Red-shifted Emission Band Research Articles

Shell Thickness Dependent Photocatalytic Properties of ZnO/CdS Core–Shell Nanorods

Core/shell nanorod arrays of ZnO/CdS have been synthesized with varying shell thickness and their shell thickness dependent photocatalytic properties have been investigated. Core/shell nanorod arrays of core diameter of 100 nm with variable shell thickness (10–30 nm) are synthesized by varying the concentration of the citric acid. XRD analysis reveals that tensile strain is obtained for ZnO nanorods and the compressive strain is obtained for core/shell nanorods. The UV–visible absorption spectra of the core/shell nanorod arrays show a red shift of the band edge of uncoated ZnO with shell growth. Steady-state photoluminescence (PL) spectra of the core/shell nanorod arrays show red shift of emission band with the increase in shell thickness. Decay kinetics indicate that the average lifetime (⟨τ⟩) of the core/shell nanorod arrays is larger than that of the uncoated ZnO nanorods due to charge separation. I–V studies show a 16-fold enhancement in current using the ZnO/CdS core/shell nanorod arrays having CdS s...

Glutaraldehyde–chitosan and poly (vinyl alcohol) blends, and fluorescence of their nano-silica composite films

In this study, a commercial chitosan cross-linked with glutaraldehyde (GA–chitosan) having the autofluorescent property was effectively blended with a poly (vinyl alcohol) (PVA) matrix, in the formation of a transparent and fluorescent blend film. The fluorescent efficiency of the film was enhanced with red-shifted emission band by increasing the concentrations of the GA–chitosan and decreasing the PVA crystallinity. It was found that the incorporation of silica nanoparticles could further decrease the PVA crystallinity, enhance the fluorescent efficiency, and largely redshift the emission band, as compared with the neat GA–chitosan–PVA blend film. This fluorescent property could be finely tuned by careful doping of the silica nanoparticles and change of the PVA crystallinity. These phenomena could be reasonably explained by high extent of isolation of the fluorophores, increase of the stiffness of the fluorescent conjugated planar structure, and further decrease of the PVA crystallinity. In addition, the introduction of the nano-silica could improve the water and heat resistances of the GA–chitosan–PVA based silica nanocomposites.

Studies of the solvatochromic emission properties of N-aroylurea derivatives I: Influence of the substitution pattern

The influence of the substituent of the N-aroylurea functionality on the solvatochromic properties of this class of compounds was investigated with eight examples. The absorption spectra of these compounds exhibit the characteristic spectroscopic properties of the corresponding arene fragment and are only slightly dependent on the solvent. In contrast, all investigated aroylurea derivatives exhibit a strong solvatochromism with a good linear correlation between the emission energy and the acceptor numbers (AN) of the solvents; that is, the emission maximum shifts bathochromically (Δλ = 50-93 nm) with increasing AN. Furthermore, in media with increasing viscosity, as established in glycerol or ethanol solutions with decreasing temperature, the emission maxima are significantly shifted to shorter wavelengths and the full width at half maximum (FWHM) changes. All experimental data point to two emitting states, namely the locally excited (LE) state and the charge-transfer (CT) state. Thus, after initial photoexcitation to the LE state an internal charge transfer (ICT) takes place due to the donor-acceptor interplay between the arene unit and the N-acylureido functionality, mainly assisted by the intramolecular hydrogen bond between the terminal NH group and the aryl-substituted carbonyl functionality, hence interconverting the latter to a stronger acceptor. In the polarized CT state the acylurea unit develops a negative charge, which, after solvent relaxation, is stabilized by solvents with high acceptor number. Time-resolved emission spectroscopy revealed additional conformational changes in the excited state. Two emissive species were identified at room temperature, whose lifetimes depend strongly on the chemical environment. In addition, time-resolved emission spectra (TRES) showed red-shifted emission bands at longer delays after the excitation pulse in polar solvents. These findings are rationalized by the presence of two different emitting rotational conformers.

Liquid Crystalline Polythiophene Bearing Phenylnaphthalene Side-Chain

Polythiophene bearing a 2-phenylnaphthalene side group at 3-position was synthesized from a 2,5-dibromothiophene monomer by two polymerization methods, i.e., Yamamoto dehalogenative polycondensation using Ni(cod)2 and Ni-catalyzed chain-growth polymerization. Polymers prepared by the former method had good solubility for organic solvents, 6300–8400 g mol–1 of number-average molecular weights, absorption bands at around 300 and 385 nm due to π–π* transitions at the phenylnaphthalene moiety and polythiophene backbone, a main fluorescence emission band at around 540 nm from the polythiophene backbone in solution and film state, and presence of enantiotropic liquid crystalline phases which enabled to construct an arrayed state. On the other hand, the latter polymer showed considerably red-shifted absorption and emission bands at around 444 and 585 nm in solution and 509 and 720 nm in film state respectively, but had poor solubility and unresolved mesophases.

