds with dppy (2b, 3b) were also potent against fungi.

Novel Benzanthrone Aminoderivatives for Membrane Studies

The potential of novel benzanthrone aminoderivatives to trace the changes in physicochemical properties of lipid bilayer has been evaluated. Binding of the dyes to the lipid bilayers composed of zwitterionic phospholipid phosphatidylcholine (PC) and its mixtures with anionic phospholipid cardiolipin (CL) and cholesterol (Chol) was followed by significant quantum yield increase with small blue shift of emission maximum. Analysis of partition coefficients of the dyes under study showed that all aminobenzanthrones possess high lipid-associating ability. The dyes A8 and AM2 proved to be sensitive to the variations in membrane chemical composition responding to the changes in bilayer hydration induced by CL and Chol.

Construction of soft porous crystal with silole derivative: strategy of framework design, multiple structural transformability and mechanofluorochromism

Novel fluorescent organic soft porous crystals have been designed and prepared based on a multi-substituted silole bearing 1-phenyl-2,2-dicyanoethene moieties (molecule 8). 8 exhibited a series of emission colors, ranging from yellow to dark red with an over 70 nm shift of emission maximum. Molecule 8 also showed the ability to reversibly switch between different solid states, and a typical mechanofluorochromism was observed by cyclic operation of the grinding–heating–cooling processes. In addition, two single crystals (O and R) were successfully obtained in proper conditions, and the crystallographic data indicated that crystal O and R had reasonable hollow structures, inside which different solvent molecules were selectively encapsulated. More importantly, we have presented a proof-of-concept example of the strategy for the designation of organic soft porous crystals with a conjugated fluorophore and demonstrated the successful achievement of softness, porosity and crystallization ability. This design strategy is instructive to design and construct organic soft porous crystals with other conjugated building blocks and develop novel smart and stimuli-responsive photo/electronic materials.