Simulated changes in biogenic VOC emissions and ozone formation from habitat expansion of Acer Rubrum (red maple)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Drewniak, Beth A.; Snyder, Peter K.; Steiner, Allison L.

A new vegetation trend is emerging in northeastern forests of the United States, characterized by an expansion of red maple at the expense of oak. This has changed emissions of biogenic volatile organic compounds (BVOCs), primarily isoprene and monoterpenes. Oaks strongly emit isoprene while red maple emits a negligible amount. This species shift may impact nearby urban centers because the interaction of isoprene with anthropogenic nitrogen oxides can lead to tropospheric ozone formation and monoterpenes can lead to the formation of particulate matter. Here in this study the Global Biosphere Emissions and Interactions System was used to estimate the spatialmore » changes in BVOC emission fluxes resulting from a shift in forest composition between oak and maple. A 70% reduction in isoprene emissions occurred when oak was replaced with maple. Ozone simulations with a chemical box model at two rural and two urban sites showed modest reductions in ozone concentrations of up to 5–6 ppb resulting from a transition from oak to red maple, thus suggesting that the observed change in forest composition may benefit urban air quality. This study illustrates the importance of monitoring and representing changes in forest composition and the impacts to human health indirectly through changes in BVOCs.« less

Simulated changes in biogenic VOC emissions and ozone formation from habitat expansion of Acer Rubrum (red maple)

NASA Astrophysics Data System (ADS)

Drewniak, Beth A.; Snyder, Peter K.; Steiner, Allison L.; Twine, Tracy E.; Wuebbles, Donald J.

2014-01-01

A new vegetation trend is emerging in northeastern forests of the United States, characterized by an expansion of red maple at the expense of oak. This has changed emissions of biogenic volatile organic compounds (BVOCs), primarily isoprene and monoterpenes. Oaks strongly emit isoprene while red maple emits a negligible amount. This species shift may impact nearby urban centers because the interaction of isoprene with anthropogenic nitrogen oxides can lead to tropospheric ozone formation and monoterpenes can lead to the formation of particulate matter. In this study the Global Biosphere Emissions and Interactions System was used to estimate the spatial changes in BVOC emission fluxes resulting from a shift in forest composition between oak and maple. A 70% reduction in isoprene emissions occurred when oak was replaced with maple. Ozone simulations with a chemical box model at two rural and two urban sites showed modest reductions in ozone concentrations of up to 5-6 ppb resulting from a transition from oak to red maple, thus suggesting that the observed change in forest composition may benefit urban air quality. This study illustrates the importance of monitoring and representing changes in forest composition and the impacts to human health indirectly through changes in BVOCs.

Enhanced performances for top-emitting white organic light-emitting diodes by utilizing green phosphor as energy transfer medium

NASA Astrophysics Data System (ADS)

Deng, Lingling; Bao, Yiyang; Zhang, Yanan; Peng, Ling; Zhu, Wenjing; Zhao, Yue; Xu, Yewen; Chen, Shufen

2016-06-01

In top-emitting white organic light-emitting diodes (TWOLEDs), the device performances attribute to the several important factors, such as exciton profile, energy transfer, and microcavity effect. In this paper, a TWOLED containing a heterojunction blue emission layer (EML) and a red EML is reported. A host material with high triplet energy level is employed for the adjacent blue and red EML, while the inefficient red emission reduces the emission efficiency of the TWOLED. In order to enhance the red emission efficiency, mixed-host and co-doping technologies are used in the red EML. By mixing the hole transporting and electron transporting host materials, the exciton recombination zone extends to the red EML to increase the red emission intensity and reduce the efficiency roll-off. And by co-doping a green phosphor into the red EML as the energy transfer medium, the energy transfer rate is enhanced, and then the current efficiency increases. Besides, both the mixed-host and co-doping change the carrier transport and the exciton recombination zone, which further affects the microcavity resonance in the devices. Due to the enhancement on the red emission intensity and the shift of resonant wavelength, the chromaticity of the TWOLED is improved.

Multi-stimuli responsive luminescent azepane-substituted β-diketones and difluoroboron complexes.

PubMed

Wang, Fang; DeRosa, Christopher A; Daly, Margaret L; Song, Daniel; Fraser, Cassandra L

2017-09-01

Difluoroboron β-diketonate (BF 2 bdk) compounds show environment-sensitive optical properties in solution, aggregation-induced emission (AIE) and multi-stimuli responsive fluorescence switching in the solid state. Here, a series of 4-azepane-substituted β-diketone (bdk) ligands ( L-H , L-OMe , L-Br ) and their corresponding difluoroboron dyes ( D-H , D-OMe , D-Br ) were synthesized, and various responsive fluorescence properties of the compounds were studied, including solvatochromism, viscochromism, AIE, mechanochromic luminescence (ML) and halochromism. Compared to the β-diketones, the boron complexes exhibited higher extinction coefficients but lower quantum yields, and red-shifted absorption and emission in CH 2 Cl 2 . Computational studies showed that intramolecular charge transfer (ICT) dominated rather than π-π* transitions in all the compounds regardless of boron coordination. In solution, all the bdk ligands and boron dyes showed red-shifted emission in more polar solvents and increased fluorescence intensity in more viscous media. Upon aggregation, the emission of the β-diketones was quenched, however, the boronated dyes showed increased emission, indicative of AIE. Solid-state emission properties, ML and halochromism, were investigated on spin cast films. For ML, smearing caused a bathochromic emission shift for L-Br , and powder X-ray diffraction (XRD) patterns showed that the "as spun" and thermally annealed states were more crystalline and the smeared state was amorphous. No obvious ML emission shift was observed for L-H or L-OMe , and the boronated dyes were not mechano-active. Trifluoroacetic acid (TFA) and triethylamine (TEA) vapors were used to study halochromism. Large hypsochromic emission shifts were observed for all the compounds after TFA vapor was applied, and reversible fluorescence switching was achieved using the acid/base pair.

Dust masses for SN 1980K, SN1993J and Cassiopeia A from red-blue emission line asymmetries

NASA Astrophysics Data System (ADS)

Bevan, Antonia; Barlow, M. J.; Milisavljevic, D.

2017-03-01

We present Monte Carlo line transfer models that investigate the effects of dust on the very late time emission line spectra of the core-collapse supernovae SN 1980K and SN 1993J and the young core collapse supernova remnant Cassiopeia A. Their blueshifted emission peaks, resulting from the removal by dust of redshifted photons emitted from the far sides of the remnants, and the presence of extended red emission wings are used to constrain dust compositions and radii and to determine the masses of dust in the remnants. We estimate dust masses of between 0.08 and 0.15 M⊙ for SN 1993J at year 16, 0.12 and 0.30 M⊙ for SN 1980K at year 30 and ∼1.1 M⊙ for Cas A at year ∼330. Our models for the strong oxygen forbidden lines of Cas A require the overall modelled profiles to be shifted to the red by between 700 and 1000 km s-1, consistent with previous estimates for the shift of the dynamical centroid of this remnant.

Fluorinated Alq3 derivatives with tunable optical properties.

PubMed

Shi, Yue-Wen; Shi, Min-Min; Huang, Jia-Chi; Chen, Hong-Zheng; Wang, Mang; Liu, Xiao-Dong; Ma, Yu-Guang; Xu, Hai; Yang, Bing

2006-05-14

This communication reports that not only the emission colour but also the photoluminescence quantum yield of Alq3 can be tuned by introducing fluorine atoms at different positions; with fluorination at C-5 the emission is red-shifted with a tremendously decreased intensity, fluorination at C-6 causes a blue-shift with a significantly increased intensity, and fluorination at C-7 has a minor effect on both the colour and intensity of Alq3's emission.

Photoswitchable red fluorescent protein with a large Stokes shift.

PubMed

Piatkevich, Kiryl D; English, Brian P; Malashkevich, Vladimir N; Xiao, Hui; Almo, Steven C; Singer, Robert H; Verkhusha, Vladislav V

2014-10-23

A subclass of fluorescent proteins (FPs), large Stokes shift (LSS) FP, are characterized by increased spread between excitation and emission maxima. We report a photoswitchable variant of a red FP with an LSS, PSLSSmKate, which initially exhibits excitation and emission at 445 and 622 nm, but violet irradiation photoswitches PSLSSmKate into a common red form with excitation and emission at 573 and 621 nm. We characterize spectral, photophysical, and biochemical properties of PSLSSmKate in vitro and in mammalian cells and determine its crystal structure in the LSS form. Mass spectrometry, mutagenesis, and spectroscopy of PSLSSmKate allow us to propose molecular mechanisms for the LSS, pH dependence, and light-induced chromophore transformation. We demonstrate the applicability of PSLSSmKate to superresolution photoactivated localization microscopy and protein dynamics in live cells. Given its promising properties, we expect that PSLSSmKate-like phenotype will be further used for photoactivatable imaging and tracking multiple populations of intracellular objects.

Tunable trimers: Using temperature and pressure to control luminescent emission in gold(I) pyrazolate-based trimers

DOE PAGES

Woodall, Christopher H.; Fuertes, Sara; Beavers, Christine M.; ...

2014-10-21

A systematic investigation into the relationship between the solid-state luminescence and the intermolecular Au∙∙∙Au interactions in a series of pyrazolate-based gold(I) trimers; tris(μ 2-pyrazolato-N,N')-tri-gold(I) (1), tris(μ 2-3,4,5-trimethylpyrazolato-N,N')-tri-gold(I) (2), tris(μ 2-3-methyl-5-phenylpyrazolato-N,N')-tri-gold(I) (3) and tris(μ 2-3,5-diphenylpyrazolato-N,N')-tri-gold(I) (4) has been carried out using variable temperature and high pressure X-ray crystallography, solid-state emission spectroscopy, Raman spectroscopy and computational techniques. Single-crystal X-ray studies show that there is a significant reduction in the intertrimer Au∙∙∙Au distances both with decreasing temperature and increasing pressure. In the four complexes, the reduction in temperature from 293 to 100 K is accompanied by a reduction in the shortest intermolecular Au∙∙∙Aumore » contacts of between 0.04 and 0.08 Å. The solid-state luminescent emission spectra of 1 and 2 display a red shift with decreasing temperature or increasing pressure. Compound 3 does not emit under ambient conditions but displays increasingly red-shifted luminescence upon cooling or compression. Compound 4 remains emissionless, consistent with the absence of intermolecular Au∙∙∙Au interactions. The largest pressure induced shift in emission is observed in 2 with a red shift of approximately 630 cm -1 per GPa between ambient and 3.80 GPa. The shifts in all the complexes can be correlated with changes in Au∙∙∙Au distance observed by diffraction.« less

Engineering of mCherry variants with long Stokes shift, red-shifted fluorescence, and low cytotoxicity

PubMed Central

Shen, Yi; Chen, Yingche; Wu, Jiahui; Shaner, Nathan C.; Campbell, Robert E.

2017-01-01

MCherry, the Discosoma sp. mushroom coral-derived monomeric red fluorescent protein (RFP), is a commonly used genetically encoded fluorophore for live cell fluorescence imaging. We have used a combination of protein design and directed evolution to develop mCherry variants with low cytotoxicity to Escherichia coli and altered excitation and emission profiles. These efforts ultimately led to a long Stokes shift (LSS)-mCherry variant (λex = 460 nm and λem = 610 nm) and a red-shifted (RDS)-mCherry variant (λex = 600 nm and λem = 630 nm). These new RFPs provide insight into the influence of the chromophore environment on mCherry’s fluorescence properties, and may serve as templates for the future development of fluorescent probes for live cell imaging. PMID:28241009

Rational and random mutagenesis of firefly luciferase to identify an efficient emitter of red bioluminescence

NASA Astrophysics Data System (ADS)

Branchini, Bruce R.; Southworth, Tara L.; Khattak, Neelum F.; Murtiashaw, Martha H.; Fleet, Sarah E.

2004-06-01

Firefly luciferase, which emits yellow-green (557 nm) light, and the corresponding cDNA have been used successfully as a bioluminescence reporter of gene expression. One particularly exciting application is in the area of in vivo bioluminescence imaging. Our interest is in developing improved reagents by identifying Photinus pyralis luciferase mutants that efficiently emit red bioluminescence. In this way, the proven advantages of the P. pyralis protein can be combined with the potential advantages of a red-shifted emitter. Using site-directed mutagenesis techniques, we have identified many mutants emitting red bioluminescence. Unfortunately, these enzymes generally have significantly decreased bioluminescence activity. Interestingly, we discovered a mutation, Ile351Ala, that produced a moderate 16 nm red-shift, while maintaining excellent bioluminescence activity. We then undertook a random mutagenesis approach to identify luciferase mutants that emit further red-shifted bioluminescence with minimal loss of activity. Libraries of mutants were created using an error-prone PCR method and the Ile351Ala luciferase mutant as the template DNA. The libraries were screened by in vivo bacterial assays and the promising mutants were purified to enable accurate determination of bioluminescence emission spectra and total bioluminescence activity. We will report the characterization results, including the identification of the randomly altered amino acids, of several mutants that catalyze bioluminescence with emission maxima of approximately 600 nm.

Super RLuc8: A novel engineered Renilla luciferase with a red-shifted spectrum and stable light emission.

PubMed

Rahnama, Somaieh; Saffar, Behnaz; Kahrani, Zahra Fanaei; Nazari, Mahboobeh; Emamzadeh, Rahman

2017-01-01

Renilla luciferase is a bioluminescent enzyme which is broadly used as a reporter protein in molecular biosensors. In this study, a novel luciferase with desired light emission wavelength and thermostability is reported. The results indicated that the new luciferase, namely super RLuc8, had a red-shifted spectrum and showed stable light emission. Super RLuc8 showed a 10-fold (p-value=0.0084) increase in the thermostability at 37°C after 20min incubation, in comparison to the native enzyme. The optimum temperature of the mutant increased from 30 to 37°C. Molecular dynamics simulation analysis indicated that the increased thermostability was most probably caused by a better structural compactness and more local rigidity in the regions out of the emitter site. Copyright © 2016 Elsevier Inc. All rights reserved.

Guide to red fluorescent proteins and biosensors for flow cytometry.

PubMed

Piatkevich, Kiryl D; Verkhusha, Vladislav V

2011-01-01

Since the discovery of the first red fluorescent protein (RFP), named DsRed, 12 years ago, a wide pallet of red-shifted fluorescent proteins has been cloned and biotechnologically developed into monomeric fluorescent probes for optical microscopy. Several new types of monomeric RFPs that change the emission wavelength either with time, called fluorescent timers, or after a brief irradiation with violet light, known as photoactivatable proteins, have been also engineered. Moreover, RFPs with a large Stokes shift of fluorescence emission have been recently designed. Because of their distinctive excitation and fluorescence detection conditions developed specifically for microscopy, these fluorescent probes can be suboptimal for flow cytometry. Here, we have selected and summarized the advanced orange, red, and far-red fluorescent proteins with the properties specifically required for the flow cytometry applications. Their effective brightness was calculated for the laser sources available for the commercial flow cytometers and sorters. Compatibility of the fluorescent proteins of different colors in a multiparameter flow cytometry was determined. Novel FRET pairs, utilizing RFPs, RFP-based intracellular biosensors, and their application to a high-throughput screening, are also discussed. Copyright © 2011 Elsevier Inc. All rights reserved.

Search for Doppler-shifted gamma-ray emission from SS 433 using the SMM spectrometer

NASA Technical Reports Server (NTRS)

Geldzahler, B. J.; Share, G. H.; Kinzer, R. L.; Magura, J.; Chupp, E. L.

1989-01-01

Data accumulated from 1980 to 1983 with the Gamma Ray Spectrometer aboard NASA's Solar Maximum Mission (SMM) satellite were searched for evidence of red and blue Doppler-shifted 1.37 MeV Mg-24 nuclear lines from SS 433. The SMM data base covers 270 days when SS 433 was in the field of view and includes periods of radio flaring and quiescence. No evidence was found for Doppler-shifted line emission in any of the spectra. The range of 3-sigma upper limits for individual 9 day integration periods was 0.0008-0.0023 photons/sq cm per sec for the blue beam, encompassing the reported about 1.5 MeV line, and 0.0008-0.002 photons/sq cm per sec for the red beam, encompassing the reported about 1.2 MeV line; the average 3-sigma upper limit in each beam for shifted about 1.37 MeV lines is 0.0015 photons/sq cm per sec for single 9 day integrations. The 3-sigma upper limit on 1.37 MeV gamma-ray emission over 23 9-day integration intervals for the red beam and 28 intervals for the blue beam is 0.0002 photons/sq cm per sec. These new limits from SMM can be reconciled with the HEAO 3 results only if SS 433 emits gamma radiation at or above the SMM sensitivity limit on rare occasions due to variable physical conditions in the system.

Improved color stability of white organic light-emitting diodes without interlayer between red, orange and blue emission layers

NASA Astrophysics Data System (ADS)

Xue, Kaiwen; Chen, Ping; Duan, Yu; Sheng, Ren; Han, Guangguang; Zhao, Yi

2016-03-01

We demonstrated color stability improved white phosphorescent organic light-emitting diodes (WOLEDs) based on red, orange and blue emission layers. Iridium(III) Bis(3,5-diflouro)-2-(2-pyridyl)phenyl-(2-carboxypyridyl) was doped into red emission layer (R-EML) and orange emission layer (O-EML) to lower the electrons injection barrier and facilitate the ambipolar charge carriers balance. Consequently, the recombination region was extended to the R-EML and O-EML, leading to the excellently stable spectra and the reduction of triplet-triplet annihilation. Then the resulting device with a negligible Commission International de L'Eclairage coordinates shift of (0.003, 0.007) within a wide luminance range as well as a high color rendering index of 90 was gained, which was comparable to the profit caused by the conventional method of introducing the interlayer. And the emission mechanism of the WOLEDs was also discussed.

Freestanding silicon quantum dots: origin of red and blue luminescence.

PubMed

Gupta, Anoop; Wiggers, Hartmut

2011-02-04

In this paper, we studied the behavior of silicon quantum dots (Si-QDs) after etching and surface oxidation by means of photoluminescence (PL) measurements, Fourier transform infrared spectroscopy (FTIR) and electron paramagnetic resonance spectroscopy (EPR). We observed that etching of red luminescing Si-QDs with HF acid drastically reduces the concentration of defects and significantly enhances their PL intensity together with a small shift in the emission spectrum. Additionally, we observed the emergence of blue luminescence from Si-QDs during the re-oxidation of freshly etched particles. Our results indicate that the red emission is related to the quantum confinement effect, while the blue emission from Si-QDs is related to defect states at the newly formed silicon oxide surface.

Engineering ESPT pathways based on structural analysis of LSSmKate red fluorescent proteins with large Stokes shift.

PubMed

Piatkevich, Kiryl D; Malashkevich, Vladimir N; Almo, Steven C; Verkhusha, Vladislav V

2010-08-11

LSSmKate1 and LSSmKate2 are monomeric red fluorescent proteins (RFPs) with large Stokes shifts (LSSs), which allows for efficient separation of absorbance and emission maxima, as well as for excitation with conventional two-photon laser sources. These LSSmKates differ by a single amino acid substitution at position 160 and exhibit absorbance maxima around 460 nm, corresponding to a neutral DsRed-like chromophore. However, excitation at 460 nm leads to fluorescence emission above 600 nm. Structures of LSSmKate1 and LSSmKate2, determined at resolutions of 2.0 and 1.5 A, respectively, revealed that the predominant DsRed-chromophore configurations are cis for LSSmKate1 but trans for LSSmKate2. Crystallographic and mutagenesis analyses, as well as isotope and temperature dependences, suggest that an excited-state proton transfer (ESPT) is responsible for the LSSs observed in LSSmKates. Hydrogen bonding between the chromophore hydroxyl and Glu160 in LSSmKate1 and a proton relay involving the chromophore tyrosine hydroxyl, Ser158, and the Asp160 carboxylate in LSSmKate2 represent the putative ESPT pathways. Comparisons with mKeima LSS RFP suggest that similar proton relays could be engineered in other FPs. Accordingly, we mutated positions 158 and 160 in several conventional red-shifted FPs, including mNeptune, mCherry, mStrawberry, mOrange, and mKO, and the resulting FP variants exhibited LSS fluorescence emission in a wide range of wavelengths from 560 to 640 nm. These data suggest that different chromophores formed by distinct tripeptides in different environments can be rationally modified to yield RFPs with novel photochemical properties.