ZnO-coated carbon nanotubes: an enhanced and red-shifted emission band at UV-VIS wavelength

Porous arrays of ZnO-coated carbon nanotubes exhibit multi-excitations and the intensity of light emission at UV wavelengths is significantly enhanced. Carbon diffusion into the oxide is also observed and resultant effects include red-shift and an additional emission centre at 387 nm.

Synthesis and Photophysical Behavior of Two Novel Bis(1,8-naphthalimides) Containing Triazine Spacers

以1,8-萘酰亚胺和三聚氯氰为主要原料, 合成了两种由三嗪环桥连的双1,8-萘酰亚胺化合物3 和5. 采用紫外-可见光谱和荧光光谱等手段考察了两种化合物在不同溶剂中的光物理行为. 与参比化合物N-丁基-1,8-萘酰亚胺相比, 在二氯甲烷、三氯甲烷和甲醇等极性溶剂中, 化合物3和5除了在短波区（λ〈400 nm）存在1,8-萘酰亚胺的特征荧光发射峰外, 在长波区（〉450 nm）均产生一个较强的新荧光发射峰, 表现出分子内激基缔合物的光物理行为. 与化合物5相比, 由于化合物3特殊的构象异构, 其荧光强度发生严重的猝灭. 在非极性溶剂甲基环己烷中, 化合物5 由于存在较强的分子间氢键作用而聚集, 受激后形成了较稳定的分子间激基缔合物, 但未观察到明显的分子内激基缔合物的形成. 在甲苯溶剂中, 化合物3和5与甲苯分子形成了激基复合物, 并未形成分子内激基缔合物. 进一步研究3和5的固态激发态性质, 发现化合物3和5的固体薄膜受激后分别在465和469 nm处出现激基缔合物的特征荧光发射峰.

From red to near infra-red OLEDs: the remarkable effect of changing from X = –Cl to –NCS in a cyclometallated [Pt(N∧C∧N)X] complex {N∧C∧N = 5-mesityl-1,3-di-(2-pyridyl)benzene}

[PtL(6)X] {X = Cl or NCS and L(6) = 5-mesityl-1,3-di(2-pyridyl)-benzene} display similar luminescence in solution but, in the solid state, the packing of the molecules is different, with short PtPt interactions for X = NCS, leading to a red-shifted emission band. The effect has been used to generate OLEDs that emit squarely in the NIR region (855 nm).

A series of copper(I) complexes with electron donor/acceptor embedded ligands: Synthesis, photophysical and electroluminescent properties

In this paper, we report the synthesis of four diimine ligands incorporated with an electron donor/acceptor, as well as their corresponding Cu(I) complexes with bis(2-(diphenylphosphanyl)phenyl) ether as an ancillary ligand, resulting in four phosphorescent Cu(I) complexes. Their crystal structures as well as photophysical and thermal properties are discussed in detail. Experimental data and theoretical calculations confirm that electron donor moieties and limited conjugation system may self-restrict geometry relaxation in excited states, leading to narrowed and blue-shifted emission bands. On the other hand, electron acceptor moieties and large coplanar conjugation system are ineffective in restricting geometry relaxation, leading to broadened and red-shifted emission bands. However, the introduction of electron donors compromises thermal stability of Cu(I) complexes. We also explore one of the Cu(I) complexes as a dopant for electroluminescence application, and a maximum luminance of 680 cd/m2 peaking at 620 nm is achieved.

Impact of ion-implantation-induced band gap engineering on the temperature-dependent photoluminescence properties of InAs/InP quantum dashes

We report on the effects of the As/P intermixing induced by phosphorus ion implantation in InAs/InP quantum dashes (QDas) on their photoluminescence (PL) properties. For nonintermixed QDas, usual temperature-dependent PL properties characterized by a monotonic redshift in the emission band and a continual broadening of the PL linewidth as the temperature increases, are observed. For intermediate ion implantation doses, the inhomogeneous intermixing enhances the QDas size dispersion and the enlarged distribution of carrier confining potential depths strongly affects the temperature-dependent PL properties below 180 K. An important redshift in the PL emission band occurs between 10 and 180 K which is explained by a redistribution of carriers among the different intermixed QDas of the ensemble. For higher implantation doses, the homogeneous intermixing reduces the broadening of the localized QDas state distribution and the measured linewidth temperature behavior matches that of the nonintermixed QDas. An anomalous temperature-dependent emission energy behavior has been observed for extremely high implantation doses, which is interpreted by a possible QDas dissolution.

