Red-edge Effect Research Articles

Intrinsic photoluminescence properties of amorphous Si3B3N7 ceramic

Amorphous Si 3 B 3 N 7 ceramic shows intrinsic photoluminescence. Three distinctive emission regions have been observed. Excitation with wavelengths between 254 and 330 nm stimulates intense blue emissions with peak maxima ranging from 447 to 479 nm. Exciting between 315 and 420 nm results in two broad emission peaks; the first in the range between 400 and 440 nm, and the second between 560 and 690 nm. Of these two latter emissions, the one in the violet region dominates in intensity over the other one in the red region, thus a violet color is perceived with the eye via excitation with 330 nm or higher wavelengths. The three distinct intrinsic emissions in the photoluminescence spectrum of amorphous Si 3 B 3 N 7 ceramic are related to defect centers in three topologically different regions in its structure. Dependence of emission on excitation wavelength is associated with the Red-Edge Effect and can be explained with a reabsorption mechanism at the red excitation edge.

A multifaceted ferrocene-benzobisimidazole derivative: fluorogenic probe for Pb2+ and Zn2+ cations and unconventional fluorescence behaviour towards Cu2+ metal cations

The ferrocene-benzobisimidazole derivative shows high affinity for Pb(2+) and Zn(2+) metal cations over a range of other metal cations examined. In the presence of Pb(2+) the emission spectrum is red-shifted by 13 nm with an important chelation-enhanced fluorescence effect (CHEF) CHEF = 55. The presence of Zn(2+) cations also induced a perturbation of the emission spectrum although to a lesser extent than that found for Pb(2+) cations (CHEF = 37). Upon complexation with Cu(2+) cations, not only is the emission band red-shifted (Deltalambda = 67 nm) with a noticeable CHEF = 20, but also the maximum of such fluorescence emission exhibits a concomitant shift towards higher wavelengths when the excitation wavelength is gradually shifted to the red-edge of the absorption band (red-edge effect).

Characterizing deep soils from an impacted subtropical isolated wetland: implications for phosphorus storage

Soils within the Lake Okeechobee drainage basin, FL, USA, have been impacted by beef cattle and dairy operations and the landscape ditched and drained to facilitate stocking and grazing pastures. Restoring wetlands located on pastures has been proposed to reduce overland loss of phosphorus (P) by retaining it within the soils. However, soil properties of deeper horizons within impacted wetlands are rarely investigated due to the assumption that most dominant biogeochemical interactions occur at the soil–water interface. In this paper, we investigate soil properties up to 160 cm below the surface from an impacted isolated wetland and its surrounding upland pasture. Four intact soil cores were collected using the vibracoring technique, sectioned at 2-cm intervals, and analyzed for organic matter content by loss on ignition, total P by acid persulfate digestion, and water-soluble P using 0.01-M KCl solution. Bulk density and digital imaging were conducted using a multisensor core logger. Clay-sized phyllosilicates were identified using a computer-controlled X-ray diffractometer. Saturated hydraulic conductivity was measured using the slug-out technique, and the Hvorslev method was used to evaluate results. Unobliterated stratification was observed within the wetland in contrast to the pedologically formed A, E, and B horizons within the upland. The presence of clay horizons composed of smectite and kaolinite was dominant below 120 cm, posing potential hydrological and chemical implications, such as low conductivity and higher P sorption capacity. Saturated hydraulic conductivity of the soils was 1.22 m day−1 (±0.4). Diagnostic features such as increase in bulk density due to compaction, and the “red-edge effect” were useful in correlating the effect of cattle activity and hydrology on soil profiles. Soil organic matter content (38–48%) and total P (100–600 mg kg−1) concentrations were highest and well-correlated (r 2 = 0.81) at the surface. However, a significant amount of P was also present in the deeper horizons associated with clay. The deeper clay horizons account for up to 25% of P per hectare of the entire soil profile. These estimates are nontrivial and need to be accounted for while dealing with belowground P budgets, especially because subsurface lateral flows are dominant within the region.