Post-polymerization C-H Borylation of Donor-Acceptor Materials Gives Highly Efficient Solid State Near-Infrared Emitters for Near-IR-OLEDs and Effective Biological Imaging.

PubMed

Crossley, Daniel L; Urbano, Laura; Neumann, Robert; Bourke, Struan; Jones, Jennifer; Dailey, Lea Ann; Green, Mark; Humphries, Martin J; King, Simon M; Turner, Michael L; Ingleson, Michael J

2017-08-30

Post-polymerization modification of the donor-acceptor polymer, poly(9,9-dioctylfluorene-alt-benzothiadiazole), PF8-BT, by electrophilic C-H borylation is a simple method to introduce controllable quantities of near-infrared (near-IR) emitting chromophore units into the backbone of a conjugated polymer. The highly stable borylated unit possesses a significantly lower LUMO energy than the pristine polymer resulting in a reduction in the band gap of the polymer by up to 0.63 eV and a red shift in emission of more than 150 nm. Extensively borylated polymers absorb strongly in the deep red/near-IR and are highly emissive in the near-IR region of the spectrum in solution and solid state. Photoluminescence quantum yield (PLQY) values are extremely high in the solid state for materials with emission maxima ≥ 700 nm with PLQY values of 44% at 700 nm and 11% at 757 nm for PF8-BT with different borylation levels. This high brightness enables efficient solution processed near-IR emitting OLEDs to be fabricated and highly emissive borylated polymer loaded conjugated polymer nanoparticles (CPNPs) to be prepared. The latter are bright, photostable, low toxicity bioimaging agents that in phantom mouse studies show higher signal to background ratios for emission at 820 nm than the ubiquitous near-IR emissive bioimaging agent indocyanine green. This methodology represents a general approach for the post-polymerization functionalization of donor-acceptor polymers to reduce the band gap as confirmed by the C-H borylation of poly((9,9-dioctylfluorene)-2,7-diyl-alt-[4,7-bis(3-hexylthien-5-yl)-2,1,3-benzothiadiazole]-2c,2cc-diyl) (PF8TBT) resulting in a red shift in emission of >150 nm, thereby shifting the emission maximum to 810 nm.

Sensitivity of heterointerfaces on emission wavelength of quantum cascade lasers

NASA Astrophysics Data System (ADS)

Wang, C. A.; Schwarz, B.; Siriani, D. F.; Connors, M. K.; Missaggia, L. J.; Calawa, D. R.; McNulty, D.; Akey, A.; Zheng, M. C.; Donnelly, J. P.; Mansuripur, T. S.; Capasso, F.

2017-04-01

The measured emission wavelengths of AlInAs/GaInAs/InP quantum cascade lasers (QCLs) grown by metal organic vapor phase epitaxy (MOVPE) have been reported to be 0.5-1 μm longer than the designed QCL wavelength. This work clarifies the origin of the red-shifted wavelength. It was found that AlInAs/GaInAs heterointerfaces are compositionally graded over 2.5-4.5 nm, and indium accumulates at the AlInAs-to-GaInAs interface. Thus, the as-grown QCLs are far from the ideal abrupt interfaces used in QCL modeling. When graded layers are incorporated in QCL band structure and wavefunction calculations, the emission wavelengths are red shifted. Furthermore, we demonstrate that QCLs with graded interfaces can be designed without compromising performance and show greatly improved correlation between designed and measured emission wavelength. QCLs were designed for emission between 7.5 and 8.5 μm. These structures were grown and wet-etched ridge devices were fabricated. The QCLs exhibit room temperature peak powers exceeding 900 mW and pulsed efficiencies of 8 to 10%.

Ocular fundus auto-fluorescence observations at different wavelengths in patients with age-related macular degeneration and diabetic retinopathy.

PubMed

Hammer, Martin; Königsdörffer, Ekkehart; Liebermann, Christiane; Framme, Carsten; Schuch, Günter; Schweitzer, Dietrich; Strobel, Jürgen

2008-01-01

Post-translational protein modification by lipid peroxidation products or glycation is a feature of aging as well as pathologic processes in postmitotic cells at the ocular fundus exposed to an oxidative environment. The accumulation of modified proteins such as those found in lipofuscin and advanced glycation end products (AGEs) contribute greatly to the fundus auto-fluorescence. The distinct fluorescence spectra of lipofuscin and AGE enable their differentiation in multispectral fundus fluorescence imaging. A dual-centre consecutive case series of 78 pseudo-phacic patients is reported. Digital colour fundus photographs as well as auto-fluorescence images were taken from 33 patients with age related macular degeneration (AMD), 13 patients with diabetic retinopathy (RD), or from 32 cases without pathologic findings (controls). Fluorescence was excited at 475-515 nm or 476-604 nm and recorded in the emission bands 530-675 nm or 675-715 nm, respectively. Fluorescence images excited at 475-515 nm were taken by a colour CCD-camera (colour-fluorescence imaging) enabling the separate recording of green and red fluorescence. The ratio of green versus red fluorescence was calculated within a representative region of each image. The 530-675 nm auto-fluorescence in AMD patients was dominated by the red emission (green vs. red ratio, g/r = 0.861). In comparison, the fluorescence of the diabetics was green-shifted (g/r = 0.946; controls: g/r = 0.869). Atrophic areas (geographic atrophy, laser scars) showed massive hypo-fluorescence in both emission bands. Hyper-fluorescent drusen and exudates, unobtrusive in the colour fundus images as well as in the fluorescence images with emission >667 nm, showed an impressive green-shift in the colour-fluorescence image. Lipofuscin is the dominant fluorophore at long wavelengths (>675 nm or red channel of the colour fluorescence image). In the green spectral region, we found an additional emission of collagen and elastin (optic disc, sclera) as well as deposits in drusen and exudates. The green shift of the auto-fluorescence in RD may be a hint of increased AGE concentrations.

Luminescence studies of CdS spherical particles via hydrothermal synthesis

NASA Astrophysics Data System (ADS)

Xu, Guo Qin; Liu, Bing; Xu, Shi Jie; Chew, Chwee Har; Chua, Soo Jin; Gana, Leong Ming

2000-06-01

The spherical particles of CdS consisting of nanoparticles (∼100 nm) were synthesized by a hydrothermal process. The particle formation and growth depend on the rate of sulfide-ion generation and diffusion-controlled aggregation of nanoparticles. As demonstrated in the profiles of powder X-ray diffraction, the crystalline phases are governed by the reaction temperature. Photoluminescence studies on CdS particles show two emission bands at the room temperature. The red emission at 680 nm is due to sulfur vacancies, and a new infrared red (IR) emission at 760 nm is attributed to self-activated centers. A red shift of IR band with the decrease of temperature was explained with a configurational coordinate model. The different saturation limits for the red and IR bands are discussed in terms of the formation of donor-acceptor pairs and exciton in CdS particles.

Strategy for sensor based on fluorescence emission red shift of conjugated polymers: applications in pH response and enzyme activity detection.

PubMed

Tang, Yanli; Liu, Yue; Cao, Ali

2013-01-15

A new strategy was developed and applied in monitoring pH response and enzyme activity based on fluorescence emission red shift (FERS) of the conjugated polymer PPP-OR10 induced by the inner filter effect (IFE) of nitrobenzene derivatives. Neutral poly(p-phenylenes) functionalized with oligo(oxyethylene) side chains (PPP-OR10) was designed and synthesized by the Suzuki cross-coupling reaction. Nitrobenzene derivatives display different light absorption activities in the acidic or basic form due to adopting different electron-transition types. When environmental pH is higher than their pK(a) values, nitrobenzene derivatives exhibit strong absorbance around 400 nm, which is close to the maximal emission of polymer PPP-OR10. As a result, the maximal emission wavelength of PPP-OR10/nitrobenzene derivatives red shifts with the pH value increasing. Apparently, the IFE plays a very important role in this case. A new method has been designed that takes advantage of this pH-sensitive platform to sensor α-chymotrypsin (ChT) based on the IFE of p-nitroaniline, since the absorption spectrum of p-nitroaniline, the ChT-hydrolyzed product of N-benzoyl-L-tyrosine-p-nitroaniline (BTNA), overlaps with the emission spectrum of PPP-OR10. In addition, the present approach can detect α-chymotrypsin with a detection limit of 0.1 μM, which is lower than that of the corresponding absorption spectroscopy method. Furthermore, the pH response and enzyme detections can be carried out in 10% serum, which makes this new FERS-based strategy promising in applications in more complex conditions and a broader field.

Carbazole-based BODIPYs with ethynyl substituents at the boron center: solid-state excimer fluorescence in the VIS/NIR region.

PubMed

Maeda, Chihiro; Nagahata, Keiji; Ema, Tadashi

2017-09-26

Carbazole-based BODIPYs 1-6 with several different substituents at the boron atom site were synthesized. These dyes fluoresced in the solid state, and 3a with phenylethynyl groups exhibited a red-shifted and broad fluorescence spectrum, which suggested an excimer emission. Its derivatives 3b-n were synthesized, and the relationship between the solid-state emission and crystal packing was investigated. The X-ray crystal structures revealed cofacial dimers that might form excimers. From the structural optimization results, we found that the introduction of mesityl groups hindered intermolecular access and led to reduced interactions between the dimers. In addition, the red-shifted excimer fluorescence suppressed self-absorption, and dyes with ethynyl groups showed solid-state fluorescence in the vis/NIR region.

Photoinduced intramolecular charge transfer in a cross-conjugated push-pull enediyne: implications toward photoreaction.

PubMed

Singh, Anuja; Pati, Avik Kumar; Mishra, Ashok Kumar

2018-05-30

Push-pull organic fluorophores are important owing to their interesting optoelectronical properties. Here we report the photophysics of a new cross-conjugated push-pull enediynyl dye which belongs to an unexplored class of π-conjugated donor-acceptor systems. Two N,N-dimethylaniline moieties serve as donors and one pyrene ring functions as an acceptor via a common Y-shaped 'enediyne' bridge which facilitates the cross-electronic communication. The dye exhibits dual emission from locally excited (LE) and intramolecular charge transfer (ICT) states. While the LE emission is dominant in non-polar solvents, the ICT emission predominates in polar solvents. Time-resolved fluorescence decay experiments reveal a relatively shorter lifetime component (∼0.5-0.9 ns) belonging to an ICT state and a relatively longer lifetime species (∼1.6-2.8 ns) corresponding to the LE state. The strong ICT behavior of the dye is manifested through the huge red-shift (4166 cm-1) of the emission spectra from non-polar cyclohexane to polar N,N-dimethylformamide. In contrast to many small push-pull organic dyes, the LE and ICT states of the push-pull enediynyl dye follow the same excitation pathway. The dominant red-shifted ICT emission (∼550 nm) intensity of the dye in polar solvent decreases with a concomitant appearance of the blue-shifted LE emission (∼385 nm) upon prolonged exposure to photons. This opens up a new photophysical strategy of achieving high contrast two fluorescence color conversion from yellow to blue.

Controlled fluorescence in a beetle's photonic structure and its sensitivity to environmentally induced changes

PubMed Central

Kaczmarek, Anna M.; Vukusic, Peter; Deparis, Olivier; Van Hooijdonk, Eloise

2016-01-01

The scales covering the elytra of the male Hoplia coerulea beetle contain fluorophores embedded within a porous photonic structure. The photonic structure controls both insect colour (reflected light) and fluorescence emission. Herein, the effects of water-induced changes on the fluorescence emission from the beetle were investigated. The fluorescence emission peak wavelength was observed to blue-shift on water immersion of the elytra whereas its reflectance peak wavelength was observed to red-shift. Time-resolved fluorescence measurements, together with optical simulations, confirmed that the radiative emission is controlled by a naturally engineered photonic bandgap while the elytra are in the dry state, whereas non-radiative relaxation pathways dominate the emission response of wet elytra. PMID:28003460

Native fluorescence characterization of human liver abnormalities

NASA Astrophysics Data System (ADS)

Ganesan, Singaravelu; Madhuri, S.; Aruna, Prakasa R.; Suchitra, S.; Srinivasan, T. G.

1999-05-01

Fluorescence spectroscopy of intrinsic biomolecules has been extensively used in biology and medicine for the past several decades. In the present study, we report the native fluorescence characteristics of blood plasma from normal human subjects and patients with different liver abnormalities such as hepatitis, leptospirosis, jaundice, cirrhosis and liver cell failure. Native fluorescence spectra of blood plasma -- acetone extract were measured at 405 nm excitation. The average spectrum of normal blood plasma has a prominent emission peak around 464 nm whereas in the case of liver diseased subjects, the primary peak is red shifted with respect to normal. In addition, liver diseased cases show distinct secondary emission peak around 615 nm, which may be attributed to the presence of endogenous porphyrins. The red shift of the prominent emission peak with respect to normal is found to be maximum for hepatitis and minimum for cirrhosis whereas the secondary emission peak around 615 nm was found to be more prominent in the case of cirrhosis than the rest. The ratio parameter I465/I615 is found to be statistically significant (p less than 0.001) in discriminating liver abnormalities from normal.

Synthesis and Characterization of Water-Soluble Polythiophene Derivatives for Cell Imaging

NASA Astrophysics Data System (ADS)

Wang, Fengyan; Li, Meng; Wang, Bing; Zhang, Jiangyan; Cheng, Yongqiang; Liu, Libing; Lv, Fengting; Wang, Shu

2015-01-01

In this work, four water-soluble polythiophene derivatives (PT, PT-DDA, PT-ADA, and PT-ADA-PPR) with different pendant moieties were synthesized via oxidative copolymerization by FeCl3. By increasing the hydrophobic ability of side chain moieties, there is a gradually blue shift for the maximum absorption wavelength and red shift for the maximum emission wavelength, a reducing trend for fluorescence quantum yields, a growing trend for Stokes shift, and an increasing trend for the mean sizes in the order of PT, PT-ADA, and PT-DDA. All the synthesized polymers show low toxicity and good photostability and accumulate in the lysosomes of A549 cells. Furthermore, the introduction of porphyrin group to PT-ADA side chain (PT-ADA-PPR) broadens the absorption and emission ranges of PT-ADA. PT-ADA-PPR could be excited at two different excitation wavelengths (488 nm and 559 nm) and exhibits two emission pathways, and dual-color fluorescence images (orange and red) of PT-ADA-PPR accumulated in A549 cells are observed. Thus, PT-ADA-PPR could be used as an excellent dual-color fluorescent and lysosome-specific imaging material.

Photoprotective Energy Dissipation in Higher Plants Involves Alteration of the Excited State Energy of the Emitting Chlorophyll(s) in the Light Harvesting Antenna II (LHCII)*

PubMed Central

Johnson, Matthew P.; Ruban, Alexander V.

2009-01-01

Non-photochemical quenching (NPQ), a mechanism of energy dissipation in higher plants protects photosystem II (PSII) reaction centers from damage by excess light. NPQ involves a reduction in the chlorophyll excited state lifetime in the PSII harvesting antenna (LHCII) by a quencher. Yet, little is known about the effect of the quencher on chlorophyll excited state energy and dynamics. Application of picosecond time-resolved fluorescence spectroscopy demonstrated that NPQ involves a red-shift (60 ± 5 cm−1) and slight enhancement of the vibronic satellite of the main PSII lifetime component present in intact chloroplasts. Whereas this fluorescence red-shift was enhanced by the presence of zeaxanthin, it was not dependent upon it. The red-shifted fluorescence of intact chloroplasts in the NPQ state was accompanied by red-shifted chlorophyll a absorption. Nearly identical absorption and fluorescence changes were observed in isolated LHCII complexes quenched in a low detergent media, suggesting that the mechanism of quenching is the same in both systems. In both cases, the extent of the fluorescence red-shift was shown to correlate with the lifetime of a component. The alteration in the energy of the emitting chlorophyll(s) in intact chloroplasts and isolated LHCII was also accompanied by changes in lutein 1 observed in their 77K fluorescence excitation spectra. We suggest that the characteristic red-shifted fluorescence emission reflects an altered environment of the emitting chlorophyll(s) in LHCII brought about by their closer interaction with lutein 1 in the quenching locus. PMID:19567871

Photoprotective energy dissipation in higher plants involves alteration of the excited state energy of the emitting chlorophyll(s) in the light harvesting antenna II (LHCII).

PubMed

Johnson, Matthew P; Ruban, Alexander V

2009-08-28

Non-photochemical quenching (NPQ), a mechanism of energy dissipation in higher plants protects photosystem II (PSII) reaction centers from damage by excess light. NPQ involves a reduction in the chlorophyll excited state lifetime in the PSII harvesting antenna (LHCII) by a quencher. Yet, little is known about the effect of the quencher on chlorophyll excited state energy and dynamics. Application of picosecond time-resolved fluorescence spectroscopy demonstrated that NPQ involves a red-shift (60 +/- 5 cm(-1)) and slight enhancement of the vibronic satellite of the main PSII lifetime component present in intact chloroplasts. Whereas this fluorescence red-shift was enhanced by the presence of zeaxanthin, it was not dependent upon it. The red-shifted fluorescence of intact chloroplasts in the NPQ state was accompanied by red-shifted chlorophyll a absorption. Nearly identical absorption and fluorescence changes were observed in isolated LHCII complexes quenched in a low detergent media, suggesting that the mechanism of quenching is the same in both systems. In both cases, the extent of the fluorescence red-shift was shown to correlate with the lifetime of a component. The alteration in the energy of the emitting chlorophyll(s) in intact chloroplasts and isolated LHCII was also accompanied by changes in lutein 1 observed in their 77K fluorescence excitation spectra. We suggest that the characteristic red-shifted fluorescence emission reflects an altered environment of the emitting chlorophyll(s) in LHCII brought about by their closer interaction with lutein 1 in the quenching locus.

Optical waveguide and room temperature high-quality nanolasers from tin-catalyzed CdSSe nanostructures

NASA Astrophysics Data System (ADS)

Guo, Pengfei; Shen, Xia; Zhang, Baolong; Sun, Haibin; Zou, Zhijun; Yang, Wenchao; Gong, Ke; Luo, Yongsong

2018-05-01

A simple two-step CVD method is developed to realize the growth of high-quality tin-catalyzed CdSSe alloy nanowires. Microstructural characterizations demonstrate that these wires are high-quality crystalline nanostructures. Local photoluminescence investigation of these nanostructures shows a typical band edge emission at 656 nm with a full-width at half-maximum of 22.3 nm. Optical waveguide measurement along an individual nanowire indicates that the output signal of the guided light has a rapid linear decrease accompanied with maximum red-shift about 109 meV after the transmission of 102 μm. This obvious red-shift is caused by the intensive band-tail absorption during the optical transmission process. Moreover, optically pumped nanolasers are successfully realized at room temperature based on these unique wires, further demonstrating the achievement of stimulated emission from spontaneous emission, promoted by the pump power intensity. This work may find a simple route to the manufacture of superior nanowires for applications in waveguide and integrated photonic devices.

Optical waveguide and room temperature high-quality nanolasers from tin-catalyzed CdSSe nanostructures.

PubMed

Guo, Pengfei; Shen, Xia; Zhang, Baolong; Sun, Haibin; Zou, Zhijun; Yang, Wenchao; Gong, Ke; Luo, Yongsong

2018-05-04

A simple two-step CVD method is developed to realize the growth of high-quality tin-catalyzed CdSSe alloy nanowires. Microstructural characterizations demonstrate that these wires are high-quality crystalline nanostructures. Local photoluminescence investigation of these nanostructures shows a typical band edge emission at 656 nm with a full-width at half-maximum of 22.3 nm. Optical waveguide measurement along an individual nanowire indicates that the output signal of the guided light has a rapid linear decrease accompanied with maximum red-shift about 109 meV after the transmission of 102 μm. This obvious red-shift is caused by the intensive band-tail absorption during the optical transmission process. Moreover, optically pumped nanolasers are successfully realized at room temperature based on these unique wires, further demonstrating the achievement of stimulated emission from spontaneous emission, promoted by the pump power intensity. This work may find a simple route to the manufacture of superior nanowires for applications in waveguide and integrated photonic devices.

