Blue-shifted Emission Spectra Research Articles

What Is the Optoelectronic Effect of the Capsule on the Guest Molecule in Aqueous Host/Guest Complexes? A Combined Computational and Spectroscopic Perspective

Encapsulation of dye molecules is used as a means to achieve charge separation across different dielectric environments. We analyze the absorption and emission spectra of several coumarin molecules that are encapsulated within an octa-acid dimer forming a molecular capsule. The water-solvated capsule effect on the coumarin’s electronic structure and absorption spectra can be understood as due to an effective dielectric constant where the capsule partially shields electrostatically the dielectric solvent environment. Blue-shifted emission spectra are explained as resulting from a partial intermolecular charge transfer where the capsule is the acceptor, and which reduces the coumarin relaxation in the excited state.

Deformation-induced blueshift in emission spectrum of CdTe quantum dot composites

Abstract Polymer or glass films impregnated with quantum dots (QDs) have potential applications for mesoscale stress/strain sensing in the interior of materials under mechanical loading. One requirement in the development of such nanocomposite sensor materials is the establishment of calibrated relations between shifts in the emission spectrum of QD systems and the input stress/strain on the composites. Here, we use a multiscale computational framework to quantify the strain-dependent blueshift in the emission spectrum of CdTe QDs uniformly distributed in a matrix material under loading of a range of strain triaxiality. The framework, which combines the finite element method, molecular dynamics simulations and the empirical tight-binding method, captures the QD/matrix interactions, possible deformation-induced phase transformations and strain-dependent band structures of the QDs. Calculations reveal that the response of the QDs is strongly dependent on state of input strain. Under hydrostatic compression, the blueshift increases monotonically with strain. Under compression with lateral/axial strain ratios between 0.0 and 0.5, the blueshift initially increases, reaches a peak at an intermediate strain, and subsequently decreases with strain. This trend reflects a competition between increases in the energy levels associated with the conduction and valence bands of the QDs. The deformation-induced blueshift is also found to be dependent on QD orientations. The averaged blueshift over all orientations for the composite under uniaxial strain condition explains the blueshift variation trend observed in laser-driven shock compression experiments. Based on the simulation result, guidelines for developing QD composites as stress/strain sensing materials are discussed.

Synthesis and Photoluminescence of Red to Near-Infrared-Emitting CdTe( x) Se(1−x) /CdZnS Core/Shell Quantum Dots.

Red to near-infrared (NIR)-emitting ternary-alloyed CdTe (x) Se(1−x) (x = 0–0.3) quantum dots (QDs) with tetrapod and dot morphologies have been synthesized by a facile method using oleic acid (OA) as single capping agent. The controlled dot-shaped and tetrapod-shaped CdTe( x) Se(1−x) QDs can be successfully obtained by adjusting the content of Te element. It is clear that CdTe (x) Se(1−x) QDs display the tunable emission peaks from the visible light (613.4 nm) to the NIR range (791.6 nm). With an inorganic CdZnS shell coated on the surface of CdTe(0.1)Se(0.9) cores, the stability and PL efficiency of the resulting core/shell QDs can be improved dramatically, accompanied with the red-shift of emission peaks to longer wavelength (795.6 nm). Peculiarly, a large blue shift of emission spectrum of CdTe(0.3)Se(0.7)/CdZnS core/shell QDs is observed, which is mainly ascribed to the shrink of the size of QDs by the fracture of tetrapod arms.

Ex Vivo Confocal Spectroscopy of Autofluorescence in Age-Related Macular Degeneration.