Fluorescence Spectral Dynamics of Single LHCII Trimers

Single-molecule spectroscopy was employed to elucidate the fluorescence spectral heterogeneity and dynamics of individual, immobilized trimeric complexes of the main light-harvesting complex of plants in solution near room temperature. Rapid reversible spectral shifts between various emitting states, each of which was quasi-stable for seconds to tens of seconds, were observed for a fraction of the complexes. Most deviating states were characterized by the appearance of an additional, red-shifted emission band. Reversible shifts of up to 75 nm were detected. By combining modified Redfield theory with a disordered exciton model, fluorescence spectra with peaks between 670 nm and 705 nm could be explained by changes in the realization of the static disorder of the pigment-site energies. Spectral bands beyond this wavelength window suggest the presence of special protein conformations. We attribute the large red shifts to the mixing of an excitonic state with a charge-transfer state in two or more strongly coupled chlorophylls. Spectral bluing is explained by the formation of an energy trap before excitation energy equilibration is completed.

Fluorescent chemosensors for metal ions based on 3-(2-benzoxazol-5-yl)alanine skeleton

Abstract The ability of new chelate ligands, benzoxazol-5-yl-alanine derivatives substituted in position 2 by heteroaromatic substituent, to form complexes with selected metal ions in acetonitrile are studied by means of absorption and steady-state and time-resolved fluorescence spectroscopy. Among the ligands studied, only azaaromatic derivatives form stable complexes with transition metal ions in the ground state. Their absorption bands are bathochromically shifted enabling to use those ligands as ratiometric sensors. The fluorescence of each ligand is quenched by metal ions, however, in the presence of Cd(II) and Zn(II) ions a new red shifted emission band is observed.

Environment-sensitive behavior of fluorescent molecular rotors

Molecular rotors are a group of fluorescent molecules that form twisted intramolecular charge transfer (TICT) states upon photoexcitation. When intramolecular twisting occurs, the molecular rotor returns to the ground state either by emission of a red-shifted emission band or by nonradiative relaxation. The emission properties are strongly solvent-dependent, and the solvent viscosity is the primary determinant of the fluorescent quantum yield from the planar (non-twisted) conformation. This viscosity-sensitive behavior gives rise to applications in, for example, fluid mechanics, polymer chemistry, cell physiology, and the food sciences. However, the relationship between bulk viscosity and the molecular-scale interaction of a molecular rotor with its environment are not fully understood. This review presents the pertinent theories of the rotor-solvent interaction on the molecular level and how this interaction leads to the viscosity-sensitive behavior. Furthermore, current applications of molecular rotors as microviscosity sensors are reviewed, and engineering aspects are presented on how measurement accuracy and precision can be improved.

Photoinduced properties of methyl ester of 2,6-dimethyl-1-amino-4-benzoic acid: Evidence of charge transfer emission from a weak primary amino donor

Photophysical properties of methyl ester of 2,6-dimethyl-1-amino-4-benzoic acid (M26DMB) have been investigated using steady state absorption and emission spectroscopy and time-resolved emission spectroscopy. Interestingly, not only in polar solvents, the molecule M26DMB having a weak primary amino donor group shows broad red-shifted emission band even in non-polar environment which in all probability arises from closely spaced local and charge transfer (CT) states. Clear dual fluorescence in polar protic solvents comprises of less intense local emission band and strong red-shifted CT band. The position of the red-shifted emission band is dependent on both the polarity and the hydrogen-bonding ability of the solvent.

Synthesis and functionality of the storage phosphor BaFBr:Eu2+

The present paper relates to a method for synthesizing the photostimulable storage phosphor BaFBr:Eu2+ that features high stimulation characteristics for use in image plates. All previous synthesis routes consist of a multistep process whereas the presented route is a one-step synthesis. Starting compounds are BaCO3, NH4F, and NH4Br, as well as EuF3 where the ammonium compounds are highly volatile at temperatures below 300°C. Their reaction products initiate the decomposition of BaCO3 and form BaFBr. The incorporation of F-centers and europium ions occurs at temperature exceeding 550°C. The individual reaction steps are monitored by simultaneous thermal analysis (thermogravimetry/differential thermal analysis) and the gaseous reaction products are detected by in situ mass spectroscopy. Intermediate and final products are characterized by x-ray diffraction techniques to determine the involved phases. Photoluminescence spectra reveal the typical emission peak of Eu2+ accompanied by a redshifted emission band at 470nm, which was assigned to oxygen incorporated into the BaFBr lattice. The synthesized powders exhibit small grain sizes well suited for the use in image plates.