A photoswitchable orange-to-far-red fluorescent protein, PSmOrange.

PubMed

Subach, Oksana M; Patterson, George H; Ting, Li-Min; Wang, Yarong; Condeelis, John S; Verkhusha, Vladislav V

2011-07-31

We report a photoswitchable monomeric Orange (PSmOrange) protein that is initially orange (excitation, 548 nm; emission, 565 nm) but becomes far-red (excitation, 636 nm; emission, 662 nm) after irradiation with blue-green light. Compared to its parental orange proteins, PSmOrange has greater brightness, faster maturation, higher photoconversion contrast and better photostability. The red-shifted spectra of both forms of PSmOrange enable its simultaneous use with cyan-to-green photoswitchable proteins to study four intracellular populations. Photoconverted PSmOrange has, to our knowledge, the most far-red excitation peak of all GFP-like fluorescent proteins, provides diffraction-limited and super-resolution imaging in the far-red light range, is optimally excited with common red lasers, and can be photoconverted subcutaneously in a mouse. PSmOrange photoswitching occurs via a two-step photo-oxidation process, which causes cleavage of the polypeptide backbone. The far-red fluorescence of photoconverted PSmOrange results from a new chromophore containing N-acylimine with a co-planar carbon-oxygen double bond.

Spectral tuning of optical coupling between air-mode nanobeam cavities and individual carbon nanotubes

NASA Astrophysics Data System (ADS)

Machiya, Hidenori; Uda, Takushi; Ishii, Akihiro; Kato, Yuichiro K.

Air-mode nanobeam cavities allow for high efficiency coupling to air-suspended carbon nanotubes due to their unique mode profile that has large electric fields in air. Here we utilize heating-induced energy shift of carbon nanotube emission to investigate the cavity quantum electrodynamics effects. In particular, we use laser-induced heating which causes a large blue-shift of the nanotube photoluminescence as the excitation power is increased. Combined with a slight red-shift of the cavity mode at high powers, detuning of nanotube emission from the cavity can be controlled. We estimate the spontaneous emission coupling factor β at different spectral overlaps and find an increase of β factor at small detunings, which is consistent with Purcell enhancement of nanotube emission. Work supported by JSPS (KAKENHI JP26610080, JP16K13613), Asahi Glass Foundation, Canon Foundation, and MEXT (Photon Frontier Network Program, Nanotechnology Platform).

Photoinduced intramolecular charge transfer (ICT) reaction in trans-methyl p-(dimethylamino) cinnamate: A combined fluorescence measurement and quantum chemical calculations

NASA Astrophysics Data System (ADS)

Chakraborty, Amrita; Kar, Samiran; Guchhait, Nikhil

2006-01-01

The photophysical behaviour of trans-methyl p-(dimethylamino) cinnamate ( t-MDMAC) donor-acceptor system has been investigated by steady-state absorption and emission spectroscopy and quantum chemical calculations. The molecule t-MDMAC shows an emission from the locally excited state in non-polar solvents. In addition to weak local emission, a strong solvent dependent red shifted fluorescence in polar aprotic solvents is attributed to highly polar intramolecular charge transfer state. However, the formation of hydrogen-bonded clusters with polar protic solvents has been suggested from a linear correlation between the observed red shifted fluorescence band maxima with hydrogen bonding parameters ( α). Calculations by ab initio and density functional theory show that the lone pair electron at nitrogen center is out of plane of the benzene ring in the global minimum ground state structure. In the gas phase, a potential energy surface along the twist coordinate at the donor (-NMe 2) and acceptor (-CH = CHCOOMe) sites shows stabilization of S 1 state and destabilization S 2 and S 0 states. A similar potential energy calculation along the twist coordinate in acetonitrile solvent using non-equilibrium polarized continuum model also shows more stabilization of S 1 state relative to other states and supports solvent dependent red shifted emission properties. In all types of calculations it is found that the nitrogen lone pair is delocalized over the benzene ring in the global minimum ground state and is localized on the nitrogen centre at the 90° twisted configuration. The S 1 energy state stabilization along the twist coordinate at the donor site and localized nitrogen lone pair at the perpendicular configuration support well the observed dual fluorescence in terms of proposed twisted intramolecular charge transfer (TICT) model.

The role of proton precipitation in Jovian aurora: Theory and observation

NASA Technical Reports Server (NTRS)

Waite, J. H., Jr.; Curran, D. B.; Cravens, T. E.; Clarke, J. T.

1992-01-01

It was proposed that the Jovian auroral emissions observed by Voyager spacecraft could be explained by energetic protons precipitating into the upper atmosphere of Jupiter. Such precipitation of energetic protons results in Doppler-shifted Lyman alpha emission that can be quantitatively analyzed to determine the energy flux and energy distribution of the incoming particle beam. Modeling of the expected emission from a reasonably chosen Voyager energetic proton spectrum can be used in conjunction with International Ultraviolet Explorer (IUE) observations, which show a relative lack of red-shifted Lyman alpha emission, to set upper limits on the amount of proton precipitation taking place in the Jovian aurora. Such calculations indicate that less than 10 percent of the ultraviolet auroral emissions at Jupiter can be explained by proton precipitation.

A Zero-Dimensional Organic Seesaw-Shaped Tin Bromide with Highly Efficient Strongly Stokes-Shifted Deep-Red Emission

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhou, Chenkun; Lin, Haoran; Shi, Hongliang

The synthesis and characterization is reported of (C 9NH 20) 2SnBr 4, a novel organic metal halide hybrid with a zero-dimensional (0D) structure, in which individual seesaw-shaped tin (II) bromide anions (SnBr 4 2-) are co-crystallized with 1-butyl-1-methylpyrrolidinium cations (C 9NH 20 +). Upon photoexcitation, the bulk crystals exhibit a highly efficient broadband deep-red emission peaked at 695 nm, with a large Stokes shift of 332 nm and a high quantum efficiency of around 46 %. Furthermore, the unique photophysical properties of this hybrid material are attributed to two major factors: 1) the 0D structure allowing the bulk crystals tomore » exhibit the intrinsic properties of individual SnBr 4 2- species, and 2) the seesaw structure then enables a pronounced excited state structural deformation as confirmed by density functional theory (DFT) calculations.« less

Intravital multiphoton photoconversion with a cell membrane dye.

PubMed

Turcotte, Raphaël; Wu, Juwell W; Lin, Charles P

2017-02-01

Photoconversion, an irreversible shift in a fluorophore emission spectrum after light exposure, is a powerful tool for marking cellular and subcellular compartments and tracking their dynamics in vivo. This paper reports on the photoconversion properties of Di-8-ANEPPS, a commercially available membrane dye. When illuminated with near-infrared femtosecond laser pulses, Di-8-ANEPPS undergoes multiphoton photoconversion as indicated by the supralinear dependence of the conversion rate ρ pc on the incident power (ρpc∝Iexc2.27), and by the ability to photoconvert a thin optical section in a three-dimensional matrix. The characteristic emission spectrum changed from red to blue, and ratiometric analysis on single cells in vitro revealed a 65-fold increase in the blue to red wavelength ratio after photoconversion. The spectral shift is preserved in vivo for hours, making Di-8-ANEPPS a useful dye for intravital cell marking and tracking applications. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The recombination mechanisms leading to amplified spontaneous emission at the true-green wavelength in CH3NH3PbBr3 perovskites

NASA Astrophysics Data System (ADS)

Priante, D.; Dursun, I.; Alias, M. S.; Shi, D.; Melnikov, V. A.; Ng, T. K.; Mohammed, O. F.; Bakr, O. M.; Ooi, B. S.

2015-02-01

We investigated the mechanisms of radiative recombination in a CH3NH3PbBr3 hybrid perovskite material using low-temperature, power-dependent (77 K), and temperature-dependent photoluminescence (PL) measurements. Two bound-excitonic radiative transitions related to grain size inhomogeneity were identified. Both transitions led to PL spectra broadening as a result of concurrent blue and red shifts of these excitonic peaks. The red-shifted bound-excitonic peak dominated at high PL excitation led to a true-green wavelength of 553 nm for CH3NH3PbBr3 powders that are encapsulated in polydimethylsiloxane. Amplified spontaneous emission was eventually achieved for an excitation threshold energy of approximately 350 μJ/cm2. Our results provide a platform for potential extension towards a true-green light-emitting device for solid-state lighting and display applications.

Substantial Intramolecular Charge Transfer Induces Long Emission Wavelengths and Mega Stokes Shifts in 6-Aminocoumarins

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liu, Xiaogang; Cole, Jacqueline M.; Xu, Zhaochao

Coumarins are deployed in numerous bioimaging and biosensing applications. Among various coumarin derivatives, 6-aminocoumarins attract increasing attention for their red-shifted emissions, mega Stokes shifts, and significant solvatochromism. These spectral characteristics together with weak emission intensities have historically been ascribed to the formation of the twisted intramolecular charge transfer (TICT) state in 6-aminocoumarins. In this work, we demonstrate that it is actually substantial intramolecular charge transfer (ICT) that is responsible for these fluorescent properties. Based on this new understanding, we reanalyzed the sensing mechanism of a 6-aminocouarmin based fluorescent probe and obtained close agreement with experimental data. Lastly, our results leadmore » to a deeper understanding of the photophysics of 6-aminocoumarins and will inspire the rational development of novel fluorescent probes.« less

Substantial Intramolecular Charge Transfer Induces Long Emission Wavelengths and Mega Stokes Shifts in 6-Aminocoumarins

DOE PAGES

Liu, Xiaogang; Cole, Jacqueline M.; Xu, Zhaochao

2017-06-01

Coumarins are deployed in numerous bioimaging and biosensing applications. Among various coumarin derivatives, 6-aminocoumarins attract increasing attention for their red-shifted emissions, mega Stokes shifts, and significant solvatochromism. These spectral characteristics together with weak emission intensities have historically been ascribed to the formation of the twisted intramolecular charge transfer (TICT) state in 6-aminocoumarins. In this work, we demonstrate that it is actually substantial intramolecular charge transfer (ICT) that is responsible for these fluorescent properties. Based on this new understanding, we reanalyzed the sensing mechanism of a 6-aminocouarmin based fluorescent probe and obtained close agreement with experimental data. Lastly, our results leadmore » to a deeper understanding of the photophysics of 6-aminocoumarins and will inspire the rational development of novel fluorescent probes.« less

Approximate description of Stokes shifts in ICT fluorescence emission

NASA Astrophysics Data System (ADS)

Saielli, Giacomo; Braun, David; Polimeno, Antonino; Nordio, Pier Luigi

1996-07-01

The time-resolved emission spectrum of a dual fluorescent prototype system like DMABN is associated with an intramolecular adiabatic charge-transfer reaction and the simultaneous relaxation of the polarization coordinate describing the dynamic behaviour of the polar solvent. The dynamic Stokes shift of the frequency maximum of the long-wavelength emission band related to the charge-transfer (CT) state towards the red region is interpreted as a consequence of a kinetic pathway which deviates from steepest descent to the CT state, the rate-determining step being the solvent relaxation. The present stochastic treatment is based on the assumption that internal and solvent coordinates could be described separately, neglecting coupling elements in the case of slow solvent relaxation.

Emission shaping in fluorescent proteins: role of electrostatics and π-stacking.

PubMed

Park, Jae Woo; Rhee, Young Min

2016-02-07

For many decades, simulating the excited state properties of complex systems has been an intriguing but daunting task due to its high computational cost. Here, we apply molecular dynamics based techniques with interpolated potential energy surfaces toward calculating fluorescence spectra of the green fluorescent protein (GFP) and its variants in a statistically meaningful manner. With the GFP, we show that the diverse electrostatic tuning can shape the emission features in many different ways. By computationally modulating the electrostatic interactions between the chromophore phenoxy oxygen and its nearby residues, we demonstrate that we indeed can shift the emission to the blue or to the red side in a predictable manner. We rationalize the shifting effects of individual residues in the GFP based on the responses of both the adiabatic and the diabatic electronic states of the chromophore. We next exhibit that the yellow emitting variant, the Thr203Tyr mutant, generates changes in the electrostatic interactions and an additional π-stacking interaction. These combined effects indeed induce a red shift to emit the fluorescence into the yellow region. With the series of demonstrations, we suggest that our approach can provide sound rationales and useful insights in understanding different responses of various fluorescent complexes, which may be helpful in designing new light emitting proteins and other related systems in future studies.

Extended Stokes shift in fluorescent proteins: chromophore-protein interactions in a near-infrared TagRFP675 variant.

PubMed

Piatkevich, Kiryl D; Malashkevich, Vladimir N; Morozova, Kateryna S; Nemkovich, Nicolai A; Almo, Steven C; Verkhusha, Vladislav V

2013-01-01

Most GFP-like fluorescent proteins exhibit small Stokes shifts (10-45 nm) due to rigidity of the chromophore environment that excludes non-fluorescent relaxation to a ground state. An unusual near-infrared derivative of the red fluorescent protein mKate, named TagRFP675, exhibits the Stokes shift, which is 30 nm extended comparing to that of the parental protein. In physiological conditions, TagRFP675 absorbs at 598 nm and emits at 675 nm that makes it the most red-shifted protein of the GFP-like protein family. In addition, its emission maximum strongly depends on the excitation wavelength. Structures of TagRFP675 revealed the common DsRed-like chromophore, which, however, interacts with the protein matrix via an extensive network of hydrogen bonds capable of large flexibility. Based on the spectroscopic, biochemical, and structural analysis we suggest that the rearrangement of the hydrogen bond interactions between the chromophore and the protein matrix is responsible for the TagRFP675 spectral properties.

Red-shifted aequorin-based bioluminescent reporters for in vivo imaging of Ca2 signaling.

PubMed

Curie, Thomas; Rogers, Kelly L; Colasante, Cesare; Brûlet, Philippe

2007-01-01

Real-time visualization of calcium (Ca(2+)) dynamics in the whole animal will enable important advances in understanding the complexities of cellular function. The genetically encoded bioluminescent Ca(2+) reporter green fluorescent protein-aequorin (GA) allows noninvasive detection of intracellular Ca(2+) signaling in freely moving mice. However, the emission spectrum of GA is not optimal for detection of activity from deep tissues in the whole animal. To overcome this limitation, two new reporter genes were constructed by fusing the yellow fluorescent protein (Venus) and the monomeric red fluorescent protein (mRFP1) to aequorin. Transfer of aequorin chemiluminescence energy to Venus (VA) is highly efficient and produces a 58 nm red shift in the peak emission spectrum of aequorin. This substantially improves photon transmission through tissue, such as the skin and thoracic cage. Although the Ca(2+)-induced bioluminescence spectrum of mRFP1-aequorin (RA) is similar to that of aequorin, there is also a small peak above 600 nm corresponding to the peak emission of mRFP1. Small amounts of energy transfer between aequorin and mRFP1 yield an emission spectrum with the highest percentage of total light above 600 nm compared with GA and VA. Accordingly, RA is also detected with higher sensitivity from brain areas. VA and RA will therefore improve optical access to Ca(2+) signaling events in deeper tissues, such as the heart and brain, and offer insight for engineering new hybrid molecules.

Angle-resolved photoluminescence spectrum of a uniform phosphor layer

NASA Astrophysics Data System (ADS)

Fujieda, Ichiro; Ohta, Masamichi

2017-10-01

A photoluminescence spectrum depends on an emission angle due to self-absorption in a phosphor material. Assuming isotropic initial emission and Lambert-Beer's law, we have derived simple expressions for the angle-resolved spectra emerging from the top and bottom surfaces of a uniform phosphor layer. The transmittance of an excitation light through the phosphor layer can be regarded as a design parameter. For a strongly-absorbing phosphor layer, the forward flux is less intense and more red-shifted than the backward flux. The red-shift is enhanced as the emission direction deviates away from the plane normal. When we increase the transmittance, the backward flux decreases monotonically. The forward flux peaks at a certain transmittance value. The two fluxes become similar to each other for a weakly-absorbing phosphor layer. We have observed these behaviors in experiment. In a practical application, self-absorption decreases the efficiency of conversion and results in angle-dependent variations in chromaticity coordinates. A patterned phosphor layer with a secondary optical element such as a remote reflector alleviates these problems.

Novel type of red-shifted chlorophyll a antenna complex from Chromera velia. I. Physiological relevance and functional connection to photosystems.

PubMed

Kotabová, Eva; Jarešová, Jana; Kaňa, Radek; Sobotka, Roman; Bína, David; Prášil, Ondřej

2014-06-01

Chromera velia is an alveolate alga associated with scleractinian corals. Here we present detailed work on chromatic adaptation in C. velia cultured under either blue or red light. Growth of C. velia under red light induced the accumulation of a light harvesting antenna complex exhibiting unusual spectroscopic properties with red-shifted absorption and atypical 710nm fluorescence emission at room temperature. Due to these characteristic features the complex was designated "Red-shifted Chromera light harvesting complex" (Red-CLH complex). Its detailed biochemical survey is described in the accompanying paper (Bina et al. 2013, this issue). Here, we show that the accumulation of Red-CLH complex under red light represents a slow acclimation process (days) that is reversible with much faster kinetics (hours) under blue light. This chromatic adaptation allows C. velia to maintain all important parameters of photosynthesis constant under both light colors. We further demonstrated that the C. velia Red-CLH complex is assembled from a 17kDa antenna protein and is functionally connected to photosystem II as it shows variability of chlorophyll fluorescence. Red-CLH also serves as an additional locus for non-photochemical quenching. Although overall rates of oxygen evolution and carbon fixation were similar for both blue and red light conditions, the presence of Red-CLH in C. velia cells increases the light harvesting potential of photosystem II, which manifested as a doubled oxygen evolution rate at illumination above 695nm. This data demonstrates a remarkable long-term remodeling of C. velia light-harvesting system according to light quality and suggests physiological significance of 'red' antenna complexes. Copyright © 2014 Elsevier B.V. All rights reserved.

High-Performance Blue-Excitable Yellow Phosphor Obtained from an Activated Solvochromic Bismuth-Fluorophore Metal–Organic Framework

DOE PAGES

Deibert, Benjamin J.; Velasco, Ever; Liu, Wei; ...