PurposeWe investigated the autofluorescence (AF) signature of the microscopic features of retina with age-related macular degeneration (AMD) using 488 nm excitation.MethodsThe globes of four donors with AMD and four age-matched controls were embedded in paraffin and sectioned through the macula. Sections were excited using a 488 nm argon laser, and the AF emission was captured using a laser scanning confocal microscope (496–610 nm, 6 nm resolution). The data cubes were then analyzed to compare peak emission spectra between the AMD and the controls. Microscopic features, including individual lipofuscin and melanolipofuscin granules, Bruch’s Membrane, as well macroscopic features, were considered.ResultsOverall, the AMD eyes showed a trend of blue-shifted emission peaks compared with the controls. These differences were statistically significant when considering the emission of the combined RPE/Bruch’s Membrane across all the tissue cross-sections (p = 0.02).ConclusionsThe AF signatures of ex vivo AMD RPE/BrM show blue-shifted emission spectra (488 nm excitation) compared with the control tissue. The magnitude of these differences is small (~4 nm) and highlights the potential challenges of detecting these subtle spectral differences in vivo.

Effects of silver nanoparticles doping on morphology and luminescence behaviour of ferroelectric liquid crystals Langmuir–Blodgett films

ABSTRACTWe report the deposition of Langmuir–Blodgett (LB) thin films of low-weight dispersed composite systems of ferroelectric liquid crystals (FLCs)–functionalised silver (Ag) nanoparticles. Because of their amphiphilic nature the molecules form stable Langmuir monolayers, which were transferred to silicon substrates. We noticed that absorption wave numbers are present for each bond constituting FLC–nanoparticles composite system, ensuring a complete transfer of molecules from water sub-phase. XRD showed intense peaks at 2θ = 3.2° due to the layer structure of FLC molecules. We infer from the morphology of LB films that doping of nanoparticles do not provide any hindrance to SmC* layer structure of FLC molecules. The photoluminescence study indicates blue shift in emission spectra and peak intensity increases with Ag nanoparticles concentration.

Chemical-Biological Properties of Zinc Sensors TSQ and Zinquin: Formation of Sensor-Zn-Protein Adducts versus Zn(Sensor)2 Complexes.

Fluorescent zinc sensors are the most commonly used tool to study the intracellular mobile zinc status within cellular systems. Previously, we have shown that the quinoline-based sensors Zinquin and 6-methoxy-8-p-toluenesulfonamido-quinoline (TSQ) predominantly form ternary adducts with members of the Zn-proteome. Here, the chemistries of these sensors are further characterized, including how Zn(sensor)2 complexes may react in an intracellular environment. We demonstrate that these sensors are typically used in higher concentrations than needed to obtain maximum signal. Exposing cells to either Zn(Zinquin)2 or Zn(TSQ)2 resulted in efficient cellular uptake and the formation of sensor-Zn-protein adducts as evidenced by both a fluorescence spectral shift toward that of ternary adducts and the localization of the fluorescence signal within the proteome after gel filtration of cellular lysates. Likewise, reacting Zn(sensor)2 with the Zn-proteome from LLC-PK1 cells resulted in the formation of sensor-Zn-protein ternary adducts that could be inhibited by first saturating the Zn- proteome with excess sensor. Further, a native SDS-PAGE analysis of the Zn-proteome reacted with either the sensor or the Zn(sensor)2 complex revealed that both reactions result in the formation of a similar set of sensor-Zn-protein fluorescent products. The results of this experiment also demonstrated that TSQ and Zinquin react with different members of the Zn-proteome. Reactions with the model apo-Zn-protein bovine serum albumin showed that both Zn(TSQ)2 and Zn(Zinquin)2 reacted to form ternary adducts with its apo-Zn-binding site. Moreover, incubating Zn(sensor)2 complexes with non-zinc binding proteins failed to elicit a spectral shift in the fluorescence spectrum, supporting the premise that blue-shifted emission spectra are due to sensor-Zn-protein ternary adducts. It was concluded that Zn(sensors)2 species do not play a significant role in the overall reaction between these sensors and intact cells. In turn, this study further supports the formation of sensor-Zn-protein adducts as the principal observed fluorescent product during experiments employing these two sensors.

Lasing modes of a microdisk with a ring gain area and of an active microring

Microcavity lasers shaped as thin circular disks are famous for the ultra-low thresholds of their whispering-gallery modes. We considered a two-dimensional model of such a laser in free space with a ring-like active region and compared the characteristics of its modes with the modes of an active microring, i.e. a similar disk with a concentric hole. The comparison showed that a microring has considerable rarefaction effect in terms of emission thresholds, accompanied by the blue-shift of emission spectra. If the ring becomes narrower than a half-wavelength in material, then all lasing modes obtain catastrophically high thresholds.