Interaction of the major protein from bovine seminal plasma, PDC-109 with phospholipid membranes and soluble ligands investigated by fluorescence approaches

The major protein from bovine seminal plasma, PDC-109 binds selectively to choline phospholipids on the sperm plasma membrane and plays a crucial role in priming spermatozoa for fertilization. The microenvironment and accessibility of tryptophans of PDC-109 in the native state, in the presence of phosphorylcholine (PrC) and phospholipid membranes as well as upon denaturation have been investigated by fluorescence approaches. Quenching of the protein intrinsic fluorescence by different quenchers decreased in the order: acrylamide>succinimide≫Cs+>I−. Ligand binding afforded considerable protection from quenching, with shielding efficiencies following the order: dimyristoylphosphatidylcholine (DMPC)>lysophosphatidylcholine (Lyso-PC)>PrC. This has been attributed to a partial penetration of the protein into the DMPC membranes and Lyso-PC micelles, as well as a further stabilization of the binding due to the interaction of PDC-109 with lipid acyl chains and the resulting tightening of the protein structure, leading to a decreased accessibility of the tryptophan residues. Red-edge excitation shift (REES) studies yielded REES values of 4 nm for both native and denatured PDC-109, whereas reduced and denatured protein gave a REES of only 0.5 nm, clearly indicating that the structural and dynamic features of the microenvironment around the tryptophan residues are retained even after denaturation, presumably due to the constraints imposed on the protein structure by disulfide bonds. Upon binding of PDC-109 to DMPC membranes and Lyso-PC micelles the REES values were reduced to 2.5 and 1.0 nm, respectively, which could be due to the penetration of some parts of the protein, especially the segment containing Trp-90 into the membrane interior, where the red-edge effects are considerably reduced.

Modular Fluorescent Benzobis(imidazolium) Salts: Syntheses, Photophysical Analyses, and Applications

A series of benzobis(imidazolium) (BBI) salts has been prepared and studied as a new class of versatile fluorescent materials. Using a high yielding, modular synthetic strategy, BBI salts with a range of functionality poised for investigating fundamental and applications-oriented characteristics, including emission wavelength tunability, solvatochromism, red-edge excitation, chemical stability, multiphoton excitation, and protein conjugation, were prepared in overall yields of 40-97%. Through structural variation, the BBIs exhibited lambda(em) ranging between 329 and 561 nm while displaying phi(f)s up to 0.91. In addition, the emission characteristics of these salts were found to exhibit strong solvent dependencies with Stokes shifts ranging from 4570 to 13 793 cm(-1), depending on the nature of the BBI core. Although red-edge effects for BBI salts with Br and BF4 counterions were found to be similar, unique characteristics were displayed by an analogue with MeSO4 anions. The stability of an amphiphilic BBI was quantified in aqueous solutions of varying pH, and >85% of the emission intensity was retained after 2 h at pH 3-9. Through multiphoton excitation experiments in aqueous solutions, a BBI salt was found to exhibit three-photon fluorescence action cross sections similar to serotonin. The application of BBI salts as fluorescent protein tags was demonstrated by conjugating bovine serum albumin to a maleimide-functionalized derivative.

On the angular dependence of the optical polarization anisotropy in ladder-type polymers

Two ladder-type polymers have been examined using polarized optical absorption and fluorescence spectroscopy in solution and solid state. The fluorescence anisotropy excitation spectra of ladder-type methyl-substituted poly(para-phenylene) and poly(naphthylene-phenylene) follow their absorption profiles, contrary to the typical behavior in other conjugated polymers, which show excitation wavelength dependent anisotropy until the onset of the typical red edge effect. Using Raman microscopy and linear dichroism of aligned stretched polyethylene films containing the ladder polymer, it has been found that the orientation of the absorption transition dipole moment is dependent on the conjugation length. The transition dipole of the shorter conjugation lengths of the distribution is localized approximately 7 degrees off axis, and that of the longer conjugation lengths is delocalized along the chain.