2016-06-23

Here, we report the synthesis, structure, and photoluminescence properties of a new bismuth based luminescent metal-organic framework (LMOF). The framework is comprised of a 9-coordinated Bi 3+ building unit and 4', 4''', 4''''', 4'''''''-(ethene-1,1,2,2-tetrayl)tetrakis([1,1'-biphenyl]-4-carboxylic acid) (H 4tcbpe) organic linker, which has strong yellow aggregation induced emission (AIE). The structure can be viewed as two interpenetrated 4,4-anionic nets that are stabilized by K + ions forming one-dimensional helical inorganic chains by connecting bismuth nodes through shared oxygen bonds. The as-made LMOF has a bluish emission centered at 459 nm with an internal quantum yield of 57% when excited at 360 nm.more » The emission properties of the LMOF were found to be highly solvochromic with respect to DMF. Upon partial solvent removal, the framework undergoes significant red-shifting to a greenish emission centered at 500 nm. Complete removal of DMF results in additional red-shifting fluorescence coupled with structural changes. The resulting material has strong blue-excitable (455 nm) yellow emission centered at 553 nm, with a quantum yield of 74%, which is maintained after heating in air for 5 days at 90°C. This is the second highest quantum yield value for blue-excited yellow emission among all reported LMOFs.« less

High-Performance Blue-Excitable Yellow Phosphor Obtained from an Activated Solvochromic Bismuth-Fluorophore Metal–Organic Framework

DOE Office of Scientific and Technical Information (OSTI.GOV)

Deibert, Benjamin J.; Velasco, Ever; Liu, Wei

Here, we report the synthesis, structure, and photoluminescence properties of a new bismuth based luminescent metal-organic framework (LMOF). The framework is comprised of a 9-coordinated Bi 3+ building unit and 4', 4''', 4''''', 4'''''''-(ethene-1,1,2,2-tetrayl)tetrakis([1,1'-biphenyl]-4-carboxylic acid) (H 4tcbpe) organic linker, which has strong yellow aggregation induced emission (AIE). The structure can be viewed as two interpenetrated 4,4-anionic nets that are stabilized by K + ions forming one-dimensional helical inorganic chains by connecting bismuth nodes through shared oxygen bonds. The as-made LMOF has a bluish emission centered at 459 nm with an internal quantum yield of 57% when excited at 360 nm.more » The emission properties of the LMOF were found to be highly solvochromic with respect to DMF. Upon partial solvent removal, the framework undergoes significant red-shifting to a greenish emission centered at 500 nm. Complete removal of DMF results in additional red-shifting fluorescence coupled with structural changes. The resulting material has strong blue-excitable (455 nm) yellow emission centered at 553 nm, with a quantum yield of 74%, which is maintained after heating in air for 5 days at 90°C. This is the second highest quantum yield value for blue-excited yellow emission among all reported LMOFs.« less

Mn2+ concentration manipulated red emission in BaMg2Si2O7:Eu2+,Mn2+

NASA Astrophysics Data System (ADS)

Ye, Song; Zhang, Jiahua; Zhang, Xia; Lu, Shaozhe; Ren, Xinguang; Wang, Xiaojun

2007-02-01

The luminescent properties of concentration dependence are reported in BaMg2Si2O7:Eu2+,Mn2+ red phosphor. It is observed that the broad red emission of Mn2+ consists of two bands, located at 620 and 675 nm, respectively, which are attributed to two different Mn2+ centers [Mn2+(I) and Mn2+(II)] substituting for two nonidentical Mg2+ sites [Mg2+(I) and Mg2+(II)] in the host. It is also found that the relative emission intensity of the Mn2+(II) to the Mn2+(I) increases with increasing Mn2+ concentration, leading to a red-shift of the overall emission. A detail analysis on the energy transfer from Eu2+ to the two Mn2+ centers is presented, which indicates that the number ratio of Mn2+(II) to Mn2+(I) increases with increasing Mn2+ concentration. This result is interpreted by the preferential formation of Mn2+(I) substituting for Mg2+(I) site. Based on energy transfer, the emission intensity ratios of Mn2+(I) to Eu2+ and Mn2+(II) to Eu2+, which is Mn2+ concentration dependent, are calculated using related fluorescence lifetimes. The calculated results are in good agreement with that obtained experimentally in the emission spectra.

Energy transfer in aggregated CuInS2/ZnS core-shell quantum dots deposited as solid films

NASA Astrophysics Data System (ADS)

Gardelis, S.; Fakis, M.; Droseros, N.; Georgiadou, D.; Travlos, A.; Nassiopoulou, A. G.

2017-01-01

We report on the morphology and optical properties of CuInS2/ZnS core-shell quantum dots in solid films by means of AFM, SEM, HRTEM, steady state and time-resolved photoluminescence (PL) spectroscopy. The amount of aggregation of the CuInS2/ZnS QDs was controlled by changing the preparation conditions of the films. A red-shift of the PL spectrum of CuInS2/ZnS core-shell quantum dots, deposited as solid films on silicon substrates, is observed upon increasing the amount of aggregation. The presence of larger aggregates was found to lead to a larger PL red-shift. Besides, as the degree of aggregation increased, the PL decay became slower. We attribute the observed PL red-shift to energy transfer from the smaller to the larger dots within the aggregates, with the emission being realized via a long decay recombination mechanism (100-200 ns), the origin of which is discussed.

ICT-Isomerization-Induced Turn-On Fluorescence Probe with a Large Emission Shift for Mercury Ion: Application in Combinational Molecular Logic.

PubMed

Bhatta, Sushil Ranjan; Mondal, Bijan; Vijaykumar, Gonela; Thakur, Arunabha

2017-10-02

A unique turn-on fluorescent device based on a ferrocene-aminonaphtholate derivative specific for Hg 2+ cation was developed. Upon binding with Hg 2+ ion, the probe shows a dramatic fluorescence enhancement (the fluorescence quantum yield increases 58-fold) along with a large red shift of 68 nm in the emission spectrum. The fluorescence enhancement with a red shift may be ascribed to the combinational effect of C═N isomerization and an extended intramolecular charge transfer (ICT) mechanism. The response was instantaneous with a detection limit of 2.7 × 10 -9 M. Upon Hg 2+ recognition, the ferrocene/ferrocenium redox peak was anodically shifted by ΔE 1/2 = 72 mV along with a "naked eye" color change from faint yellow to pale orange for this metal cation. Further, upon protonation of the imine nitrogen, the present probe displays a high fluorescence output due to suppression of the C═N isomerization process. Upon deprotonation using strong base, the fluorescence steadily decreases, which indicates that H + and OH - can be used to regulate the off-on-off fluorescence switching of the present probe. Density functional theory studies revealed that the addition of acid leads to protonation of the imine N (according to natural bond orbital analysis), and the resulting iminium proton forms a strong H-bond (2.307 Å) with one of the triazole N atoms to form a five-membered ring, which makes the molecule rigid; hence, enhancement of the ICT process takes place, thereby leading to a fluorescence enhancement with a red shift. The unprecedented combination of H + , OH - , and Hg 2+ ions has been used to generate a molecular system exhibiting the INHIBIT-OR combinational logic operation.

Explaining observed red and blue-shifts using multi-stranded coronal loops

NASA Astrophysics Data System (ADS)

Regnier, S.; Walsh, R. W.; Pearson, J.

2012-03-01

Magnetic plasma loops have been termed the building blocks of the solar atmosphere. However, it must be recognised that if the range of loop structures we can observe do consist of many ''sub-resolution'' elements, then current one-dimensional hydrodynamic models are really only applicable to an individual plasma element or strand. Thus a loop should be viewed is an amalgamation of these strands. They could operate in thermal isolation from one another with a wide range of temperatures occurring across the structural elements. This scenario could occur when the energy release mechanism consists of localised, discrete bursts of energy that are due to small scale reconnection sites within the coronal magnetic field- the nanoflare coronal heating mechanism. These energy bursts occur in a time-dependent manner, distributed along the loop/strand length, giving a heating function that depends on space and time. An important observational discovery with the Hinode/EIS spectrometer is the existence of red and blue-shifts in coronal loops depending on the location of the footpoints (inner or outer parts of the active region), and the temperature of the emission line in which the Doppler shifts are measured. Based on the multi-stranded model developed by Sarkar and Walsh (2008, ApJ, 683, 516), we show that red and blue-shifts exist in different simulated Hinode/EIS passbands: cooler lines (OV-SiVII) being dominated by red-shifts, whilst hotter lines (FeXV-CaXVII) are a combination of both. The distribution of blue-shifts depends on the energy input and not so much on the heating location. Characteristic Doppler shifts generated fit well with observed values. We also simulate the Hinode/EIS rasters to closely compare our simulation with the observations. Even if not statistically significant, loops can have footpoints with opposite Doppler shifts.

Color-tunable, aggregation-induced emission of a butterfly-shaped molecule comprising a pyran skeleton and two cholesteryl wings.

PubMed

Tong, Hui; Hong, Yuning; Dong, Yongqiang; Ren, Yan; Häussler, Matthias; Lam, Jacky W Y; Wong, Kam Sing; Tang, Ben Zhong

2007-03-01

A chiral pyran derivative containing two cholesteryl groups (1) is synthesized, and its optical properties are investigated. Whereas the isolated molecule of 1 is virtually nonluminescent in dilute solutions, it becomes highly emissive with a 2 orders of magnitude increase in fluorescence quantum yield upon aggregation in poor solvents or in solid state, showing a novel phenomenon of aggregation-induced emission (AIE). The color and efficiency of the AIE of 1 can be tuned by varying the morphology of its aggregates: photoluminescence of its aggregates formed in a tetrahydrofuran/water mixture progressively red-shifts (green --> yellow --> red) with increasing water content of the mixture, with the crystalline aggregates emitting bluer lights in higher efficiencies than their amorphous counterparts.

Ultraviolet and optical observations of metal deficient red giants and chromospheric models

NASA Technical Reports Server (NTRS)

Duprele, A. K.; Avrett, E. H.; Hartmann, L.; Smith, G.

1984-01-01

Three metal deficient field stars were observed in the ultraviolet and optical spectral regions: HD 165195, HD 110281, and HD 232078. High dispersion spectra near H alpha, and low dispersion, long wavelength IUE spectra were obtained. The H alpha profiles have strong asymmetric emission with absorption cores that are frequently asymmetric. The surface flux of Mg II lines is similar to that of luminous Pop I stars in spite of the lower metal abundance. Semi-empirical atmospheric models suggest that the characteristic emission in the wings of the H alpha line can arise within static chromospheres. Radial expansion gives an asymmetric, blue-shifted H alpha core accompanied by greater emission in the red line wing than the blue wing. Wind models with extended atmospheres suggest mass loss rates - 2 billion M/yr. Thus H alpha provides no evidence that steady mass loss is substantial enough to significantly affect the evolution of stars on the red giant branch of globular clusters.

A search for N-type galaxies

NASA Technical Reports Server (NTRS)

Jefferies, J. T.

1971-01-01

A large number of distant clusters of galaxies was examined for the presence of a bright compact galaxy or blue stellar object. Nearly 600 square degrees of sky were searched using glass copies of the National Geographic Society-Palomar Observatory Sky Survey plates, and over 20 fields were selected for observation. The objects were examined for infrared and ultraviolet excesses, using wideband filter photography and spectroscopy. Initial findings include a faint, distant cluster of galaxies near the quasi-stellar radio source 4C 37.43 with a red shift of 0.370. One of these galaxies has an emission line at 6895 A, indicating a possible red shift of 0.377 of the 5007 A line of (0 III).

Spectrally and angularly resolved measurements of three-halves harmonic emission from laser-produced plasmas

NASA Astrophysics Data System (ADS)

Kang, N.; Liu, H.; Lin, Z.; Lei, A.; Zhou, S.; Fang, Z.; An, H.; Li, K.; Fan, W.

2017-10-01

Spectra of three-halves harmonic emissions (3{ω }0/2) from laser-produced plasmas were measured at different angles, including both forward and backward sides, from the direction of incident laser beams. The 3{ω }0/2 emitted from carbon-hydrogen (CH) targets was observed to be larger than that from aluminum (Al) targets with the same incident laser intensity, which supports the argument that the two-plasmon decay (TPD) instability could be inhibited by using medium-Z ablator instead of CH ablator in direct-drive inertial confinement fusion. Besides, the measured 3{ω }0/2-incident intensity curves for both materials suggest relatively lower threshold of TPD than the calculated values. In experiments with thin Al targets, the angular distribution of the blue- and red-shifted peaks of 3{ω }0/2 spectra were obtained, which shows that the most intense blue- and red-shifted peaks may not be produced in paired plasmons, but the spectra produced by their ‘twin’ plasmons were not observed. Because 3{ω }0/2 may have been influenced by other physical processes during their propagation from their birth places to the detectors, the mismatches on emission angle, wavelength shift, and threshold may be qualitatively explained through the assumption that small-scale light filaments widely existed in the corona of laser-produced plasmas.

Hg-Xe exciplex formation in mixed Xe/Ar matrices: molecular dynamics and luminescence study.

PubMed

Lozada-García, Rolando; Rojas-Lorenzo, Germán; Crépin, Claudine; Ryan, Maryanne; McCaffrey, John G

2015-03-19

Luminescence of Hg((3)P1) atoms trapped in mixed Ar/Xe matrices containing a small amount of Xe is reported. Broad emission bands, strongly red-shifted from absorption are recorded which are assigned to strong complexes formed between the excited mercury Hg* and xenon atoms. Molecular dynamics calculations are performed on simulated Xe/Ar samples doped with Hg to follow the behavior of Hg* in the mixed rare gas matrices leading to exciplex formation. The role of Xe atoms in the first solvation shell (SS1) around Hg was investigated in detail, revealing the formation of two kinds of triatomic exciplexes; namely, Xe-Hg*-Xe and Ar-Hg*-Xe. The first species exists only when two xenon atoms are present in SS1 with specific geometries allowing the formation of a linear or quasi-linear exciplex. In the other geometries, or in the presence of only one Xe in SS1, a linear Ar-Hg*-Xe exciplex is formed. The two kinds of exciplexes have different emission bands, the most red-shifted being that involving two Xe atoms, whose emission is very close to that observed in pure Xe matrices. Simulations give a direct access to the analysis of the experimental absorption, emission, and excitation spectra, together with the dynamics of exciplexes formation.

Emission wavelength red-shift by using ;semi-bulk; InGaN buffer layer in InGaN/InGaN multiple-quantum-well

NASA Astrophysics Data System (ADS)

Alam, Saiful; Sundaram, Suresh; Li, Xin; El Gmili, Youssef; Elouneg-Jamroz, Miryam; Robin, Ivan Christophe; Patriarche, Gilles; Salvestrini, Jean-Paul; Voss, Paul L.; Ougazzaden, Abdallah

2017-12-01

We report an elongation of emission wavelength by inserting a ∼70 nm thick high quality semi-bulk (SB) InyGa1-yN buffer layer underneath the InxGa1-xN/InyGa1-yN (x > y) multi-quantum-well (MQW).While the MQW structure without the InGaN SB buffer is fully strained on the n-GaN template, the MQW structure with the buffer has ∼15% relaxation. This small relaxation along with slight compositional pulling induced well thickness increase of MQW is believed to be the reason for the red-shift of emission wavelength. In addition, the SB InGaN buffer acts as an electron reservoir and also helps to reduce the Quantum Confined Stark Effect (QCSE) and thus increase the emission intensity. In this way, by avoiding fully relaxed buffer induced material degradation, a longer emission wavelength can be achieved by just using InGaN SB buffer while keeping all other growth conditions the same as the reference structure. Thus, a reasonably thick fully strained or very little relaxed InGaN buffer, which is realized by ;semi-bulk; approach to maintain good InGaN material quality, can be beneficial for realizing LEDs, grown on top of this buffer, emitting in the blue to cyan to green regime without using excess indium (In).

Spectral Properties of Er3+/Tm3+ Co-Doped ZBLAN Glasses and Fibers

PubMed Central

Liao, Xili; Jiang, Xiaobo; Yang, Qiuhong; Wang, Longfei; Chen, Danping

2017-01-01

A series of Er3+/Tm3+ co-doped fluoride (ZBLAN) glasses and fibers was prepared and their fluorescence spectra was measured under excitation at 793 nm and 980 nm. Correlation between the self-absorption effect of rare-earth ions and the shift of the emission peak was investigated. With the increasing length of fiber, the emission peaks red-shift when self-absorption occurs at the upper level of emission transition or blue-shift when that occurs at the lower level. As a result of the strong self-absorption effect, Er3+/Tm3+ co-doped fibers mainly yield 1390–1470, 1850–1980, and 2625–2750 nm emissions when excited at 793 nm, and 1480–1580, 1800–1980, and 2625–2750 nm emissions when excited at 980 nm. Further, a broadband emission in the range of 1410–1580 nm covering the S + C communication band was obtained by the dual-pumping scheme of 793 nm and 980 nm. Results suggest that the dual-pumping scheme would be more effective and important for an Er3+/Tm3+ co-doped fiber amplifier working in the S + C communication band. PMID:28772846

Spectral Properties of Er3+/Tm3+ Co-Doped ZBLAN Glasses and Fibers.

PubMed

Liao, Xili; Jiang, Xiaobo; Yang, Qiuhong; Wang, Longfei; Chen, Danping

2017-05-03

A series of Er 3+ /Tm 3+ co-doped fluoride (ZBLAN) glasses and fibers was prepared and their fluorescence spectra was measured under excitation at 793 nm and 980 nm. Correlation between the self-absorption effect of rare-earth ions and the shift of the emission peak was investigated. With the increasing length of fiber, the emission peaks red-shift when self-absorption occurs at the upper level of emission transition or blue-shift when that occurs at the lower level. As a result of the strong self-absorption effect, Er 3+ /Tm 3+ co-doped fibers mainly yield 1390-1470, 1850-1980, and 2625-2750 nm emissions when excited at 793 nm, and 1480-1580, 1800-1980, and 2625-2750 nm emissions when excited at 980 nm. Further, a broadband emission in the range of 1410-1580 nm covering the S + C communication band was obtained by the dual-pumping scheme of 793 nm and 980 nm. Results suggest that the dual-pumping scheme would be more effective and important for an Er 3+ /Tm 3+ co-doped fiber amplifier working in the S + C communication band.

Study on electrical structure and magneto-optical properties of W-doped ZnO

NASA Astrophysics Data System (ADS)

Li, Yong; Hou, Qingyu; Zhao, Chunwang; Xu, Zhenchao

2018-04-01

For W-doping amounts ranging from 0.0417 to 0.0833, experimental UV-visible absorption spectra blue shift and red shift results have been reported in the literatures. However, there is few literature reported research on magnetic mechanism. To solve this problem, this study investigates the disagreement about blue shift and red shift results and research on magnetic mechanism. The band structures, density of states, absorption spectra and magnetism have been investigated using first-principles planewave ultrasoft pseudopotential method based on the density functional theory. The calculated results showed that increased W-doping amounts first increase the volumes, and then reduce the volumes, decrease the formation energies, and stabilize the doped system. The band gaps become narrower and the absorption spectrum exhibits a significant red shift in UV and visible light emission. Moreover, the covalent bond vertical to c-axis strengthens, and the ionic bond parallel to c-axis weakens. Increased W-doping amounts decrease the magnetism of doped system. The magnetism of doped system originates from the electron exchange among W-5d, O-2p and Zn-3d orbitals of the W-doped ZnO. In W double-doped system, the ferromagnetic Curie temperature can be above room temperature when the doped system has a longer W-W distance.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dong, Wen-Wen; Xia, Liang; Peng, Zhen

Under solvothermal conditions, the reactions of Co{sup II}/Zn{sup II} ions with bent ligand 3-(pyridin-4-yl)-5-(pyrazin-2-yl)-1H-1,2,4-triazole (4-Hpzpt) afford two compounds {[M(4-pzpt)_2] guest}{sub n} (guest=H{sub 2}O, M=Co{sup II} (1), Zn{sup II} (2)). Both compounds are the thermally and hydrolytically robust 4-connected 3D NbO framework, which formed by double helical chains to give rise to 1D hollow nanochannel with uncoordinated nitrogens completely exposed on the pore surface. Compound 1 exhibits improved N{sub 2}, CO{sub 2} and H{sub 2} uptake capacities, while compound 2 displays the strong luminescent emission with obvious red shift. - Graphical abstract: Two 2-fold interpenetrated NbO-type MOFs with 1D nanochannel weremore » synthesized. Compound 1 exhibits improved N{sub 2}, CO{sub 2} and H{sub 2} uptake capacities, while compound 2 displays the strong fluorescent emission with obvious red shift. Display Omitted.« less

New localized/delocalized emitting state of Eu 2+ in orange-emitting hexagonal EuAl 2O 4

DOE PAGES

Liu, Feng; Meltzer, Richard S.; Li, Xufan; ...