The effect of CN-substitution on the electronic and photophysical properties of bis(carbene) Ir(III) complexes containing 2-(1H-pyrazol-5-yl)pyridinato ancillary ligand: A theoretical perspective

The electronic structures and photophysical properties of four heteroleptic Ir(III) complexes 1 [(Mepmi)2Ir(pypz)], 2 [(CNpmi)(Mepmi)Ir(pypz)], 3 [(Mepmi)(CNpmi)Ir(pypz)] and 4 [(CNpmi)2Ir(pypz)] (where Mepmi=1-(4-methyl-phenyl)-3-methylimdazolin-2-ylidene-C,C2′; CNpmi=1-(4-cyano-phenyl)-3-methylimdazolin-2-ylidene-C,C2′; pypz=2-(1H-pyrazol-5-yl)pyridinato) are investigated using the density functional method. The influence of different positions and numbers of CN-substitution has been explored. The calculated results reveal that the introduction of CN substituent leads to lowered HOMO and LUMO energy levels, increased HOMO–LUMO energy gaps, and the enhanced intensity of the absorption spectra. Meanwhile, the CN-substitution in carbene ligand is found to be an efficient approach of tuning the emitting color. The one CN substituent in 2 leads to an obvious blue shift of emission spectra, while a slight red shift is observed for the 3 and 4 in comparison with 1. The qualitative analysis on the quantum yields of four complexes has been carried out with the assistance of ΔES1−T1 (singlet–triplet energy splitting), MLCT% (metal-based charge transfer contribution in T1 state) and μS1 (S0→S1 transition electric dipole moment). It showed that the designed complex 2 and 3 with one CN substituent in carbene ligand may be the potential blue-emitting materials and possess high quantum efficiency.

Freeze-thaw stress of Alhydrogel® alone is sufficient to reduce the immunogenicity of a recombinant hepatitis B vaccine containing native antigen

Preventing losses in vaccine potency due to accidental freezing has recently become a topic of interest for improving vaccines. All vaccines with aluminum-containing adjuvants are susceptible to such potency losses. Recent studies have described excipients that protect the antigen from freeze-induced inactivation, prevent adjuvant agglomeration and retain potency. Although these strategies have demonstrated success, they do not provide a mechanistic understanding of freeze–thaw (FT) induced potency losses. In the current study, we investigated how adjuvant frozen in the absence of antigen affects vaccine immunogenicity and whether preventing damage to the freeze-sensitive recombinant hepatitis B surface antigen (rHBsAg) was sufficient for maintaining vaccine potency. The final vaccine formulation or Alhydrogel® alone was subjected to three FT-cycles. The vaccines were characterized for antigen adsorption, rHBsAg tertiary structure, particle size and charge, adjuvant elemental content and in-vivo potency. Particle agglomeration of either vaccine particles or adjuvant was observed following FT-stress. In vivo studies demonstrated no statistical differences in IgG responses between vaccines with FT-stressed adjuvant and no adjuvant. Adsorption of rHBsAg was achieved; regardless of adjuvant treatment, suggesting that the similar responses were not due to soluble antigen in the frozen adjuvant-containing formulations. All vaccines with adjuvant, including the non-frozen controls, yielded similar, blue-shifted fluorescence emission spectra. Immune response differences could not be traced to differences in the tertiary structure of the antigen in the formulations. Zeta potential measurements and elemental content analyses suggest that FT-stress resulted in a significant chemical alteration of the adjuvant surface. This data provides evidence that protecting a freeze-labile antigen from subzero exposure is insufficient to maintain vaccine potency. Future studies should focus on adjuvant protection. To our knowledge, this is the first study to systematically investigate how FT-stress to adjuvant alone affects immunogenicity. It provides definitive evidence that this damage is sufficient to reduce vaccine potency.