Luminescence studies of o-hydroxy p-amino and p-dimethylamino methyl benzoate

Steady-state and time-resolved spectroscopic studies of two bisubstituted derivatives of methyl benzoate dissolved in methylcyclohexane (McH), tetrahydrofuran (THF), and ethanol (EtOH) have been performed at 293 and 77 K. The compounds under study are capable of showing multimode fluorescence emission at room temperature. The kind of emission, i.e., locally excited state emission Fl(LE), proton-transfer emission Fl(PT) and twisted intramolecular charge-transfer emission Fl(CT) dependent on the solvent. Low temperature measurements show that for those molecules a phosphorescence enhancement via a proton-transfer tunneling is observed. For the molecules under study compositeness of the emission process is explained on an energy scheme, which is based on experimentally determined and theoretically calculated data. Stated dynamic Stokes shift and phosphorescence red-edge effect indicates that both molecules form an inhomogeneous emitting system in solvents used. The experiments are supported with quantum chemical semiempirical calculations.

Red-edge and inhomogeneous broadening effects of the electronic spectra of ethyl 5-(4-aminophenyl)-3-amino-2,4-dicyanobenzoate

Fluorescence excitation, fluorescence and phosphorescence spectra of ethyl 5-(4-aminophenyl)-3-amino-2,4-dicyanobenzoate (EAADCy) were recorded in tetrahydrofuran (THF) at room (293 K) and low-temperature (77 K). In our previous publication [M. Józefowicz, M. Aleksiejew, J.R. Heldt, A. Bajorek, J. Pączkowski, J. Heldt, Chem. Phys. 338 (2007) 53], it was shown that at room temperature, the fluorescence spectrum of EAADCy in THF consists of two bands. The short-wavelength emission corresponds to the molecular conformation in which the donor and acceptor moieties are orthogonal to each other, on the other hand, the long-wavelength emission is assumed to originate from a singlet excited state of molecule in which two moieties are coplanar. In present communication, the fluorescence and phosphorescence behavior of the EAADCy has been studied as a function of the excitation wavelength. The luminescence spectra of the molecule under study in THF glass at 77 K show considerable dependence on the excitation wavelengths. Such dependence of the wavelength of maximum intensity of luminescence (fluorescence and phosphorescence) spectrum and the full width at half maximum of phosphorescence spectrum ( Δ ν ˜ 1 / 2 ph ) on the excitation wavelength is a characteristic demonstration of the red-edge effect. These results along our previous studies [M. Józefowicz, M. Aleksiejew, J.R. Heldt, A. Bajorek, J. Pączkowski, J. Heldt, Chem. Phys. 338 (2007) 53] indicate that EAADCy forms a typically spectrally inhomogeneous system.

On the investigation of the bilayer functionalities of 1,2-di-oleoyl- sn-glycero-3-phosphatidylcholine (DOPC) large unilamellar vesicles using cationic hemicyanines as optical probes: A wavelength-selective fluorescence approach

The behavior of the cationic hemicyanines trans-4-[4-(dimethylamino)-styryl]-1-methylpyridinium iodide (HC) and 4,(4-(dihexadecylamino)styryl- N-methyl-pyridinium iodide (DIA) were studied in large unilamellar vesicles (LUV) of 1,2-di-oleoyl- sn-glycero-3-phosphatidylcholine (DOPC) using absorption, emission, depolarization and time resolved spectroscopies. Also, thorough spectroscopic studies were performed in homogeneous media to investigate the different interactions that the dyes can experience with its microenvironment. These results help us to comprehend the dye performance under different media and, consequently find interesting features of the DOPC membrane properties. The studies in homogeneous media analyzed by the Kamlet and Taft's solvatochromic comparison method demonstrate, for the first time, that the cationic hemycianines undergo specific interactions with the medium through the solvents ability to donate an electron pair as measured by the β parameter. Thus, the absorption bands shifts bathochromically with β while, the emission band shifts hypsochromically. In addition, for the relaxed hemicyanines the 00 energy, ν 00 , is invariant with the solvent properties. The results in LUV of DOPC show that, DIA undergoes a strong association with the vesicle bilayer while HC partitions between the water and the bilayer pseudophases. To monitor directly the microenvironment and dynamics around HC and DIA inside the DOPC bilayer, we use the wavelength-selective fluorescence approach, which is based on the red edge effect in fluorescence spectroscopy, in addition with the ν 00 energy of the hemicyanines. The results show that the fluid state of the DOPC bilayer resembles the microenvironment of sodium bis (2-ethylhexyl) sulfosuccinate (AOT) reverse micelles at W = [H 2O]/[AOT] below 10 where there is no free water forming the water pool. Moreover, it is demonstrated for the first time, that the region of the bilayer close to the polar head of DOPC is a powerful electron donor environment.