2014-11-18

Eu 2+-activated phosphors are being widely used in illuminations and displays. Some of these phosphors feature an extremely broad and red-shifted Eu 2+ emission band; however, convincing explanation of this phenomenon is lacking. Here we report a new localized/delocalized emitting state of Eu 2+ ions in a new hexagonal EuAl 2O 4 phosphor whose Eu 2+ luminescence exhibits a very large bandwidth and an extremely large Stokes shift. At 77 K, two luminescent sites responsible for 550 nm and 645 nm broadband emissions are recognized, while at room temperature only the 645 nm emission band emits. The 645 nm emissionmore » exhibits a typical radiative lifetime of 1.27 μs and an unusually large Stokes shift of 0.92 eV. We identify the 645 nm emission as originating from a new type of emitting state whose composition is predominantly that of localized 4f 65d character but which also contains a complementary component with delocalized conduction-band-like character. This investigation gives new insights into a unique type of Eu 2+ luminescence in solids whose emission exhibits both a very large bandwidth and an extremely large Stokes shift.« less

Resonant Pump-dump Quantum Control of Solvated Dye Molecules with Phase Jumps

NASA Astrophysics Data System (ADS)

Konar, Arkaprabha; Lozovoy, Vadim; Dantus, Marcos

2014-03-01

Quantum coherent control of two photon and multiphoton excitation processes in atomic and condensed phase systems employing phase jumps has been well studied and understood. Here we demonstrate coherent quantum control of a two photon resonant pump-dump process in a complex solvated dye molecule. Phase jump in the frequency domain via a pulse shaper is employed to coherently enhance the stimulated emission by an order of magnitude when compared to transform limited pulses. Red shifted stimulated emission from successive low energy Stokes shifted excited states leading to narrowband emission are observed upon scanning the pi step across the excitation spectrum. A binary search space routine was also employed to investigate the effects of other types of phase jumps on stimulated emission and to determine the optimum phase that maximizes the emission. Understanding the underlying mechanism of this kind of enhancement will guide us in designing pulse shapes for enhancing stimulated emission, which can be further applied in the field of imaging.

LIVING WITH A RED DWARF: ROTATION AND X-RAY AND ULTRAVIOLET PROPERTIES OF THE HALO POPULATION KAPTEYN’S STAR

DOE Office of Scientific and Technical Information (OSTI.GOV)

Guinan, Edward F.; Engle, Scott G.; Durbin, Allyn, E-mail: scott.engle@villanova.edu

As part of Villanova’s Living with a Red Dwarf program, we have obtained UV, X-ray, and optical data of the Population II red dwarf—Kapteyn’s Star. Kapteyn’s Star is noteworthy for its large proper motions and high radial velocity of ∼+245 km s{sup −1}. As the nearest Pop II red dwarf, it serves as an old age anchor for calibrating activity/irradiance–rotation–age relations, and an important test bed for stellar dynamos and the resulting X-ray–UV emissions of slowly rotating, near-fully convective red dwarf stars. Adding to the notoriety, Kapteyn’s Star has recently been reported to host two super-Earth candidates, one of whichmore » (Kapteyn b) is orbiting within the habitable zone. However, Robertson et al. questioned the planet’s existence since its orbital period may be an artifact of activity, related to the star’s rotation period. Because of its large Doppler-shift, measures of the important, chromospheric H i Lyα 1215.67 Å emission line can be reliably made, because it is mostly displaced from ISM and geo-coronal sources. Lyα emission dominates the FUV region of cool stars. Our measures can help determine the X-ray–UV effects on planets hosted by Kapteyn’s Star, and planets hosted by other old red dwarfs. Stellar X-ray and Lyα emissions have strong influences on the heating and ionization of upper planetary atmospheres and can (with stellar winds and flares) erode or even eliminate planetary atmospheres. Using our program stars, we have reconstructed the past exposures of Kapteyn’s Star's planets to coronal—chromospheric XUV emissions over time.« less

Spectrophotometric Study of the Region of the Sky Around the Galaxies Markarian 261 and 262

NASA Astrophysics Data System (ADS)

Khachikian, E. Ye.; Sargsyan, L. A.

2005-10-01

Results are presented from a detailed spectrophotometric study of a unique system of physically coupled galaxies whose spectra contain identical emission lines. This system consists of four galaxies, three of which have a double or multiple structure in their central portions and are, by definition, galaxies with two or multiple nuclei. Two of these objects are the galaxies with an ultraviolet excess (UVE), Mark 261 and Mark 262, while one is a galaxy made up of two identical starlike nuclei that are referred to as the “twin objects.” In the DSS2 charts, the latter show up as two adjacent stars without any surroundings. However, there are two condensations between these starlike nuclei. The fourth object has a triplet structure. It is shown here that all these objects have the same emission (line) spectra and red shifts. All the physical characteristics that can be determined from the spectra are determined: red shifts, relative intensities of emission lines, their equivalent widths, distances to the galaxies, etc. It is concluded that the members of this system have a common origin, more or less consistent with Ambartsumyan's idea of the fragmentation of an isolated, high density body.

Hydrogen bond strengthening induces fluorescence quenching of PRODAN derivative by turning on twisted intramolecular charge transfer

NASA Astrophysics Data System (ADS)

Yang, Yonggang; Li, Donglin; Li, Chaozheng; Liu, YuFang; Jiang, Kai

2017-12-01

Researchers have proposed different effective mechanisms of hydrogen bonding (HB) on the fluorescence of 6-propionyl-2-dimethylaminonaphthalene (PRODAN) and its derivatives. Herein, excited state transition and dynamics analysis confirm that the fluorescence of PD (a derivative of PRODAN with ethyl replaced by 3-hydroxy-2,2-dimethylpropan) emits from the planar intramolecular charge transfer (PICT) state rather than twist ICT (TICT) state, because the fluorescence emission and surface hopping from the TICT state to the twist ground (T-S0) state is energy forbidden. Nevertheless, the strengthening of intramolecular-HB (intra-HB) and intermolecular-HB (inter-HB) of PD-(methanol)2 smooth the pathway of surface hopping from TICT to T-S0 state and the external conversion going to planar ground state by decreasing the energy difference of the two states. This smoothing changes the fluorescence state of PD-(methanol)2 to the TICT state in which fluorescence emission does not occur but surface hopping, leading to the partial fluorescence quenching of PD in methanol solvent. This conclusion is different from previous related reports. Moreover, the inter-HB strengthening of PD-methanol in PICT state induces the cleavage of intra-HB and a fluorescence red-shift of 54 nm compared to PD. This red-shift increases to 66 nm for PD-(methanol)2 for the strengthening of the one intra-HB and two inter-HBs. The dipole moments of PD-methanol and PD-(methanol)2 respectively increase about 10.3D and 8.1D in PICT state compared to PD. The synergistic effect of intra-HB and inter-HB induces partial quenching of PD in methanol solvent by turning on the TICT state and fluorescence red-shift. This work gives a reasonable description on the fluorescence red-shift and partial quenching of PD in methanol solvent, which will bring insight into the study of spectroscopic properties of molecules owning better spectral characteristics.

Hydrogen bond strengthening induces fluorescence quenching of PRODAN derivative by turning on twisted intramolecular charge transfer.

PubMed

Yang, Yonggang; Li, Donglin; Li, Chaozheng; Liu, YuFang; Jiang, Kai

2017-12-05

Researchers have proposed different effective mechanisms of hydrogen bonding (HB) on the fluorescence of 6-propionyl-2-dimethylaminonaphthalene (PRODAN) and its derivatives. Herein, excited state transition and dynamics analysis confirm that the fluorescence of PD (a derivative of PRODAN with ethyl replaced by 3-hydroxy-2,2-dimethylpropan) emits from the planar intramolecular charge transfer (PICT) state rather than twist ICT (TICT) state, because the fluorescence emission and surface hopping from the TICT state to the twist ground (T-S 0 ) state is energy forbidden. Nevertheless, the strengthening of intramolecular-HB (intra-HB) and intermolecular-HB (inter-HB) of PD-(methanol) 2 smooth the pathway of surface hopping from TICT to T-S 0 state and the external conversion going to planar ground state by decreasing the energy difference of the two states. This smoothing changes the fluorescence state of PD-(methanol) 2 to the TICT state in which fluorescence emission does not occur but surface hopping, leading to the partial fluorescence quenching of PD in methanol solvent. This conclusion is different from previous related reports. Moreover, the inter-HB strengthening of PD-methanol in PICT state induces the cleavage of intra-HB and a fluorescence red-shift of 54nm compared to PD. This red-shift increases to 66nm for PD-(methanol) 2 for the strengthening of the one intra-HB and two inter-HBs. The dipole moments of PD-methanol and PD-(methanol) 2 respectively increase about 10.3D and 8.1D in PICT state compared to PD. The synergistic effect of intra-HB and inter-HB induces partial quenching of PD in methanol solvent by turning on the TICT state and fluorescence red-shift. This work gives a reasonable description on the fluorescence red-shift and partial quenching of PD in methanol solvent, which will bring insight into the study of spectroscopic properties of molecules owning better spectral characteristics. Copyright © 2017 Elsevier B.V. All rights reserved.

Physicochemical Investigation of 2,4,5-Trimethoxybenzylidene Propanedinitrile (TMPN) Dye as Fluorescence off-on Probe for Critical Micelle Concentration (CMC) of SDS and CTAB.

PubMed

Khan, Salman A; Asiri, Abdullah M

2015-11-01

2,4,5-trimethoxybenzylidene propanedinitrile (TMPN) was synthesized by Knoevenagel condensation. Structure of the TMPN was conformed by the elemental analysis and EI-MS, FT-IR, (1)H-NMR, (13)C-NMR spectroscopy. Absorbance and emission spectrum of the TMPN was studied in different solvent provide that TMPN is good absorbent and emission red shift in absorbance and emission spectra as polarity of the solvents increase. Photophysical properties including, oscillator strength, extinction coefficient, transition dipole moment, stokes shift and fluorescence quantum yield were investigated in order to investigate the physicochemical behaviors of TMPN. Dye undergoes solubilization in different micelles and may be used as a probe to determine the critical micelle concentration (CMC) of SDS and CTAB.

Synthesis of a Far-Red Photoactivatable Silicon-Containing Rhodamine for Super-Resolution Microscopy.

PubMed

Grimm, Jonathan B; Klein, Teresa; Kopek, Benjamin G; Shtengel, Gleb; Hess, Harald F; Sauer, Markus; Lavis, Luke D

2016-01-26

The rhodamine system is a flexible framework for building small-molecule fluorescent probes. Changing N-substitution patterns and replacing the xanthene oxygen with a dimethylsilicon moiety can shift the absorption and fluorescence emission maxima of rhodamine dyes to longer wavelengths. Acylation of the rhodamine nitrogen atoms forces the molecule to adopt a nonfluorescent lactone form, providing a convenient method to make fluorogenic compounds. Herein, we take advantage of all of these structural manipulations and describe a novel photoactivatable fluorophore based on a Si-containing analogue of Q-rhodamine. This probe is the first example of a "caged" Si-rhodamine, exhibits higher photon counts compared to established localization microscopy dyes, and is sufficiently red-shifted to allow multicolor imaging. The dye is a useful label for super-resolution imaging and constitutes a new scaffold for far-red fluorogenic molecules. © 2015 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

Manipulating the alkali metal charge compensation and tungsten oxide to continuously enhance the red fluorescence in (Li,Na,K)Ca(Mo,W)O4:Eu3+ solid solution compounds

NASA Astrophysics Data System (ADS)

Xie, Wei; Li, Jiaxin; Tian, Canxin; Wang, Zesong; Xie, Mubiao; Zou, Changwei; Sun, Guohuan; Kang, Fengwen

2018-02-01

When compared to other phosphors typically the blue and green phosphors, red phosphors, which can be used for white light-emitting diodes (wLEDs), always suffer from various problems such as higher cost, lower luminescence efficiency and bad thermal stability. And thus, great interests have been paid to how to enhance the red fluorescence intensity in the recent years. Here we report on a red-emitting solid solutions, (Li,Na,K)Ca(Mo,W)O4:Eu3+, which enable exhibiting continuous Eu3+ emission enhancement through manipulating the alkali metal ions and the relative content ratios between tungsten and molybdenum oxides. X-ray powder diffraction (XRD) has been employed to check the phase purity, and results show that all samples crystallize in a scheelite structure with space group of I41/a (No.88). A regular blue-shifting of XRD peaks, which indicates the increase of crystal plane spacing, appears as the alkali cationic radius increases from 0.92 Å (for Li), 1.18 Å (for Na) and to 1.38 Å (for K). Replacing Mo ion (0.41 Å) by W ion (0.42 Å) enables not only forming the solid solution compounds (Li,Na,K)Ca(Mo,W)O4:Eu3+, but also blue-shifting the XRD position. Similar to the XRD position shifting, our samples also exhibit the regular change in the photoluminescence (PL) spectra, in which the charge transfer (CT) band position as the alkali cationic radii increase from Li, Na and to K and further from Mo to W shows a continuous red-shifting behavior. As for the CT and Eu3+ intensity, our experimental results show that the alkali ion that corresponds to the maximum intensity is Li, and this intensity can be further enhanced by adding W. In coincidence with the change in the excitation spectral intensity, the continuous enhanced Eu3+ emission intensity can be observed up excitation at the CT band and Eu3+ lines. We have discussed the above CT band shifting and Eu3+ fluorescence enhancement and give a feasible mechanism profile that base on the energy transfer from CT band to Eu3+ dopant.

Structure and luminescence properties of 10-BN sheets

NASA Astrophysics Data System (ADS)

Han, Wei-Qiang; Liu, Lijia; Sham, T. K.; Liu, Zhenxian

2012-10-01

Isotopic 10BN sheets were first prepared using graphene sheets as templates to react with 10B2O3. The edge-areas of BN sheets have much higher oxygen-doping ratios compared to other areas. The emission peak of X-ray excited optical luminescence spectra of the 10BN-sheets is broader and red-shifted because of the isotopic effect. A broad violet-blue emission at a wavelength centered at ~400 nm is assigned to the defect emission due to oxygen-doping and defects in the BN network.

Solid-state radioluminescent compositions

DOEpatents

Clough, Roger L.; Gill, John T.; Hawkins, Daniel B.; Renschler, Clifford L.; Shepodd, Timothy J.; Smith, Henry M.

1991-01-01

A solid state radioluminescent composition for light source comprises an optically clear polymer organic matrix containing tritiated organic materials and dyes capable of "red" shifting primary scintillation emissions from the polymer matrix. The tritiated organic materials are made by reducing, with tritium, an unsaturated organic compound that prior to reduction contains olefinic or alkynylic bonds.

Investigations on the effects of the Stark splitting on the fluorescence behaviors in Yb3+-doped silicate, tellurite, germanate, and phosphate glasses

NASA Astrophysics Data System (ADS)

Zhang, Liaolin; Xia, Yu; Shen, Xiao; Yang, Runlan; Wei, Wei

2018-01-01

In this work, we systematically studied the spectroscopic characteristics of Yb3+ doped germanate, phosphate, silicate, and tellurite glasses. The emission peak beyond 976 nm showed irregular shift from 1001 nm to 1023 nm when Yb3+ in different glass matrices. It was associated with the Stark splitting of 2F7/2 and the emission intensities ratio between the transition from the lowest Stark splitting energy level of 2F5/2 to the Stark splitting energy levels of 2F7/2, e to b and that of e to d. Larger Stark splitting of 2F7/2 results in the red-shift of the near infrared emission band at room temperature and larger ratio results in the blue-shift of emission band. The fluorescence lifetimes of Yb3+ doped germanate, phosphate, silicate, and tellurite glasses were measured to be 0.94, 0.82, 1.51, and 0.66 ms, respectively. The fluorescence lifetime was associated with the reabsorption of Yb3+, which larger absorption cross section at the emission band results in larger reabsorption, then leads to the shorter near infrared fluorescence lifetime.

Polymorph-Dependent Green, Yellow, and Red Emissions of Organic Crystals for Laser Applications.

PubMed

Xu, Zhenzhen; Zhang, Zhiwei; Jin, Xue; Liao, Qing; Fu, Hongbing

2017-12-05

Color tuning of organic solid-state luminescent materials remains difficult and time-consuming through conventional chemical synthesis. Herein, we reported highly efficient polymorph-dependent green (P1), yellow (P2), and red (P3) emissions of organic crystals made by the same molecular building blocks of 4-(2-{4-[2-(4-diphenylamino-phenyl)-vinyl]-phenyl}-vinyl)-benzonitrile (DOPVB). Single-crystal X-ray diffraction (XRD) and spectroscopic data reveal that all three polymorphs follow the herringbone packing motif in H-type aggregations. On the one hand, from P1, P2 to P3, the reduced pitch translation along π stacks increases the intermolecular interactions between adjacent molecules, therefore leading to gradually red-shifted emissions from 540, 570 to 614 nm. On the other hand, the edge-to-face arrangement and large roll translations avoid strong π-π overlap, making P1, P2 and P3 highly emissive with record-high solid-state fluorescence quantum yields of 0.60, 0.98, and 0.68, respectively. Furthermore, the optically allowed 0-1 transitions of herringbone H-aggregates of P1, P2 and P3 naturally provide a four-level scheme, enabling green and yellow amplified spontaneous emissions (ASE) with very low thresholds. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Probing Bioluminescence Resonance Energy Transfer in Quantum Rod-Luciferase Nanoconjugates.

PubMed

Alam, Rabeka; Karam, Liliana M; Doane, Tennyson L; Coopersmith, Kaitlin; Fontaine, Danielle M; Branchini, Bruce R; Maye, Mathew M

2016-02-23

We describe the necessary design criteria to create highly efficient energy transfer conjugates containing luciferase enzymes derived from Photinus pyralis (Ppy) and semiconductor quantum rods (QRs) with rod-in-rod (r/r) microstructure. By fine-tuning the synthetic conditions, CdSe/CdS r/r-QRs were prepared with two different emission colors and three different aspect ratios (l/w) each. These were hybridized with blue, green, and red emitting Ppy, leading to a number of new BRET nanoconjugates. Measurements of the emission BRET ratio (BR) indicate that the resulting energy transfer is highly dependent on QR energy accepting properties, which include absorption, quantum yield, and optical anisotropy, as well as its morphological and topological properties, such as aspect ratio and defect concentration. The highest BR was found using r/r-QRs with lower l/w that were conjugated with red Ppy, which may be activating one of the anisotropic CdSe core energy levels. The role QR surface defects play on Ppy binding, and energy transfer was studied by growth of gold nanoparticles at the defects, which indicated that each QR set has different sites. The Ppy binding at those sites is suggested by the observed BRET red-shift as a function of Ppy-to-QR loading (L), where the lowest L results in highest efficiency and furthest shift.

Synthesis and binding properties of arylethyne-linked porphyrin-zinc complexes for organic electronics applications.

PubMed

Reainthippayasakul, W; Paosawatyanyong, B; Bhanthumnavin, W

2013-05-01

Conjugated meso-alkynyl 5,15-dimesitylporphyrin metal complexes have been synthesized by Sonogashira coupling reaction in good yields. Alkynyl groups were chosen as a link at the meso positions in order to extend the pi-conjugated length of porphyrin rings. These synthesized porphyrin derivatives were characterized by 1H NMR spectroscopy and MALDI-TOF mass spectrometry. Moreover, UV-visible spectroscopy and fluorescence spectroscopy were also used to investigate their photophysical properties. It has been demonstrated that central metal ions as well as meso substituents on porphyrin rings affected the electronic absorption and emission spectra of the compounds. Spectroscopic results revealed that alkyne-linked porphyrin metal complexes showed higher pi-conjugation compared with porphyrin building blocks resulting in red shifts in both absorption and emission spectra. Coordination properties of synthesized porphyrins were preliminarily investigated by UV-visible absorption and fluorescence emission spectroscopic titration with pyridine as axial ligand. The formation of porphyrin-pyridine complexes resulted in significant red shifts in absorption spectra and decrease of fluorescence intensity in emission spectra. Moreover, the 1H NMR titration experiments suggested that central metal ions play an important role to coordinate with pyridine and the coordination of porphyrin zinc(II) complex with pyridine occur in a 1:1 ratio. From these spectroscopic results, alkyne-linked porphyrin metal complexes offer potential applications as materials for optical organic nanosensors.

Monomeric red fluorescent proteins with a large Stokes shift.