A DFT/TDDFT study on the effect of CN substitution on color tuning and phosphorescence efficiency of a series of Ir(iii) complexes with phosphine-silanolate ligands

A DFT/TDDFT investigation was performed on the electronic structures, absorption and emission spectra, as well as the phosphorescence efficiency of [(ppy)2Ir(P^SiO)] (1) and the derivatives (1a, 1b, 1c and 1d) with CN-substitution at different positions in ppy ligands, as well as [(dfppy)2Ir(P^SiO)] (2) [where ppy = 2-phenylpyridine, dfppy = 2-(2,4-difluorophenyl)pyridine and (P^SiO) is an organosilanolate ancillary chelate]. The calculated results reveal that the introduction of CN leads to a significant red shift for 1a-1d in absorption spectra compared with that of 1. Moreover, the CN substitution at different positions on C^N ligands may be an efficient approach towards tuning emitting color. 1b, 1c, and 1d lead to a blue shift of emission spectra compared with 1, while an obvious red shift is observed for 1a. The high quantum yield of 1 (0.90) compared to 2 (0.59) is explained based on the S1-Tn splitting energies and energy gap between (3)MLCT/π-π* and (3)MC d-d states, and the evaluation of the radiative and nonradiative rate constants for all the complexes is also studied. The designed complexes 1a, 1c and 1d are expected to be potential phosphorescence emitters in OLEDs with high quantum efficiency.

Synthesis, optical and morphological characterization of doped InP/ZnSe NCs

We report on the Ag-, Fe-, and Co-doping of InP/ZnSe QDs using the growth-doping method. Doping the InP/ZnSe NCs with Ag caused a red-shift in the emission spectra with increasing dopant levels while the PL intensity decreased. Fe-doping resulted in blue-shifted emission spectra. The cobalt-doping (Co-doping) had no effect on the emission peak position. Instead, it had a quenching effect on the PL intensities. The HRTEM images showed well-defined lattice fringes for the doped InP/ZnSe NCs while the XRD analyses showed that they retained their zinc blende structure even after doping.

Intake of Xylooligosaccharides Alters the Structural Organization of Liver Plasma Membrane Bilayer

Xylooligosaccharides (XOS) are non-digestible carbohydrate prebiotics that beneficially affect the host by selective stimulation of specific bacteria in the gastro-intestinal tract. The impact of XOS on gastrointestinal microflora and blood lipids is well known but the exact mechanism of action on liver membranes is still unclear. The organization of membrane lipids in domains is known to be important for the proper functioning of various receptors and mechanisms triggering cell signaling. In this study the influence of XOS-enriched diet on the lipid bilayer structure of rat liver plasma membrane was investigated. XOS intake caused a slight decrease of the fluidity of lipid extracts from liver plasma membranes compared to the controls. This observation was based on the increased generalized polarization (GP) and blue shifted emission spectra of Laurdan. The elevated amount of membrane sphingomyelin may be one possible reason for the reported effects. The micron-scale phase separation of the lipid extracts was also investigated by fluorescence microscopy. A different temperature of phase separation and domain pattern was observed in plasma membrane lipid extracts from XOS-fed animals. We presume that it could be assigned to the altered lipid composition of the membrane bilayer, in particular to the changes in the sphingomyelin/cholesterol ratio. All observed alterations are discussed in the light of the impact of XOS on human health and physiology.

Gas-phase thermometry in a high-pressure cell using BaMgAl10O17:Eu as a thermographic phosphor

We demonstrate the feasibility of laser-induced phosphorescence thermography for gas-phase temperature field measurement in a high-pressure cell. BaMgAl10O17:Eu (BAM) was used as a thermographic phosphor; it shows a blue-shifted laser-induced emission spectrum with increasing temperature. Local temperature was determined from the intensity ratio of two disjunctive emission bands. A new seeding device was developed to suspend the solid thermographic phosphor particles in a gas environment. The particle suspension time was modeled and validated by experiments. The influence of multiple scattering and other aspects of quantitative measurement were examined. The technique is currently capable of measuring up to 650 K, limited by signal intensity. The 2D temperature distributions were measured with a precision better than 60 K at 650 K. Multiple scattering limits the spatial resolution to only about 10 mm along the line of sight.