Origin of the low-energy emission band in epitaxially grown para-sexiphenyl nanocrystallites

A comparative study of steady-state and time-resolved photoluminescence of para-sexiphenyl (PSP) films grown by organic molecular beam epitaxy (OMBE) and hot wall epitaxy (HWE) under comparable conditions is presented. Using different template substrates [mica(001) and KCl(001) surfaces] as well as different OMBE growth conditions has enabled us to vary greatly the morphology of the PSP crystallites while keeping their chemical structure virtually untouched. We prove that the broad redshifted emission band has a structure-related origin rather than being due to monomolecular oxidative defects. We conclude that the growth conditions and type of template substrate impacts substantially on the film morphology (measured by atomic force microscopy) and emission properties of the PSP films. The relative intensity of the defect emission band observed in the delayed spectra was found to correlate with the structural quality of PSP crystallites. In particular, the defect emission has been found to be drastically suppressed when (i) a KCl template substrate was used instead of mica in HWE-grown films, and (ii) in the OMBE-grown films dominated by growth mounds composed of upright standing molecules as opposed to the films consisting of crystallites formed by molecules lying parallel to the substrate.

Exploring RNA-ligand interactions

Abstract RNA molecules play essential roles in biological processes and are evolving as important targets for therapeutic intervention. Small molecules that specifically bind unique RNA sites and prevent the formation of functional RNA folds or RNA-protein complexes can modulate cell functions and can become of therapeutic potential. To explore such recognition events and to fabricate discovery assays, effective biophysical tools need to be advanced. When carefully designed, new fluorescent nucleosides can serve an unparalleled role in such studies. Our criteria for "ideal" fluorescent nucleoside analogs include: (a) high structural similarity to the native nucleobases to faithfully mimic their size and shape, as well as hybridization and recognition properties; (b) red-shifted absorption bands; (c) red-shifted emission band (preferably in the visible); (d) a reasonable emission quantum efficiency; and, importantly, (e) sensitivity of their photophysical parameters to changes in the microenvironment. Our program, aimed at the development of new emissive isomorphic nucleoside analogs, has yielded several useful nucleobases. Selected analogs were implemented in fluorescence-based assays. This overview presents the motivation for this work by introducing RNA-ligand interactions and discusses the design and synthesis of fluorescent isosteric nucleobase analogs and their utilization for the fabrication of "real-time" fluorescence-based biophysical assays.

Syntheses, Structures, and Photophysical Properties of Mono- and Dinuclear Sulfur-Rich Gold(I) Complexes

The dinuclear gold complexes [{Au(PPh 3)} 2(mu- dmid)] ( 1) ( dmid = 1,3-dithiole-2-one-4,5-dithiolate) and [{Au(PPh 3)} 2(mu- dddt)] ( 2) ( dddt = 5,6-dihydro-1,4-dithiine-2,3-dithiolate) were synthesized and characterized by X-ray crystallography. Both complexes exhibit intramolecular aurophilic interactions with Au...Au distances of 3.1984(10) A for 1 and 3.1295(11) A for 2. A self-assembly reaction between 4,5-bis(2-hydroxyethylthio)-1,3-dithiole-2-thione ( (HOCH 2 CH 2 ) 2 dmit) and [AuCl(tht)] affords the complex [AuCl{ (HOCH 2 CH 2 ) 2 dmit}] 2 ( 4), which possesses an antiparallel dimeric arrangement resulting from a short aurophilic contact of 3.078(6) A. This motif is extended into two dimensions due to intra- and intermolecular hydrogen bonds via the hydroxyethyl groups, giving rise to a supramolecular network. Three compounds were investigated for their rich photophysical properties at 298 and 77 K in 2-MeTHF and in the solid state; [Au 2(mu- dmid)(PPh 3) 2] ( 1), [Au 2(mu- dddt)(PPh 3) 2] ( 2), and [AuCl{( HOCH 2 CH 2 ) 2 dmit}] ( 4). 1 exhibits relatively long-lived LMCT (ligand-to-metal charge transfer) emissions at 298 K in solution (370 nm; tau e approximately 17 ns, where M is a single gold not interacting with the other gold atom; i.e., the fluxional C-SAuPPh 3 units are away from each other) and in the solid state (410 nm; tau e approximately 70 mus). At 77 K, a new emission band is observed at 685 nm (tau e = 132 mus) and assigned to a LMCT emission where M is representative for two gold atoms interacting together consistent with the presence of Au...Au contacts as found in the crystal structure. In solution at 77 K, the LMCT emission is also red-shifted to 550 nm (tau e approximately 139 mus). It is believed to be associated to a given rotamer. 2 also exhibits LMCT emissions at 380 nm at 298 K in solution and at 470 nm in the solid state. 4 exhibits X/MLCT emission (halide/metal to ligand charge transfer) where M is a dimer in the solid state with obvious Au...Au interactions, resulting in red-shifted emission band, and is a monomer in solution in the 10 (-5) M concentration (i.e., no Au...Au interactions) resulting in blue-shifted luminescence. Both fluorescence and phosphorescence are observed for 4.