Room-Temperature Ionic Liquids: Slow Dynamics, Viscosity, and the Red Edge Effect

Ionic liquids (ILs) have recently attracted significant attention from academic and industrial sources. This is because, while their vapor pressures are negligible, many of them are liquids at room temperature and can dissolve a wide range of polar and nonpolar organic and inorganic molecules. In this Account, we discuss the progress of our laboratory in understanding the dynamics, spectroscopy, and fluid dynamics of selected imidazolium-based ILs using computational and analytical tools that we have recently developed. Our results indicate that the red edge effect, the non-Newtonian behavior, and the existence of locally heterogeneous environments on a time scale relevant to chemical and photochemical reactivity are closely linked to the viscosity and highly structured character of these liquids.

Photoinduced Electron Transfer in Arylacridinium Conjugates in a Solid Glass Matrix

The photophysical properties of a series of 9-arylacridinium conjugates in solid glass matrices composed of sucrose octaacetate have been determined. The fluorescence of the charge-shift states is significantly enhanced because of the retardation of nonradiative pathways for back-electron transfer. Changes of more than 3 orders of magnitude in back-electron-transfer rates (sucrose octaacetate glass vs conventional solvents at room temperature) were observed. Transient spectra displayed long-lived charge-shift species in the microsecond time regime for thianthrene acridinium conjugates. The rate retardation is associated with slow solvation times for surrounding solvent layers in the solid matrix. The red-edge effect (excitation wavelength-dependent fluorescence) for the arylacridinium ions in solid glass confirms the microheterogeneity of the sucrose octaacetate medium.

Correction for Hu and Margulis, Heterogeneity in a room-temperature ionic liquid: Persistent local environments and the red-edge effect

Correction for Hu and Margulis, Heterogeneity in a room-temperature ionic liquid: Persistent local environments and the red-edge effect

Conformational Flexibility of Cytokine-Like C-Module of Tyrosyl-tRNA Synthetase Monitored by Trp144 Intrinsic Fluorescence

The non-catalytic COOH-terminal module formed after proteolytic cleavage of full-length mammalian tyrosyl-tRNA synthetase displays dual function: tRNA binding ability and cytokine activity. With the aim to explore the intramolecular dynamics of C-module in solution we used fluorescence spectroscopy to study conformational changes of isolated protein. We used information from fluorescence spectra and computational model for characterization of a microenvironment of a single tryptophan residue (Trp144). Its fluorescence parameters and protection from quenching by Cs+ ions indicate the internal localization--buried into protein globule. The fluorescence quenching of Trp144 by acrylamide suggests rapid conformation dynamics of the C-module in nanosecond time scale. The temperature-induced conformational changes in the C-module were monitored by the fluorescence measurements of Trp144 emission and by red-edge excitation shift. An emission maximum shift up to approximately 349 nm and significant decrease of the red-edge shift effect at 37-52 degrees C indicated a major conformational transition of Trp144 from buried native state into highly relaxing polar solvent environment.

Intramolecular Charge Transfer Assisted by Conformational Changes in the Excited State of Fluorene-dibenzothiophene-S,S-dioxide Co-oligomers