PubMed

Piatkevich, Kiryl D; Hulit, James; Subach, Oksana M; Wu, Bin; Abdulla, Arian; Segall, Jeffrey E; Verkhusha, Vladislav V

2010-03-23

Two-photon microscopy has advanced fluorescence imaging of cellular processes in living animals. Fluorescent proteins in the blue-green wavelength range are widely used in two-photon microscopy; however, the use of red fluorescent proteins is limited by the low power output of Ti-Sapphire lasers above 1,000 nm. To overcome this limitation we have developed two red fluorescent proteins, LSS-mKate1 and LSS-mKate2, which possess large Stokes shifts with excitation/emission maxima at 463/624 and 460/605 nm, respectively. These LSS-mKates are characterized by high pH stability, photostability, rapid chromophore maturation, and monomeric behavior. They lack absorbance in the green region, providing an additional red color to the commonly used red fluorescent proteins. Substantial overlap between the two-photon excitation spectra of the LSS-mKates and blue-green fluorophores enables multicolor imaging using a single laser. We applied this approach to a mouse xenograft model of breast cancer to intravitally study the motility and Golgi-nucleus alignment of tumor cells as a function of their distance from blood vessels. Our data indicate that within 40 mum the breast cancer cells show significant polarization towards vessels in living mice.

Mass motion in upper solar chromosphere detected from solar eclipse observation

NASA Astrophysics Data System (ADS)

Li, Zhi; Qu, Zhongquan; Yan, Xiaoli; Dun, Guangtao; Chang, Liang

2016-05-01

The eclipse-observed emission lines formed in the upper solar atmosphere can be used to diagnose the atmosphere dynamics which provides an insight to the energy balance of the outer atmosphere. In this paper, we analyze the spectra formed in the upper chromospheric region by a new instrument called Fiber Arrayed Solar Optic Telescope (FASOT) around the Gabon total solar eclipse on November 3, 2013. The double Gaussian fits of the observed profiles are adopted to show enhanced emission in line wings, while red-blue (RB) asymmetry analysis informs that the cool line (about 104 K) profiles can be decomposed into two components and the secondary component is revealed to have a relative velocity of about 16-45 km s^{-1}. The other profiles can be reproduced approximately with single Gaussian fits. From these fittings, it is found that the matter in the upper solar chromosphere is highly dynamic. The motion component along the line-of-sight has a pattern asymmetric about the local solar radius. Most materials undergo significant red shift motions while a little matter show blue shift. Despite the discrepancy of the motion in different lines, we find that the width and the Doppler shifts both are function of the wavelength. These results may help us to understand the complex mass cycle between chromosphere and corona.

Synthesis, computational, and spectroscopic analysis of tunable highly fluorescent BN-1,2-azaborine derivatives containing the N-BOH moiety.

PubMed

Saint-Louis, Carl Jacky; Shavnore, Renée N; McClinton, Caleb D C; Wilson, Julie A; Magill, Lacey L; Brown, Breanna M; Lamb, Robert W; Webster, Charles Edwin; Schrock, Alan K; Huggins, Michael T

2017-12-13

Nine new polycyclic aromatic BN-1,2-azaborine analogues containing the N-BOH moiety were synthesized using a convenient two-step, one-pot procedure. Characterization of the prepared compounds show the luminescence wavelength and the quantum yields of the azaborines were tunable by controlling the power and location of the donor and acceptor substituents on the chromophore. UV-visible spectroscopy and density functional theory (DFT) computations revealed that the addition of electron-donating moieties to the isoindolinone hemisphere raised the energy of the HOMO, resulting in the reduction of the HOMO-LUMO gap. The addition of an electron-accepting moiety to the isoindolinone hemisphere and an electron-donating group to the boronic acid hemisphere decreased the HOMO-LUMO gap considerably, leading to emission properties from partial intramolecular charge transfer (ICT) states. The combined effect of an acceptor on the isoindolinone side and a donor on the boronic acid side (strong acceptor-π-donor) gave the most red-shifted absorption. The polycyclic aromatic BN-1,2-azaborines emitted strong fluorescence in solution and in the solid-state with the largest red-shifted emission at 640 nm and a Stokes shift of Δλ = 218 nm, or Δν = 8070 cm -1 .

Wide-Field InfraRed Survey Telescope (WFIRST) Slitless Spectrometer: Design, Prototype, and Results

NASA Technical Reports Server (NTRS)

Gong, Qian; Content, David; Dominguez, Margaret; Emmett, Thomas; Griesmann, Ulf; Hagopian, John; Kruk, Jeffrey; Marx, Catherine; Pasquale, Bert; Wallace, Thomas;

Laser characteristics at 1535 nm and thermal effects of an Er:Yb phosphate glass microchip pumped by Ti:sapphire laser

NASA Astrophysics Data System (ADS)

Cai, Zhiping; Chardon, Alain; Xu, Huiying; Féron, Patrice; Michel Stéphan, Guy

2002-03-01

An Er:Yb codoped phosphate glass microchip laser has been studied under pumping with a Ti:sapphire laser ranging from 945 to 990 nm. The characteristics (threshold, slope efficiency) are first described for an optimized laser. The gain spectrum is calculated for the transition 4I13/2→ 4I15/2 around 1535 nm from fundamental spectroscopic data and from experimental results. Red-shift effect on the frequency of a single mode is experimentally observed when the pump power is increased, originating from thermal effects. Temperature inside the microchip cavity and thermal expansion coefficient were determined by employing the intensity ratio of two green upconversion emission line centered at 530 and 554 nm, respectively, which quantitatively explain this red shift.

Novel type of red-shifted chlorophyll a antenna complex from Chromera velia: II. Biochemistry and spectroscopy.

PubMed

Bína, David; Gardian, Zdenko; Herbstová, Miroslava; Kotabová, Eva; Koník, Peter; Litvín, Radek; Prášil, Ondřej; Tichý, Josef; Vácha, František

2014-06-01

A novel chlorophyll a containing pigment-protein complex expressed by cells of Chromera velia adapted to growth under red/far-red illumination [1]. Purification of the complex was achieved by means of anion-exchange chromatography and gel-filtration. The antenna is shown to be an aggregate of ~20kDa proteins of the light-harvesting complex (LHC) family, unstable in the isolated form. The complex possesses an absorption maximum at 705nm at room temperature in addition to the main chlorophyll a maximum at 677nm producing the major emission band at 714nm at room temperature. The far-red absorption is shown to be the property of the isolated aggregate in the intact form and lost upon dissociation. The purified complex was further characterized by circular dichroism spectroscopy and fluorescence spectroscopy. This work thus identified the third different class of antenna complex in C. velia after the recently described FCP-like and LHCr-like antennas. Possible candidates for red antennas are identified in other taxonomic groups, such as eustigmatophytes and the relevance of the present results to other known examples of red-shifted antenna from other organisms is discussed. This work appears to be the first successful isolation of a chlorophyll a-based far-red antenna complex absorbing above 700nm unrelated to LHCI. Copyright © 2014 Elsevier B.V. All rights reserved.

Synthesis and photophysical properties of a series of cyclopenta[b]naphthalene solvatochromic fluorophores.

PubMed

Benedetti, Erica; Kocsis, Laura S; Brummond, Kay M

2012-08-01

The synthesis and photophysical properties of a series of naphthalene-containing solvatochromic fluorophores are described within. These novel fluorophores are prepared using a microwave-assisted dehydrogenative Diels-Alder reaction of styrene, followed by a palladium-catalyzed cross coupling reaction to install an electron donating amine group. The new fluorophores are structurally related to Prodan. Photophysical properties of the new fluorophores were studied and intriguing solvatochromic behavior was observed. For most of these fluorophores, high quantum yields (60-99%) were observed in methylene chloride in addition to large Stokes shifts (95-226 nm) in this same solvent. As the solvent polarity increased, so did the observed Stokes shift with one derivative displaying a Stokes shift of ~300 nm in ethanol. All fluorophore emission maxima, and nearly all absorption maxima were significantly red-shifted when compared to Prodan. Shifting the absorption and emission maxima of a fluorophore into the visible region increases its utility in biological applications. Moreover, the cyclopentane portion of the fluorophore structure provides an attachment point for biomolecules that will minimize disruptions of the photophysical properties.

Interstellar absorption in the Mg II resonance line k2 and h2 emissions

NASA Technical Reports Server (NTRS)

Boehm-Vitense, E.

1981-01-01

High-resolution (0.2 A) IUE spectra for the long wavelength range (1800-3000 A) have been studied. It is shown that narrow interstellar Mg II lines are seen in the center of the k2 and h2 emissions from nearby stars with large rotational velocities. For all observed stars, the radial velocity of the central k3 absorption component in the rest system of the star is strongly correlated with the mirror image of the radial velocity of the stars; this shows that a major fraction if not all of the k3 absorption is due to interstellar absorption in the solar neighborhood. The violet to red asymmetry of the k2 emission also correlates with the radial velocities of the star; this shows that the shift of k3 is due to the velocity shift of the local interstellar cloud with respect to the star.

Synthesis and Photoluminescent Properties of Arylethynyl substituted 9,10-Anthraquinones

NASA Technical Reports Server (NTRS)

Yang, Jin-Hua; Dass, Amala; Sotiriou-Leventis, Chariklia; Leventis, Nicholas

2003-01-01

A series of arylethynyl substituted anthraquinones were synthesized via Sonogashira coupling reactions of 2,7- dibromo-, 2,6-dibromo- and 2-bromoanthraquinone with para-substituted phenylacetylenes. While the redox properties of those compounds are almost insensitive to substitution, their absorption maxima are linearly related to the Hammett constants for electron donating and electron withdrawing groups separately. All compounds are photoluminescent both in solution (quantum yield of emission approximately 2%) and as solids. X-ray crystallographic characterization of 2,7-bisphenylethynyl anthraquinone indicates a monoclinic p2(l/n) space group and no indication for pi-overlap that would promote self-quenching. The emission maxima are red- shifted by both electron donating and electron withdrawing groups alike. The Stokes shifts of all compounds are significant and are correlated to the electronic properties of the substituents. The reduced forms of these compounds are also photoluminescent and the emission originates from the dihydroanthraquinone core.

Achieving deep-red-to-near-infrared emissions in Sn-doped Cu-In-S/ZnS quantum dots for red-enhanced white LEDs and near-infrared LEDs.

PubMed

Chen, Jixin; Li, Ye; Wang, Le; Zhou, Tianliang; Xie, Rong-Jun

2018-05-16

Semiconductor quantum dots (QDs) are promising luminescent materials for use in lighting, display and bio-imaging, and the color tuning is a necessity for such applications. In this work, we report tunable colors and deep-red or near infrared (NIR) emissions in Cu-In-S and Cu-In-S/ZnS QDs by incorporating Sn. These QDs (with a size of 5 nm) with varying Sn concentrations and/or Cu/In ratios were synthesized by a non-injection method, and characterized by a variety of analytical techniques (i.e., XRD, TEM, XPS, absorption, photoluminescence, decay time, etc.). The Cu-Sn-In-S and Cu-Sn-In-S/ZnS QDs with Cu/In = 1/2 show the emission maximum in the ranges of 701-894 nm and 628-785 nm, respectively. The red-shift in emission is ascribed to the decrease of the band gap with the Sn doping. The highest quantum yield of 75% is achieved in Cu-Sn-In-S/ZnS with 0.1 mmol Sn and Cu/In = 1/2. Both the white and NIR LEDs were fabricated by using Cu-Sn-In-S/ZnS QDs and a 365 nm LED chip. The white LED exhibits superhigh color rendering indices of Ra = 97.2 and R9 = 91 and a warm color temperature of 2700 K. And the NIR LED shows an interesting broadband near-infrared emission centered at 741 nm, allowing for applications in optical communication, sensing and medical devices.

Red shift in the spectrum of a chlorophyll species is essential for the drought-induced dissipation of excess light energy in a poikilohydric moss, Bryum argenteum.

PubMed

Shibata, Yutaka; Mohamed, Ahmed; Taniyama, Koichiro; Kanatani, Kentaro; Kosugi, Makiko; Fukumura, Hiroshi

2018-05-01

Some mosses are extremely tolerant of drought stress. Their high drought tolerance relies on their ability to effectively dissipate absorbed light energy to heat under dry conditions. The energy dissipation mechanism in a drought-tolerant moss, Bryum argenteum, has been investigated using low-temperature picosecond time-resolved fluorescence spectroscopy. The results are compared between moss thalli samples harvested in Antarctica and in Japan. Both samples show almost the same quenching properties, suggesting an identical drought tolerance mechanism for the same species with two completely different habitats. A global target analysis was applied to a large set of data on the fluorescence-quenching dynamics for the 430-nm (chlorophyll-a selective) and 460-nm (chlorophyll-b and carotenoid selective) excitations in the temperature region from 5 to 77 K. This analysis strongly suggested that the quencher is formed in the major peripheral antenna of photosystem II, whose emission spectrum is significantly broadened and red-shifted in its quenched form. Two emission components at around 717 and 725 nm were assigned to photosystem I (PS I). The former component at around 717 nm is mildly quenched and probably bound to the PS I core complex, while the latter at around 725 nm is probably bound to the light-harvesting complex. The dehydration treatment caused a blue shift of the PS I emission peak via reduction of the exciton energy flow to the pigment responsible for the 725 nm band.

Engineering 'Golden' Fluorescence by Selective Pressure Incorporation of Non-canonical Amino Acids and Protein Analysis by Mass Spectrometry and Fluorescence.

PubMed

Baumann, Tobias; Schmitt, Franz-Josef; Pelzer, Almut; Spiering, Vivian Jeanette; Freiherr von Sass, Georg Johannes; Friedrich, Thomas; Budisa, Nediljko

2018-04-27

Fluorescent proteins are fundamental tools for the life sciences, in particular for fluorescence microscopy of living cells. While wild-type and engineered variants of the green fluorescent protein from Aequorea victoria (avGFP) as well as homologs from other species already cover large parts of the optical spectrum, a spectral gap remains in the near-infrared region, for which avGFP-based fluorophores are not available. Red-shifted fluorescent protein (FP) variants would substantially expand the toolkit for spectral unmixing of multiple molecular species, but the naturally occurring red-shifted FPs derived from corals or sea anemones have lower fluorescence quantum yield and inferior photo-stability compared to the avGFP variants. Further manipulation and possible expansion of the chromophore's conjugated system towards the far-red spectral region is also limited by the repertoire of 20 canonical amino acids prescribed by the genetic code. To overcome these limitations, synthetic biology can achieve further spectral red-shifting via insertion of non-canonical amino acids into the chromophore triad. We describe the application of SPI to engineer avGFP variants with novel spectral properties. Protein expression is performed in a tryptophan-auxotrophic E. coli strain and by supplementing growth media with suitable indole precursors. Inside the cells, these precursors are converted to the corresponding tryptophan analogs and incorporated into proteins by the ribosomal machinery in response to UGG codons. The replacement of Trp-66 in the enhanced "cyan" variant of avGFP (ECFP) by an electron-donating 4-aminotryptophan results in GdFP featuring a 108 nm Stokes shift and a strongly red-shifted emission maximum (574 nm), while being thermodynamically more stable than its predecessor ECFP. Residue-specific incorporation of the non-canonical amino acid is analyzed by mass spectrometry. The spectroscopic properties of GdFP are characterized by time-resolved fluorescence spectroscopy as one of the valuable applications of genetically encoded FPs in life sciences.

Dimeric fluorescent energy transfer dyes comprising asymmetric cyanine azole-indolenine chromophores

DOEpatents

Glazer, Alexander N.; Benson, Scott C.

1996-01-01

Novel fluorescent DNA-staining dyes are provided combining asymmetric cyanine azole-indolenine dyes, which provide for strong DNA affinity, large Stokes shifts and emission in the red region of the spectrum. The dyes find particular application in gel electrophoresis and for labels which may be bound to a variety of compositions in a variety of contexts.

Red fluorescent biofilm: the thick, the old, and the cariogenic

PubMed Central

Volgenant, Catherine M.C.; Hoogenkamp, Michel A.; Buijs, Mark J.; Zaura, Egija; ten Cate, Jacob (Bob) M.; van der Veen, Monique H.

2016-01-01

Background Some dental plaque fluoresces red. The factors involved in this fluorescence are yet unknown. Objective The aim of this study was to assess systematically the effect of age, thickness, and cariogenicity on the extent of red fluorescence produced by in vitro microcosm biofilms. Design The effects of biofilm age and thickness on red fluorescence were tested in a constant depth film fermentor (CDFF) by growing biofilms of variable thicknesses that received a constant supply of defined mucin medium (DMM) and eight pulses of sucrose/day. The influence of cariogenicity on red fluorescence was tested by growing biofilm on dentin disks receiving DMM, supplemented with three or eight pulses of sucrose/day. The biofilms were analyzed at different time points after inoculation, up to 24 days. Emission spectra were measured using a fluorescence spectrophotometer (λexc405 nm) and the biofilms were photographed with a fluorescence camera. The composition of the biofilms was assessed using 454-pyrosequecing of the 16S rDNA gene. Results From day 7 onward, the biofilms emitted increasing intensities of red fluorescence as evidenced by the combined red fluorescence peaks. The red fluorescence intensity correlated with biofilm thickness but not in a linear way. Biofilm fluorescence also correlated with the imposed cariogenicity, evidenced by the induced dentin mineral loss. Increasing the biofilm age or increasing the sucrose pulsing frequency led to a shift in the microbial composition. These shifts in composition were accompanied by an increase in red fluorescence. Conclusions The current study shows that a thicker, older, or more cariogenic biofilm results in a higher intensity of red fluorescence. PMID:27060056

Synthesis of Carbon Dots with Multiple Color Emission by Controlled Graphitization and Surface Functionalization.

PubMed

Miao, Xiang; Qu, Dan; Yang, Dongxue; Nie, Bing; Zhao, Yikang; Fan, Hongyou; Sun, Zaicheng

2018-01-01

Multiple-color-emissive carbon dots (CDots) have potential applications in various fields such as bioimaging, light-emitting devices, and photocatalysis. The majority of the current CDots to date exhibit excitation-wavelength-dependent emissions with their maximum emission limited at the blue-light region. Here, a synthesis of multiple-color-emission CDots by controlled graphitization and surface function is reported. The CDots are synthesized through controlled thermal pyrolysis of citric acid and urea. By regulating the thermal-pyrolysis temperature and ratio of reactants, the maximum emission of the resulting CDots gradually shifts from blue to red light, covering the entire light spectrum. Specifically, the emission position of the CDots can be tuned from 430 to 630 nm through controlling the extent of graphitization and the amount of surface functional groups, COOH. The relative photoluminescence quantum yields of the CDots with blue, green, and red emission reach up to 52.6%, 35.1%, and 12.9%, respectively. Furthermore, it is demonstrated that the CDots can be uniformly dispersed into epoxy resins and be fabricated as transparent CDots/epoxy composites for multiple-color- and white-light-emitting devices. This research opens a door for developing low-cost CDots as alternative phosphors for light-emitting devices. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

pH-dependent optical properties of N-acetyl-L-cysteine-capped ZnSe(S) nanocrystals with intense/stable emissions

NASA Astrophysics Data System (ADS)

Soheyli, Ehsan; Sahraei, Reza; Nabiyouni, Gholamreza

2017-03-01

In the present study, a series of aqueous-based ZnSe(S) nanocrystals (NCs) was prepared at different solution pH ranging from 8 to 11.9, and using N-acetyl-L-cysteine (NAC) as capping agent. In addition to zinc blende structure, the X-ray diffraction studies demonstrated the quantum size regime of the ZnSe(S) NCs. To gain further insight toward the influence of the quantum confinement and pH values on optical properties of the as-prepared NCs, their UV-visible absorption and photoluminescence spectra were systematically analyzed. The absorption spectra experienced a red shift from 340 to 382 nm as the pH increased from 8.0 to 11.9, indicating the growth of the as-prepared ZnSe(S) NCs. The emission spectra also show the obvious red shift and the relative area of excitonic to trap emission, firstly increases from pH = 8.0 to 10.7, and then decreases by further increasing of the solution pH. The initial behavior might be due to the improved surface passivation of the trap dangling states by better deprotonation of thiol groups in NAC, whereas at pH >10.7, the faster growth rate of the ZnSe(s) NCs may lead to the formation of many defect sites. All of these phenomena were combined in the scheme which displays the effect of quantum confinement and solution pH on variation of the excitonic and trap-related emissions.

Photoluminescence Study of Gallium Nitride Thin Films Obtained by Infrared Close Space Vapor Transport.