A Spectroscopic Survey of Substituted Indoles Reveals Effects of 1LB Transition Stabilization

Although tryptophan is a natural probe of protein structure, interpretation of its fluorescence emission spectrum is complicated by the presence of two electronic transitions, 1La and 1Lb. Theoretical calculations show that a point charge adjacent to either ring of the indole can shift the emission maximum. This study explores the effect of pyrrole and benzyl ring substitutions on the transitions' energy via absorption and fluorescence spectroscopy, and lifetime measurements. The survey of indole derivatives shows that methyl substitutions on the pyrrole ring effect 1La and 1Lb energies in tandem while benzyl ring substitutions with electrophilic groups lift the 1La/1Lb degeneracy. For 5- and 6-hydroxyindole in cyclohexane, 1La and 1Lb transitions are resolved (5-hydroxyindole absorbance, shown, solid line). This finding provides for 1La origin assignment in the absorption and excitation spectra for indole vapor. The 5-hydroxyindole excitation spectrum (dashed line) shows that despite a blue-shifted emission spectrum, both the 1La and 1Lb transitions contribute to emission. 10 0 ns fluorescence lifetimes for 5-hydroxyindole are consistent with a charge acceptor-induced increase in the nonradiative rate.View Large Image | View Hi-Res Image | Download PowerPoint Slide

Effect of thermal stability on performance of β-phase poly(9,9-di-n-octylfluorene) in deep blue electroluminescence

The device performances including the emission spectrum and device efficiency of blue-emitting β-phase poly(9,9-di-n-octylfluorene) (β-PFO) annealed at different temperatures from 40 to 160 °C are investigated. The relatively unchanged β-PFO content along with dominating photoluminescence (PL) and electroluminescence (EL) spectra are observed at the thermal annealing temperature (TTA) below 90 °C. As TTA > 90 °C, a gradual decrease in the β-PFO fraction is observed, and there is a significant blue shift of emission spectra at TTA > 130 °C which is due to a generation of large amount of crystalline PFO acting as an energy harvester. As for the device performance, β-PFO can give relatively stable current efficiency and brightness at a temperature between 50 and 80 °C. Based on these results, it suggests that blue-emitting β-PFO is practically applicable in display and illumination as a stable deep-blue light source.

High-efficiency fiber laser at 1018 nm using Yb-doped phosphosilicate fiber

A high-efficiency fiber laser at 1018 nm using homemade Yb-doped phosphosilicate fiber is demonstrated. The fiber shows blueshifted emission spectrum compared to Yb-doped aluminosilicate fiber, and is considered favorable for the short wavelength Yb-doped fiber laser. With a 7 m gain fiber, up to 22.8 W output at 1018 nm is achieved with an optical efficiency of 53%. The amplified spontaneous emission at 1030 nm is suppressed to 50 dB below the 1018 nm laser. This work shows that highly-efficient fiber laser at 1018 nm can be obtained with Yb-doped phosphosilicate fiber.

A Spectroscopic Survey of Substituted Indoles Reveals Consequences of a Stabilized 1Lb Transition

Although tryptophan is a natural probe of protein structure, interpretation of its fluorescence emission spectrum is complicated by the presence of two electronic transitions, (1)L(a) and (1)L(b). Theoretical calculations show that a point charge adjacent to either ring of the indole can shift the emission maximum. This study explores the effect of pyrrole and benzyl ring substitutions on the transitions' energy via absorption and fluorescence spectroscopy, and anisotropy and lifetime measurements. The survey of indole derivatives shows that methyl substitutions on the pyrrole ring effect (1)L(a) and (1)L(b) energies in tandem, whereas benzyl ring substitutions with electrophilic groups lift the (1)L(a)/(1)L(b) degeneracy. For 5- and 6-hydroxyindole in cyclohexane, (1)L(a) and (1)L(b) transitions are resolved. This finding provides for (1)L(a) origin assignment in the absorption and excitation spectra for indole vapor. The 5- and 6-hydroxyindole excitation spectra show that despite a blue-shifted emission spectrum, both the (1)L(a) and (1)L(b) transitions contribute to emission. Fluorescence lifetimes of 1(0) ns for 5-hydroxyindole are consistent with a charge acceptor-induced increase in the nonradiative rate (1).