The strong solvatochromism observed for two fluorene-dibenzothiophene-S,S-dioxide oligomers in polar solvents has been investigated using steady-state and time-resolved fluorescence techniques. A low-energy absorption band, attributed to a charge-transfer (CT) state, is identified by its red shift with increasing solvent polarity. In nonpolar solvents, the emission of these conjugated luminescent oligomers shows narrow and well-resolved features, suggesting that the emission comes from a local excited state (LE), by analogy to their conjugated fluorene-based polymer counterparts. However, in polar solvents, only a featureless broad emission is observed at longer wavelengths (CT emission). A linear correlation between the energy maximum of the fluorescence emission and the solvent orientation polarizability factor Deltaf (Lippert-Mataga equation) is observed through a large range of solvents. In ethanol, below 230 K, the emission spectra of both oligomers show dual fluorescence (LE-like and CT) with the observation of a red-edge excitation effect. The stabilization of the CT emissive state by solvent polarity is accompanied/followed by structural changes to adapt the molecular structure to the new electronic density distribution. In ethanol, above 220 K, the solvent reorganization occurs on a faster time scale (less than 10 ps at 290 K), and the structural relaxation of the molecule (CT(unrelaxed) --> CT(Relaxed)) can be followed independently. The magnitude of the forward rate constant, k(1)(20 degrees C) approximately 20 x 10(9) s(-1), and the reaction energy barrier, E(a) approximately 3.9 kcal mol(-1), close to the energy barrier for viscous flow in ethanol (3.54 kcal mol(-1)), show that large-amplitude molecular motions are present in the stabilization of the CT state.

Efficient Fabrication and Enhanced Photocatalytic Activities of 3D-Ordered Films of Titania Hollow Spheres

Facile and effective approaches were developed to fabricate 3D-ordered films of titania hollow spheres with different sphere diameters. The shell thickness of the sphere was adjusted in the range of 20-40 nm by changing the casting cycle of the titania precursor. The photonic stop band was observed for the 3D-ordered film and was tunable by the sphere diameter and the shell thickness. The stop band shifted from 930 to 547 nm. Crystal violet dye adsorbed on the film exhibited more than two times higher absorbance than that on a reference film of a flat titania layer, probably due to the red edge effect of the stop band and/or to the multiple scattering effect. The enhanced absorbance led to more efficient photodegradation of the dye under visible light and under solar light irradiation. A maximum photocatalytic enhancement of 22% is achieved. Finally, the influence of TiO2 morphology on photocatalytic activity was discussed. Compared with flat titania films, the existence of ordered macropores in titania spheres causes the stop band and a longer optical path due to multiple scattering. Both the red edge of the stop band and multiple scattering effects enhance the absorption of the dye, which results in the photocatalytic enhancement.

A Study of the Time-Resolved Fluorescence Spectrum and Red Edge Effect of ANF in a Room-Temperature Ionic Liquid

In a recent article, we have analyzed using molecular dynamics simulations the steady-state red edge effect (REE) observed by Samanta and co-workers when the fluorescent probe 2-amino-7-nitrofluorene (ANF) is photoexcited at different wavelengths in 1-butyl-3-methylimidazolium ([BMIM+]) hexafluorophosphate ([PF6-]). In this letter, we predict the time- and wavelength-dependent emission spectra of ANF in the same ionic solvent. From the analysis of our simulated data, we are able to derive an approximate time scale for reorganization of the solvent around the solute probe. The effect that slow varying local liquid environments have on the overall time-dependent signal is also discussed.

Heterogeneity in a room-temperature ionic liquid: persistent local environments and the red-edge effect.

In this work, we investigate the slow dynamics of 1-butyl-3-methylimidazolium hexafluorophosphate, a very popular room-temperature ionic solvent. Our study predicts the existence of heterogeneity in the liquid and shows that this heterogeneity is the underlying microscopic cause for the recently reported "red-edge effect" (REE) observed in the study of fluorescence of the organic probe 2-amino-7-nitrofluorene. This theoretical work explains in microscopic terms the relation between REE and dynamic heterogeneity in a room-temperature ionic liquid (IL). The REE is typical of micellar or colloidal systems, which are characterized by microscopic environments that are structurally very different. In contrast, in the case of this room-temperature IL, the REE occurs because of the long period during which molecules are trapped in quasistatic local solvent cages. This trapping time, which is longer than the lifetime of the excited-state probe, together with the inability of the surroundings to adiabatically relax, induces a set of site-specific spectroscopic responses. Subensembles of fluorescent molecules associated with particular local environments absorb and emit at different frequencies. We describe in detail the absorption wavelength-dependent emission spectra of 2-amino-7-nitrofluorene and show that this dependence on lambda(ex) is characteristic of the IL and, as is to be expected, is absent in the case of a normal solvent such as methanol.