PubMed

Santana, Guillermo; de Melo, Osvaldo; Aguilar-Hernández, Jorge; Mendoza-Pérez, Rogelio; Monroy, B Marel; Escamilla-Esquivel, Adolfo; López-López, Máximo; de Moure, Francisco; Hernández, Luis A; Contreras-Puente, Gerardo

2013-03-15

Photoluminescence (PL) studies in GaN thin films grown by infrared close space vapor transport (CSVT-IR) in vacuum are presented in this work. The growth of GaN thin films was done on a variety of substrates like silicon, sapphire and fused silica. Room temperature PL spectra of all the GaN films show near band-edge emission (NBE) and a broad blue and green luminescence (BL, GL), which can be seen with the naked eye in a bright room. The sample grown by infrared CSVT on the silicon substrate shows several emission peaks from 2.4 to 3.22 eV with a pronounced red shift with respect to the band gap energy. The sample grown on sapphire shows strong and broad ultraviolet emission peaks (UVL) centered at 3.19 eV and it exhibits a red shift of NBE. The PL spectrum of GaN films deposited on fused silica exhibited a unique and strong blue-green emission peak centered at 2.38 eV. The presence of yellow and green luminescence in all samples is related to native defects in the structure such as dislocations in GaN and/or the presence of amorphous phases. We analyze the material quality that can be obtained by CSVT-IR in vacuum, which is a high yield technique with simple equipment set-up, in terms of the PL results obtained in each case.

Photoluminescence Study of Gallium Nitride Thin Films Obtained by Infrared Close Space Vapor Transport

PubMed Central

Santana, Guillermo; de Melo, Osvaldo; Aguilar-Hernández, Jorge; Mendoza-Pérez, Rogelio; Monroy, B. Marel; Escamilla-Esquivel, Adolfo; López-López, Máximo; de Moure, Francisco; Hernández, Luis A.; Contreras-Puente, Gerardo

2013-01-01

Photoluminescence (PL) studies in GaN thin films grown by infrared close space vapor transport (CSVT-IR) in vacuum are presented in this work. The growth of GaN thin films was done on a variety of substrates like silicon, sapphire and fused silica. Room temperature PL spectra of all the GaN films show near band-edge emission (NBE) and a broad blue and green luminescence (BL, GL), which can be seen with the naked eye in a bright room. The sample grown by infrared CSVT on the silicon substrate shows several emission peaks from 2.4 to 3.22 eV with a pronounced red shift with respect to the band gap energy. The sample grown on sapphire shows strong and broad ultraviolet emission peaks (UVL) centered at 3.19 eV and it exhibits a red shift of NBE. The PL spectrum of GaN films deposited on fused silica exhibited a unique and strong blue-green emission peak centered at 2.38 eV. The presence of yellow and green luminescence in all samples is related to native defects in the structure such as dislocations in GaN and/or the presence of amorphous phases. We analyze the material quality that can be obtained by CSVT-IR in vacuum, which is a high yield technique with simple equipment set-up, in terms of the PL results obtained in each case. PMID:28809356

SU-F-J-46: Feasibility of Cerenkov Emission for Absorption Spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Oraiqat, I; Rehemtulla, A; Lam, K

2016-06-15

Purpose: Cerenkov emission (CE) is a promising tool for online tumor microenvironment interrogation and targeting during radiotherapy. In this work, we utilize CE generated during radiotherapy as a broadband excitation source for real-time absorption spectroscopy. We demonstrate the feasibility of CE spectroscopy using a controlled experiment of materials with known emission/absorption properties. Methods: A water tank is irradiated with 20 MeV electron beam to induce Cerenkov emission. Food coloring dyes (Yellow #5, Red #40, and Blue #1), which have known emission/absorption properties were added to the water tank with increasing concentration (1 drop (0.05 mL), 2 drops, and 4 dropsmore » from a dispenser bottle). The signal is collected using a condensing lens which is coupled into a 20m optical fiber that is fed into a spectrometer that measures the emitted spectra. The resulting spectra from water/food coloring dye solutions were normalized by the reference spectrum, which is the Cerenkov spectrum of pure water, correcting for both the nonlinearity of the broadband Cerenkov emission spectrum as well as the non-uniform spectral response of the spectrometer. The emitted spectra were then converted into absorbance and their characteristics were analyzed. Results: The food coloring dye had a drastic change on the Cerenkov emission, shifting its wavelength according to its visible color. The collected spectra showed various absorbance peaks which agrees with tabulated peak positions of the dyes added within 0.3% for yellow, 1.7% for red, and 0.16% for blue. The CE peak heights proportionally increased as the dye concentration is increased. Conclusion: This work shows the potential for real-time functional spectroscopy using Cerenkov emission during radiotherapy. It was demonstrated that molecule identification as well as relative concentration can be extracted from the Cerenkov emission color shift.« less

Comparative analysis of cyanobacteria inhabiting rocks with different light transmittance in the Mojave Desert: a Mars terrestrial analogue

NASA Astrophysics Data System (ADS)

Smith, Heather D.; Baqué, Mickael; Duncan, Andrew G.; Lloyd, Christopher R.; McKay, Christopher P.; Billi, Daniela

2014-05-01

The Mojave Desert has been long considered a suitable terrestrial analogue to Mars in many geological and astrobiological aspects. The Silver Lake region in the Mojave Desert hosts several different rock types (talc, marble, quartz, white carbonate and red-coated carbonate) colonized by hypoliths within a few kilometres. This provides an opportunity to investigate the effect of rock type on hypolithic colonization in a given environment. Transmission measurements from 300 to 800 nm showed that the transmission of blue and UVA varied between rock types. The wavelength at which the transmission fell to 1% of the transmission at 600 nm was 475 nm for white carbonate and quartz, 425 nm for red-coated carbonate and talc and 380 nm for marble. The comparative analysis of the cyanobacterial component of hypoliths under different rocks, as revealed by sequencing 16S rRNA gene clone libraries, showed no significant variation with rock type; hypoliths were dominated by phylotypes of the genus Chroococcidiopsis, although less abundant phylotypes of the genus Loriellopsis, Leptolyngbya and Scytonema occurred. The comparison of the confocal laser scanning microscopy-λ (CLSM-λ) scan analysis of the spectral emission of the photosynthetic pigments of Chroococcidiopsis in different rocks with the spectrum of isolated Chroococcidiopsis sp. 029, revealed a 10 nm red shift in the emission fingerprinting for quartz and carbonate and a 5 nm red shift for talc samples. This result reflects the versatility of Chroococcidiopsis in inhabiting dry niches with different light availability for photosynthesis.

Origin and Luminescence of Anomalous Red-Emitting Center in Rhombohedral Ba9Lu2Si6O24:Eu(2+) Blue Phosphor.

PubMed

Liu, Yongfu; Zhang, Changhua; Cheng, Zhixuan; Zhou, Zhi; Jiang, Jun; Jiang, Haochuan

2016-09-06

We obtain a blue phosphor, Ba9Lu2Si6O24:Eu(2+) (BLS:Eu(2+)), which shows a strong emission peak at 460 nm and a weak tail from 460 to 750 nm. A 610 nm red emission is observed for the first time in this kind of rhombohedral structure material, which is much different from the same crystal structure of Ba9Sc2Si6O24:Eu(2+) and Ba9Y2Si6O24:Eu(2+). The luminescence properties and decays from 10 to 550 K are discussed. The new red emission arises from a trapped exciton state of Eu(2+) at the Ba site with a larger coordination number (12-fold). It exhibits abnormal luminescence properties with a broad bandwidth and a large Stokes shift. Under the 400 nm excitation, the external quantum efficiency of BLS:Eu(2+) is 45.4%, which is higher than the 35.7% for the commercial blue phosphor BAM:Eu(2+). If the thermal stability of BLS:Eu(2+) can be improved, it will show promising applications in efficient near-UV-based white LEDs.

Bioluminescence of beetle luciferases with 6'-amino-D-luciferin analogues reveals excited keto-oxyluciferin as the emitter and phenolate/luciferin binding site interactions modulate bioluminescence colors.

PubMed

Viviani, Vadim R; Neves, Deimison Rodrigues; Amaral, Danilo Trabuco; Prado, Rogilene A; Matsuhashi, Takuto; Hirano, Takashi

2014-08-19

Beetle luciferases produce different bioluminescence colors from green to red using the same d-luciferin substrate. Despite many studies of the mechanisms and structural determinants of bioluminescence colors with firefly luciferases, the identity of the emitters and the specific active site interactions responsible for bioluminescence color modulation remain elusive. To address these questions, we analyzed the bioluminescence spectra with 6'-amino-D-luciferin (aminoluciferin) and its 5,5-dimethyl analogue using a set of recombinant beetle luciferases that naturally elicit different colors and different pH sensitivities (pH-sensitive, Amydetes vivianii λmax=538 nm, Macrolampis sp2 λmax=564 nm; pH-insensitive, Phrixotrix hirtus λmax=623 nm, Phrixotrix vivianii λmax=546 nm, and Pyrearinus termitilluminans λmax=534 nm), a luciferase-like enzyme (Tenebrionidae, Zophobas morio λmax=613 nm), and mutants of C311 (S314). The green-yellow-emitting luciferases display red-shifted bioluminescence spectra with aminoluciferin in relation to those with D-luciferin, whereas the red-emitting luciferases displayed blue-shifted spectra. Bioluminescence spectra with 5,5-dimethylaminoluciferin, in which enolization is blocked, were almost identical to those of aminoluciferin. Fluorescence probing using 2-(4-toluidino)naphthalene-6-sulfonate and inference with aminoluciferin confirm that the luciferin binding site of the red-shifted luciferases is more polar than in the case of the green-yellow-emitting luciferases. Altogether, the results show that the keto form of excited oxyluciferin is the emitter in beetle bioluminescence and that bioluminescence colors are essentially modulated by interactions of the 6'-hydroxy group of oxyluciferin and basic moieties under the influence of the microenvironment polarity of the active site: a strong interaction between a base moiety and oxyluciferin phenol in a hydrophobic microenvironment promotes green-yellow emission, whereas a more polar environment weakens such interaction promoting red shifts. In pH-sensitive luciferases, a pH-mediated switch from a closed hydrophobic conformation to a more open polar conformation promotes the typical red shift.

Fluorescence of nitrobenzoxadiazole (NBD)-labeled lipids in model membranes is connected not to lipid mobility but to probe location.

PubMed

Amaro, Mariana; Filipe, Hugo A L; Prates Ramalho, J P; Hof, Martin; Loura, Luís M S

2016-03-14

Nitrobenzoxadiazole (NBD)-labeled lipids are popular fluorescent membrane probes. However, the understanding of important aspects of the photophysics of NBD remains incomplete, including the observed shift in the emission spectrum of NBD-lipids to longer wavelengths following excitation at the red edge of the absorption spectrum (red-edge excitation shift or REES). REES of NBD-lipids in membrane environments has been previously interpreted as reflecting restricted mobility of solvent surrounding the fluorophore. However, this requires a large change in the dipole moment (Δμ) of NBD upon excitation. Previous calculations of the value of Δμ of NBD in the literature have been carried out using outdated semi-empirical methods, leading to conflicting values. Using up-to-date density functional theory methods, we recalculated the value of Δμ and verified that it is rather small (∼2 D). Fluorescence measurements confirmed that the value of REES is ∼16 nm for 1,2-dioleoyl-sn-glycero-3-phospho-l-serine-N-(NBD) (NBD-PS) in dioleoylphosphatidylcholine vesicles. However, the observed shift is independent of both the temperature and the presence of cholesterol and is therefore insensitive to the mobility and hydration of the membrane. Moreover, red-edge excitation leads to an increased contribution of the decay component with a shorter lifetime, whereas time-resolved emission spectra of NBD-PS displayed an atypical blue shift following excitation. This excludes restrictions to solvent relaxation as the cause of the measured REES and TRES of NBD, pointing instead to the heterogeneous transverse location of probes as the origin of these effects. The latter hypothesis was confirmed by molecular dynamics simulations, from which the calculated heterogeneity of the hydration and location of NBD correlated with the measured fluorescence lifetimes/REES. Globally, our combination of theoretical and experiment-based techniques has led to a considerably improved understanding of the photophysics of NBD and a reinterpretation of its REES in particular.

Red-to-Ultraviolet Emission Tuning of Two-Dimensional Gallium Sulfide/Selenide.

PubMed

Jung, Chan Su; Shojaei, Fazel; Park, Kidong; Oh, Jin Young; Im, Hyung Soon; Jang, Dong Myung; Park, Jeunghee; Kang, Hong Seok

2015-10-27

Graphene-like two-dimensional (2D) nanostructures have attracted significant attention because of their unique quantum confinement effect at the 2D limit. Multilayer nanosheets of GaS-GaSe alloy are found to have a band gap (Eg) of 2.0-2.5 eV that linearly tunes the emission in red-to-green. However, the epitaxial growth of monolayers produces a drastic increase in this Eg to 3.3-3.4 eV, which blue-shifts the emission to the UV region. First-principles calculations predict that the Eg of these GaS and GaSe monolayers should be 3.325 and 3.001 eV, respectively. As the number of layers is increased to three, both the direct/indirect Eg decrease significantly; the indirect Eg approaches that of the multilayers. Oxygen adsorption can cause the direct/indirect Eg of GaS to converge, resulting in monolayers with a strong emission. This wide Eg tuning over the visible-to-UV range could provide an insight for the realization of full-colored flexible and transparent light emitters and displays.

Conformation Effects on the Photoluminescence Behavior of Anchored MEH-PPV Pancakes and Brushes

NASA Astrophysics Data System (ADS)

Shih, Kuo Sheng; Chen, Po-Tsun; Yang, Arnold C.-M.

2012-02-01

Single molecular layer of poly[2-methoxy-5-(2'-ethylhexyl)oxy)-1,4- phenylenevinylene] (MEH-PPV) grafted on primed silicon wafer were synthesized, forming brushes (chain spacing 0.54 nm via graft-from) or pancakes (˜ 7nm to 34 nm via graft-to). For the tight-packed brushes, the PL emission peak, residing in the range from 434 nm to 550 nm depending on the chain length, was generally unchanged when transferring between the dry and solvent immersion states. However, for the pancakes, the emission peak blue-shifted dramatically (up to 100 nm) when dried in the air relative to that in the solvent. These shifts were fully reversible in the dry-wet cycles. The large blue shifts of the anchored pancakes were attributed to the mechanical stretching of entangled MEH-PPV segments in contact with substrate upon solvent loss. In contrast, the blue shifts disappeared and small red shifts emerged instead for extremely slowly drying (24 hrs drying time), revealing the stress-relaxation pathways in the equilibrium conditions. The drying-induced blue shift was also observed in the un-anchored drop-casting samples but the reversibility vanished. Finally, a large enhancement of PL intensity was accompanied with the blue shifts, manifesting the effect of the molecular constraints.

Protein labeling with red squarylium dyes for analysis by capillary electrophoresis with laser-induced fluorescence detection.

PubMed

Yan, Weiying; Sloat, Amy L; Yagi, Shigeyuki; Nakazumi, Hiroyuki; Colyer, Christa L

2006-04-01

Two new red luminescent asymmetric squarylium dyes (designated "Red-1c and Red-3") have been shown to exhibit absorbance shifts to longer wavelengths upon the addition of protein, along with a concomitant increase in fluorescence emission. Specifically, the absorbance maxima for Red-1c and Red-3 dyes are 607 and 622 nm, respectively, in the absence of HSA, and 642 and 640 nm in the presence of HSA, making the excitation of their protein complexes feasible with inexpensive and robust diode lasers. Fluorescence emission maxima, in the presence of HSA, are 656 and 644 nm for Red-1c and Red-3, respectively. Because of the inherently low fluorescence of the dyes in their free state, Red-1c and Red-3 were used as on-column labels (that is, with the dye incorporated into the separation buffer), thus eliminating the need for sample derivatization prior to injection and separation. A comparison of precolumn and on-column labeling of proteins with these squarylium dyes revealed higher efficiencies and greater sensitivities for on-column labeling, which, when conducted with a basic, high-salt content buffer, permitted baseline resolution of a mixture of five model proteins. LOD for model proteins, such as transferrin, alpha-lactalbumin, BSA, and beta-lactoglobulin A and B, labeled with these dyes and analyzed by CE with LIF detection (CE-LIF) were found to be dependent upon dye concentration and solution pH, and are as low as 5 nM for BSA. Satisfactory linear relationships between peak height (or peak area) and protein concentration were obtained by CE-LIF for this on-column labeling method with Red-3 and Red-1c.

Electronic band structure and optical gain of GaN{sub x}Bi{sub y}As{sub 1−x−y}/GaAs pyramidal quantum dots

DOE Office of Scientific and Technical Information (OSTI.GOV)

Song, Zhi-Gang; State Key Laboratory of Superlattices and Microstructures, Institute of Semiconductors, Chinese Academy of Sciences, P.O. Box 912, Beijing 100083; Bose, Sumanta

The electronic band structure and optical gain of GaN{sub x}Bi{sub y}As{sub 1−x−y}/GaAs pyramidal quantum dots (QDs) are investigated using the 16-band k ⋅ p model with constant strain. The optical gain is calculated taking both homogeneous and inhomogeneous broadenings into consideration. The effective band gap falls as we increase the composition of nitrogen (N) and bismuth (Bi) and with an appropriate choice of composition we can tune the emission wavelength to span within 1.3 μm–1.55 μm, for device application in fiber technology. The extent of this red shift is more profound in QDs compared with bulk material due to quantum confinement. Othermore » factors affecting the emission characteristics include virtual crystal, strain profile, band anticrossing (BAC), and valence band anticrossing (VBAC). The strain profile has a profound impact on the electronic structure, specially the valence band of QDs, which can be determined using the composition distribution of wave functions. All these factors eventually affect the optical gain spectrum. With an increase in QD size, we observe a red shift in the emission energy and emergence of secondary peaks owing to transitions or greater energy compared with the fundamental transition.« less

Effect of preparation methods and doping on the structural and tunable emissions of CdS

NASA Astrophysics Data System (ADS)

Mohamed, Mohamed Bakr; Abdel-Kader, M. H.; Alhazime, Ali A.; Almarashi, Jamal Q. M.

2018-03-01

Fe, Mn and Mg doped CdS samples were prepared by thermolysis method in air and under flow of nitrogen. Structural, compositional and optical properties of the prepared samples were investigated using x-ray powder diffraction (XRD), scanning electron microscope (SEM/EDS mapping), Fourier transform infrared red (FTIR), UV-vis absorption and photoluminescence (PL) spectroscopes. Rietveld refinement of x-ray data showed that all the undoped and doped CdS samples prepared in air and under flow of nitrogen have both cubic and hexagonal structures. The percentages of hexagonal and cubic phases for all prepared samples were determined. The crystallite size increased for CdS prepared under flow of N2 compared with the sample prepared in air. The energy gap of all the samples was calculated using UV data. The intensity of PL emission changed according to the method of preparation and the kind of doping elements. PL emission revealed a blue shift for CdS prepared in air compared with CdS prepared under flow of nitrogen; also all doped samples showed a red shift of PL spectra compared with undoped samples. Undoped and doped CdS with Fe and Mg samples emitted violet and blue sub-spectra. Mn doped CdS prepared in air revealed violet, blue and yellow sub-spectra, while the sample prepared under flow of N2 emitted violet, blue and green sub-spectra.

Programs in Materials Research

DTIC Science & Technology

1990-02-01

8217[[-FN(CFS UN I VESITY OF (1 IICA(( Repordicioni n mmi \\10c or ini pait’is Is C pc iild forI ally piirposc ol 111c 11Ijijied Slaites (;ovriiLt1i...The activation energies and their I variation with 0 agree quite well with the results of White and co- workers on Ni(100) obtained by the LID method. 3...special conformer is broad and red shifted. This broad emission resembles emission from an exciplex , and we have produced a mcdel which says that in the

Rapid intensity and velocity variations in solar transition region lines

NASA Astrophysics Data System (ADS)

Hansteen, V. H.; Betta, R.; Carlsson, M.