Dual emission from ( E)-3-(4-methylamino-phenyl)-acrylic acid ethyl ester (MAPAEE) and its application as fluorescence probe for studying micellar and protein microenvironment

Steady state absorption, fluorescence and time resolved fluorescence spectroscopy have been used for studying the photoinduced intramolecular charge transfer reaction in ( E)-3-(4-methylamino-phenyl)-acrylic acid ethyl ester (MAPAEE). The title molecule shows dual emission due to high energy local and a low energy charge transfer emission. Depending on the nature of solvent the red shifted emission band shows good correlation with the solvent polarity parameter, E T(30) parameter and hydrogen bonding parameter. Quantum chemicals calculations by density functional theory predict that a stabilized twisted intramolecular charge transfer excited state generated either by twisting of the donor group ( NHMe) or the acceptor (- = COOEt) group is responsible for the red shifted charge transfer emission. The solvent polarity dependent red shifted emission from the excited charge transfer state of MAPAEE has been used as fluorosensor to study bovine serum albumin proteinous and sodium dodecyl sulphate micellar microenvironment.

Photophysical properties of 2,3,6,7-tetrahydro-8-hydroxy-1H, 5H-benz[ i, j] quinolizine-9-carboxaldehyde: Evidence of excited state intramolecular proton transfer but not of intramolecular charge transfer process

The photophysical behaviours of 2,3,6,7-tetrahydro-8-hydroxy-1H, 5H-benzo[ i, j] quinolizine-9-carboxaldehyde (THBQC), a molecule having both the intramolecular excited state donor acceptor charge transfer and six member intramolecular hydrogen bonded proton transfer sites, have been investigated by steady state and time resolved spectroscopy in combination with quantum chemical calculations. The observed spectral characteristics of THBQC with variation of solvent properties, pH and temperature of the medium confirm the existence of different neutral and ionic species in the ground and excited states. Comparatively less solvent polarity dependent red shifted emission band of THBQC in all solvents is attributed to excited state intramolecular proton transfer of the closed conformer leading to keto-enol tautomerism but not of intramolecular charge transfer process. In polar solvents, apart from the proton transfer emission band, another band at higher energy region is attributed to the emission from the open solvated form. Evaluation of the potential energy surfaces by quantum chemical calculations using Density functional theory (DFT) and Hartree–Fock (HF) levels point towards the possibility of proton transfer reaction in the first excited state and correlate well with the experimental findings.

A New Pyrene-Based Fluorescent Probe for the Determination of Critical Micelle Concentrations

A new pyrene-based fluorescent probe for the determination of critical micelle concentrations (CMC) is described. The title compound 1 is obtained in five steps, starting from pyrene. Fluorescence spectroscopic properties of 1 are studied in homogeneous organic solvents and aqueous micellar solutions. In a wide range of organic solvents, probe 1 exhibits a characteristic monomer emission of the pyrene fluorophore, with three distinct peak maxima at 382, 404, and 425 nm. The spectra change dramatically in aqueous solution, where no monomer emission of the pyrene fluorophore is detected. Instead, only strong excimer fluorescence with a broad, red-shifted emission band at lambda(max) = 465 nm is observed. In micellar aqueous solution, a superposition of the monomer and excimer emission is found. The appearance of the monomer emission in micellar solution can be explained on the basis of solubilization of 1 by the surfactant micelles. The ratio of the monomer to excimer fluorescence intensities of 1 is highly sensitive to changes in surfactant concentration. This renders 1 a versatile and sensitive probe molecule for studying the micellization of ionic and nonionic surfactants. For a representative selection of common surfactants, the critical micelle concentrations in aqueous solution are determined, showing excellent agreement with established literature data.