Structure and dynamics of the γM4 transmembrane domain of the acetylcholine receptor in lipid bilayers: insights into receptor assembly and function

A 28-mer peptide (gammaM4) corresponding to the fourth transmembrane segment of the nicotinic acetylcholine receptor (AChR) gamma-subunit, with a single tryptophan residue (Trp6), was reconstituted into lipid bilayers of 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine (POPC), loaded with either high or low amounts of cholesterol, i.e., in the conjugated liquid-ordered and liquid-disordered phases, respectively, at room temperature. By making use of the Trp intrinsic fluorescence, both steady-state and time-resolved fluorescence techniques were employed, namely, red-edge excitation shift effect, decay-associated spectra (DAS), and time-resolved anisotropy. The results obtained here, together with previous studies on the same reconstituted peptide, indicate that: (i) Trp6 is strongly anchored in the bilayer with a defined transverse location; (ii) the modifications in the measured DAS are related to the complex result of a self-quenching process on the decay parameters; (iii) the wobbling movement of the indole moiety of Trp6 is fast but severely restricted in amplitude; and, (iv) in the liquid-ordered phase, the bilayer properties and the tilt angle of the peptide enhance peptide-peptide interactions, with the formation of peptide rich patches and possibly some anti-parallel helix-helix aggregates, showing different dynamics from that of the peptide in the liquid-disordered phase where the peptide is randomly distributed.

Relaxations in Poly(vinyl alcohol) and in Poly(vinyl acetate) Detected by Fluorescence Emission of 4-Aminophthalimide and Prodan

Steady-state and time-resolved emission spectroscopy (TRES) of the medium-sensitive probes 4-aminophthalimide (4-AP) and 6-propionyl-2-(dimethylamino)naphthalene (Prodan) were performed at 77 and 298 K in vacuum-sealed thin films of poly(vinyl alcohol) (PVA) and poly(vinyl acetate) (PVAc). The two probes show similar red-edge effect in steady state emission and a red shift with time in TRES in PVA. In PVAc the red shifts are much smaller and the spectral shift for 4-AP is slower. 4-AP locates in highly polar environments in PVA, where H-bond interaction with the polymer is important. Prodan locates in less polar environments, as evidenced by the position of the emission maximum with respect to reference solvents. Consequently, the observed monoexponential spectral red shift with time of 4-AP in PVA and in PVAc is attributed to relaxation of the interaction of the probe with the hydroxy and acetate moieties, respectively. The more intense interaction of the lighter -OH moiety with the probes explains the greater and faster spectral shift observed in PVA compared to PVAc. The lifetime of this monoexponential spectral shift is independent of temperature in PVA and takes place with a highly negative activation entropy. This fact is attributed to a collective rearrangement of -OH groups to better interact with the excited state. This relaxation nevertheless does not account for the complete accommodation of the excited state. Prodan shows a linear variation of the spectral shift with time that can be explained by microheterogeneity. In PVA, the width at half-maximum of the emission spectra does not change with time for Prodan and it decays with a lifetime similar to the lifetime of the spectral shift in the case of 4-AP. The differences in the behavior of the probes are attributed to their different average location in the polymer matrix.

Effect of hydrogen bonding on the intramolecular charge transfer fluorescence of 6-dodecanoyl-2-dimethylaminonaphtalene

The effect of hydrogen bonding on the intramolecular charge transfer (ICT) of 6-dodecanoyl-2-dimethylaminonaphtalene (laurdan) in neat and binary solvent mixtures has been investigated by using steady-state and time-resolved spectroscopic techniques. The different features of ICT emission of laurdan in methylcyclohexane–tetrahydrofuran and methylcyclohexane–ethanol are explained by the absence and presence of hydrogen bonded ICT. The presence of isosbestic point in absorption spectra of laurdan in methylcyclohexane–ethanol confirms the formation of 1:1 complex between laurdan and ethanol. The obtained data were used to determine the stoichiometric equilibrium constants. In protic rigid (77 K) the fluorescence spectra of laurdan show excitation wavelength dependence (the red-edge effect). Moreover, we reported the decay characteristics of laurdan molecule in locally excited (LE) and ICT state in methylcyclohexane–ethanol.