A method to measure pH inside mesoporous particles using protein-bound SNARF1 fluorescent probe

We use fluorescence spectroscopy to measure the pH sensed by proteins which are immobilized in mesoporous silica particles by covalently attaching the pH-probe SNARF1 to the proteins. In contrast to previous attempts where pH-probes were attached to the pore surface, the present approach allows the pH to be measured without altering the properties of the silica material. When the particles are suspended in aqueous solutions of various pH the emission spectra of the labeled proteins indicate an environment inside the pores which is closer to neutral compared to the bulk solution. In a 1-butanol/water mixture (92.5/7.5%) the emission spectra of the immobilized proteins report a pH-behavior typical of the aqueous suspensions, in contrast to the blue-shifted emission spectrum of the protein in the outside organic solvent. This observation shows that the immobilized proteins experience an aqueous pore environment even though the surrounding solution is poor in water. The spectra of SNARF1-labeled bovine serum albumin and feruloyl esterase generated similar results suggesting that the method can be applied to different types of proteins. Taken together the results show that spectroscopic probes carried by immobilized macromolecules can be used to characterize the environment inside mesoporous particles without perturbing the properties of the material.

Stable blue-green light-emitting electrochemical cells based on a cationic iridium complex with phenylpyrazole as the cyclometalated ligands

A novel blue-green light-emitting cationic iridium complex [Ir(ppz)2pzpy]PF6 (complex 1), where ppz is phenylpyrazole and pzpy is 2-(1-phenyl-1H-pyrazol-3-yl)pyridine, is developed. Its crystal, photophysical and electrochemical properties are characterized through experiments and quantum chemical calculations. The novel complex exhibits enlarged energy gap and blue-shifted emission spectrum at 77K compared to a reference complex, [Ir(ppy)2pzpy]PF6 (complex 2), with phenylpyridine (ppy) as the cyclometalated ligands. Moreover, light-emitting electrochemical cells (LECs) fabricated with complex 1 show both improved color purity with CIE (Commission Internationale de L’Eclairage) coordinates of (0.25, 0.39) and elongated lifespan (t1/2=218min, Etot=0.55mJ) compared to LECs based on complex 2.

Effects of overgrown p-layer on the emission characteristics of the InGaN/GaN quantum wells in a high-indium light-emitting diode

The counteraction between the increased carrier localization effect due to the change of composition nanostructure in the quantum wells (QWs), which is caused by the thermal annealing process, and the enhanced quantum-confined Stark effect in the QWs due to the increased piezoelectric field, which is caused by the increased p-type layer thickness, when the p-type layer is grown at a high temperature on the InGaN/GaN QWs of a high-indium light-emitting diode (LED) is demonstrated. Temperature- and excitation power-dependent photoluminescence (PL) measurements are performed on three groups of sample, including 1) the samples with both effects of thermal annealing and increased p-type thickness, 2) those only with the similar thermal annealing process, and 3) those with increased overgrowth thickness and minimized thermal annealing effect. From the comparisons of emission wavelength, internal quantum efficiency (IQE), spectral shift with increasing PL excitation level, and calibrated activation energy of carrier localization between various samples in the three groups, one can clearly see the individual effects of thermal annealing and increased p-type layer thickness. The counteraction leads to increased IQE and blue-shifted emission spectrum with increasing p-type thickness when the thickness is below a certain value (20-nm p-AlGaN plus 60-nm p-GaN under our growth conditions). Beyond this thickness, the IQE value decreases and the emission spectrum red shifts with increasing p-type thickness.