2000-08-01

We have obtained short exposure (3 s) time series of strong upper chromospheric and transition region emission lines from the quiet Sun with the SUMER instrument onboard SOHO during two 1 hour periods in 1996. With a Nyqvist frequency of 167 mHz and relatively high count rates the dataset is uniquely suited for searching for high frequency variations in intensity and Doppler velocity. From Monte-Carlo experiments taking into account the photon-counting statistics we estimate our detection limit to correspond to a wave-packet of four periods coherent over 3'' with a Doppler-shift amplitude of 2.5km s-1 in the darkest internetwork areas observed in C III. In the network the detection limit is estimated to be 1.5km s-1. Above 50 mHz we detect wave-packet amplitudes above 3km s-1 less than 0.5% of the time. Between 20 and 50 mHz we detect some wave-packets with a typical duration of four periods and amplitudes up to 8km s-1. At any given internetwork location these wave-packets are present 1% of the time. In the 10-20 mHz range we see amplitudes above 3km s-1 12% of the time. At lower frequencies our dataset is consistent with other SUMER datasets reported in the literature. The chromospheric 3-7 mHz signal is discernible in the line emission. In the internetwork this is the dominant oscillation frequency but higher frequencies (7-10 mHz) are often present and appear coherent in Doppler velocity over large spatial regions (≍ 40"). Wavelet analysis implies that these oscillations have typical durations of 1000s. The network emission also shows a 5 mHz signal but is dominated by low frequency variations (of < 4 mHz) in both intensity and velocity. The oscillations show less power in intensity than in velocity. We find that while both red and blue shifted emission is observed, the transition region lines are on average red shifted between 5-10km s-1 in the network. A net red shift is also found in the internetwork emission but it is smaller (< 4km s-1). The line widths do not differ much between the internetwork and network, the non-thermal line widths increase with increasing temperature of line formation from 30km s-1 for the C II 1334 Å line to 45km s-1 for the O VI 1032 Å line. By constructing scatterplots of velocity versus intensity we find that in the network a mean redshift is correlated with a high mean intensity. In the internetwork regions we do not find any correlation between the intensity and the Doppler velocity.

Red Fluorescent Protein-Aequorin Fusions as Improved Bioluminescent Ca2+ Reporters in Single Cells and Mice

PubMed Central

Bakayan, Adil; Vaquero, Cecilia F.; Picazo, Fernando; Llopis, Juan

2011-01-01

Bioluminescence recording of Ca2+ signals with the photoprotein aequorin does not require radiative energy input and can be measured with a low background and good temporal resolution. Shifting aequorin emission to longer wavelengths occurs naturally in the jellyfish Aequorea victoria by bioluminescence resonance energy transfer (BRET) to the green fluorescent protein (GFP). This process has been reproduced in the molecular fusions GFP-aequorin and monomeric red fluorescent protein (mRFP)-aequorin, but the latter showed limited transfer efficiency. Fusions with strong red emission would facilitate the simultaneous imaging of Ca2+ in various cell compartments. In addition, they would also serve to monitor Ca2+ in living organisms since red light is able to cross animal tissues with less scattering. In this study, aequorin was fused to orange and various red fluorescent proteins to identify the best acceptor in red emission bands. Tandem-dimer Tomato-aequorin (tdTA) showed the highest BRET efficiency (largest energy transfer critical distance R0) and percentage of counts in the red band of all the fusions studied. In addition, red fluorophore maturation of tdTA within cells was faster than that of other fusions. Light output was sufficient to image ATP-induced Ca2+ oscillations in single HeLa cells expressing tdTA. Ca2+ rises caused by depolarization of mouse neuronal cells in primary culture were also recorded, and changes in fine neuronal projections were spatially resolved. Finally, it was also possible to visualize the Ca2+ activity of HeLa cells injected subcutaneously into mice, and Ca2+ signals after depositing recombinant tdTA in muscle or the peritoneal cavity. Here we report that tdTA is the brightest red bioluminescent Ca2+ sensor reported to date and is, therefore, a promising probe to study Ca2+ dynamics in whole organisms or tissues expressing the transgene. PMID:21589654

Interaction study of collagen and sericin in blending solution.

PubMed

Duan, Lian; Yuan, Jingjie; Yang, Xiao; Cheng, Xinjian; Li, Jiao

2016-12-01

The interactions of collagen and sericin were studied by fluorescence spectra, ultraviolet spectra, FTIR spectra and dynamic light scattering. The fluorescence quenching in emission spectra and red-shift (283-330nm) in synchronous fluorescence spectra suggested the Tyr of collagen and sericin overlapped with a distance of 3Å, generating excimer. The overlapped Tyr of collagen and sericin decreased the hydrophobicity of collagen, which resulted in the red-shifts (233-240nm) in ultraviolet spectra. Moreover, the red-shifts of amide bands of collagen in FTIR spectra indicated the hydrogen bonds of collagen were weaken and it could also be explained by the overlapped Tyr. The results of 2D-FTIR spectra demonstrated the backbone of collagen molecule was varied and the most susceptible structure of collagen was the triple helix with the presence of sericin. Based on dynamic light scattering, we conjectured large pure collagen aggregates were replaced by hybrid aggregates of collagen and sericin particles after the addition of sericin. With ascending sericin ratio, the diameters of the hybrid aggregates increased and attained maximum with 60% ratio of sericin, which were on account of the increasing excimer number. The results of DSC demonstrated the presence of sericin enhanced the thermal stability of collagen. Copyright © 2016 Elsevier B.V. All rights reserved.

Tunable multicolor and enhanced red emission of monodisperse CaF2:Yb3+/Ho3+ microspheres via Mn2+ doping

NASA Astrophysics Data System (ADS)

Wang, Rui; Yuan, Maohui; Zhang, Chaofan; Wang, Hongyan; Xu, Xiaojun

2018-05-01

Transition metal ions (e.g. Mn2+) and lanthanide co-doped upconversion (UC) materials have attracted wide attention in recent years due to their promising application in multicolor display. Here, we report the hydrothermal synthesis and characterization of Mn2+ doped monodisperse CaF2:Yb3+/Ho3+ microspheres. The results of X-ray diffraction (XRD) revealed that Mn2+ doping does not change the cubic phase of CaF2 material but will lead to diffraction peaks shifting slightly towards higher angle due to the substitution of larger Ca2+ by the relatively smaller Mn2+. Under the excitation of 980 nm continuous wave (CW) laser, these microspheres exhibit green-yellow-red tuning colors and remarkable enhancement of both red to green ratio (R/G) and red to blue ratio (R/B) when increasing Mn2+ concentration from 0 to 30 mol%. The energy migration process between Ho3+ and Mn2+ was proposed and supported by time-decay and power dependence measurements of Ho3+ UC emission. These upconversion materials may have potential applications in optical devices, color display, nanoscale lasers and biomedical imaging.

Theoretical studies of ground and excited electronic States in a series of rhenium(i) bipyridine complexes containing diarylethynyl-based structure.

PubMed

Yang, Li; Ren, Ai-Min; Feng, Ji-Kang; Liu, Xiao-Dong; Ma, Yu-Guang; Zhang, Hong-Xing

2004-09-20

The photophysical properties, which vary as X is varied, of Re(I)-halide complexes (X2-bpy)ReICl(CO)3 (where X=ph, DAE, DNE, and DPE; ph = phenyl (1); DAE = di(amineoethynylbenzene) (2); DPE = di(phenylethynylbenzene) (3); DNE = di(nitroethynylbenzene) (4); bpy=2,2'bipyridine), are investigated using density functional theory (DFT). The electronic properties of the neutral molecules, in addition to the positive and negative ions, are studied using B3LYP functional. Excited singlet and triplet states are examined using time-dependent density functional theory (TDDFT). The low-lying excited-state geometries are optimized at the ab initio configuration interaction singlets level. As shown, the diarylethynyl-based structure is an integral component of the bpy pi-conjugated network, which results in a good planar structure. The occupied orbitals involved in the transitions have a significant mixture of metal Re and group Cl, and the lowest unoccupied orbital is a pi orbital, which extends from ligand bpy to diarylethynyl-based substituents. The luminescence for each complex originates from the lowest triplet excited states and is assigned to the mixing of MLCT and LLCT characters. Significant insights on the effects of these diarylethynyl conjugated structure and ending substituents (NH2, ph, and NO2) on absorption and emission spectra are observed by analysis of the results of the TDDFT method. The diarylethynyl-based pi-conjugated network makes both the absorption and emission spectra red-shifted compared with simple complex (bpy)ReICl(CO)3. Furthermore, an electron-releasing group (NH2) makes absorption and emission spectra blue-shift and an electron-withdrawing group (NO2) makes them red-shift. Copyright 2004 American Chemical Society

New observations on the pressure dependence of luminescence from Eu2+-doped MF2 (M = Ca, Sr, Ba) fluorides.

PubMed

Su, Fu Hai; Chen, Wei; Ding, Kun; Li, Guo Hua

2008-05-29

The luminescence from Eu(2+) ions in MF2 (M = Ca, Sr, Ba) fluorides has been investigated under the pressure range of 0-8 GPa. The emission band originating from the 4f(6)5d(1) --> 4f(7) transition of Eu(2+) ions in CaF2 and SrF2 shows the red-shift as increasing pressure with pressure coefficients of -17 meV/GPa for CaF2 and -18 meV/GPa for SrF2. At atmospheric pressure, the emission spectrum of BaF2:Eu(2+) comprises two peaks at 2.20 and 2.75 eV from the impurity trapped exciton (ITE) and the self-trapped exciton (STE), respectively. As the pressure is increased, both emission peaks shift to higher energies, and the shifting rate is slowed by the phase transition from the cubic to orthorhombic phase at 4 GPa. Due to the phase transition at 4-5 GPa pressure, the ITE emission disappears gradually, and the STE emission is gradually replaced by the 4f(6)5d(1) --> 4f(7) transition of Eu(2+). Above 5 GPa, the pressure behavior of the 4f(6)5d(1) --> 4f(7) transition of Eu(2+) in BaF2:Eu(2+) is the same as the normal emission of Eu(2+) in CaF2 and SrF2 phosphors.

Structure, luminescence and thermal quenching properties of Eu doped Sr2-xBaxSi5N8 red phosphors

NASA Astrophysics Data System (ADS)

Liu, Y. H.; Chen, L.; Zhou, X. F.; Liu, R. H.; Zhuang, W. D.

2017-02-01

Eu2+ doped Sr2-xBaxSi5N8 phosphors were synthesized at 1610 ℃ for 4 h via the solid-state reaction method. The XRD results confirm that the complete solid solutions are formed. With the increase of x, the emission spectra show an obvious blue-shift from 610 nm to 585 nm under the excitation of 460 nm. The color tone can be tuned from yellow to red. The corresponding mechanism for the blue-shift of peak-wavelength is studied in detail. The results of decomposed Gaussian spectra and fluorescence lifetime show that the local coordination structure surrounding activator ions changes with increasing x value. It is found that the probability of Eu occupying Sr1 and Sr2 site is dependent on Ba/Sr ratio. The variation of thermal quenching properties and the corresponding mechanism is discussed in detail. The results indicate that Eu2+ doped Sr2-xBaxSi5N8 is a promising orange red-emitting phosphor for near UV or blue light-pumped white light-emitting-diodes (wLEDs).

In vivo excitation of nanoparticles using luminescent bacteria

PubMed Central

Dragavon, Joe; Blazquez, Samantha; Rekiki, Abdessalem; Samson, Chelsea; Theodorou, Ioanna; Rogers, Kelly L.; Tournebize, Régis; Shorte, Spencer L.

2012-01-01

The lux operon derived from Photorhabdus luminescens incorporated into bacterial genomes, elicits the production of biological chemiluminescence typically centered on 490 nm. The light-producing bacteria are widely used for in vivo bioluminescence imaging. However, in living samples, a common difficulty is the presence of blue-green absorbers such as hemoglobin. Here we report a characterization of fluorescence by unbound excitation from luminescence, a phenomenon that exploits radiating luminescence to excite nearby fluorophores by epifluorescence. We show that photons from bioluminescent bacteria radiate over mesoscopic distances and induce a red-shifted fluorescent emission from appropriate fluorophores in a manner distinct from bioluminescence resonance energy transfer. Our results characterizing fluorescence by unbound excitation from luminescence, both in vitro and in vivo, demonstrate how the resulting blue-to-red wavelength shift is both necessary and sufficient to yield contrast enhancement revealing mesoscopic proximity of luminescent and fluorescent probes in the context of living biological tissues. PMID:22615349

Synthesis of a Far‐Red Photoactivatable Silicon‐Containing Rhodamine for Super‐Resolution Microscopy

PubMed Central

Grimm, Jonathan B.; Klein, Teresa; Kopek, Benjamin G.; Shtengel, Gleb; Hess, Harald F.; Sauer, Markus

2015-01-01

Abstract The rhodamine system is a flexible framework for building small‐molecule fluorescent probes. Changing N‐substitution patterns and replacing the xanthene oxygen with a dimethylsilicon moiety can shift the absorption and fluorescence emission maxima of rhodamine dyes to longer wavelengths. Acylation of the rhodamine nitrogen atoms forces the molecule to adopt a nonfluorescent lactone form, providing a convenient method to make fluorogenic compounds. Herein, we take advantage of all of these structural manipulations and describe a novel photoactivatable fluorophore based on a Si‐containing analogue of Q‐rhodamine. This probe is the first example of a “caged” Si‐rhodamine, exhibits higher photon counts compared to established localization microscopy dyes, and is sufficiently red‐shifted to allow multicolor imaging. The dye is a useful label for super‐resolution imaging and constitutes a new scaffold for far‐red fluorogenic molecules. PMID:26661345

Channeling Excitons to Emissive Defect Sites in Carbon Nanotube Semiconductors beyond the Dilute Regime.

PubMed

Powell, Lyndsey R; Piao, Yanmei; Ng, Allen L; Wang, YuHuang

2018-06-07

The exciton photoluminescence of carbon nanotube semiconductors has been intensively exploited for bioimaging, anticounterfeiting, photodetection, and quantum information science. However, at high concentrations, photoluminescence is lost to self-quenching because of the nearly complete overlap of the absorption and emissive states (∼10 meV Stokes shift). Here we show that by introducing sparse fluorescent quantum defects via covalent chemistry, self-quenching can be efficiently bypassed by means of the new emission route. The defect photoluminescence is significantly red-shifted by 190 meV for p-nitroaryl tailored (6,5)-single-walled carbon nanotubes (SWCNTs) from the native emission of the nanotube. Notably, the defect photoluminescence is more than 34 times brighter than the native photoluminescence of unfunctionalized SWCNTs in the most concentrated nanotube solution tested (2.7 × 10 14 nanotubes/mL). Moreover, we show that defect photoluminescence is more resistant to self-quenching than the native state in a dense film, which is the upper limit of concentration. Our findings open opportunities to harness nanotube excitons in highly concentrated systems for applications where photoluminescence brightness and light-collecting efficiency are mutually important.

Potential benefits of triethylamine as n-electron donor in the estimation of forskolin by electronic absorption and emission spectroscopy

NASA Astrophysics Data System (ADS)

Raju, Gajula; Ram Reddy, A.

2016-02-01

Diterpenoid forskolin was isolated from Coleus forskolii. The electronic absorption and emission studies of forskolin were investigated in various solvents with an aim to improve its detection limits. The two chromophores present in the diterpenoid are not conjugated leading to the poor absorption and emission of UV light. The absorption and fluorescence spectra were solvent specific. In the presence of a monodentate ligand, triethylamine the detection of forskolin is improved by 3.63 times in ethanol with the fluorescence method and 3.36 times in DMSO by the absorption spectral method. The longer wavelength absorption maximum is blue shifted while the lower energy fluorescence maximum is red shifted in the presence of triethylamine. From the wavelength of fluorescence maxima of the exciplex formed between excited forskolin and triethylamine it is concluded that the order of reactivity of hydroxyl groups in the excited state forskolin is in the reverse order to that of the order of the reactivity of hydroxyl groups in its ground state.

Prominence of fusion temperature and engineering heteroatoms on multifarious emissive shifts in carbon dots.

PubMed

Velusamy, Jayaramakrishnan; Ramos-Ortiz, Gabriel; Rodríguez, Mario; Hernández-Cruz, Olivia; Ponce, Arturo

2018-05-16

We present a simple but robust strategy to engineering heteroatoms (N, S) on carbon dots (CDs) surface that results in a collection of enhanced photoluminescence (PL) emissions. The use of citric acid (CA) and 2-Imidazolidinethione (2-IZT) as precursors was envisioned to study the impact of thermolysis process on the PL properties. The proposed strategy, implemented at two different temperatures (180 °C and 200 °C), is suitable to produce CDs with tunable PL and quantum yield (QY) up to ∼32%. Similar to earlier reports of CA-based CDs, the self-assembling of fluorophores integrated into the CDs edge is hypothesized, however, in our CDs a double intriguing effect of blue- and red-shifting can be observed for PL as the wavelength of excitation is increased in the range 280-480 nm. Through a comprehensive characterization and evaluation of these CDs in water suspensions, the mechanisms that lead to PL multifarious emissions are proposed. Copyright © 2018 Elsevier Inc. All rights reserved.

The Second Swift BAT Gamma-Ray Burst Catalog

NASA Technical Reports Server (NTRS)

Barthelmy, S. D.; Baumgartner, W. H.; Cummings, J. R.; Fenimore, E. E.; Gehrels, N.; Krimm, H. A.; Markwardt, C. B.; Palmer, D. M.; Parsons, A. M.; Sato, G.;

Fourfold Diels-Alder reaction of tetraethynylsilane.

PubMed

Geyer, Florian L; Rode, Alexander; Bunz, Uwe H F

2014-12-08

A series of ethynylated silanes, including tetraethynylsilane, was treated with tetraphenylcyclopentadienone at 300 °C under microwave irradiation to give the aromatized Diels-Alder adducts as sterically encumbered mini-dendrimers with up to 20 benzene rings. The sterically most congested adducts display red-shifted emission through intramolecular π-π interactions in the excited state. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Cationic Organochalcogen with Monomer/Excimer Emissions for Dual-Color Live Cell Imaging and Cell Damage Diagnosis.

PubMed

Chao, Xi-Juan; Wang, Kang-Nan; Sun, Li-Li; Cao, Qian; Ke, Zhuo-Feng; Cao, Du-Xia; Mao, Zong-Wan

2018-04-25

Studies on the development of fluorescent organic molecules with different emission colors for imaging of organelles and their biomedical application are gaining lots of focus recently. Here, we report two cationic organochalcogens 1 and 2, both of which exhibit very weak green emission (Φ 1 = 0.12%; Φ 2 = 0.09%) in dilute solution as monomers, but remarkably enhanced green emission upon interaction with nucleic acids and large red-shifted emission in aggregate state by the formation of excimers at high concentration. More interestingly, the monomer emission and excimer-like emission can be used for dual color imaging of different organelles. Upon passively diffusing into cells, both probes selectively stain nucleoli with strong green emission upon 488 nm excitation, whereas upon 405 nm excitation, a completely different stain pattern by staining lysosomes (for 1) or mitochondria (for 2) with distinct red emission is observed because of the highly concentrated accumulation in these organelles. Studies on the mechanism of the accumulation in lysosomes (for 1) or mitochondria (for 2) found that the accumulations of the probes are dependent on the membrane permeabilization, which make the probes have great potential in diagnosing cell damage by sensing lysosomal or mitochondrial membrane permeabilization. The study is demonstrative, for the first time, of two cationic molecules for dual-color imaging nucleoli and lysosomes (1)/mitochondria (2) simultaneously in live cell based on monomer and excimer-like emission, respectively, and more importantly, for diagnosing cell damage.

Numerical Modeling of Fluorescence Emission Energy Dispersion in Luminescent Solar Concentrator

NASA Astrophysics Data System (ADS)

Li, Lanfang; Sheng, Xing; Rogers, John; Nuzzo, Ralph

2013-03-01

We present a numerical modeling method and the corresponding experimental results, to address fluorescence emission dispersion for applications such as luminescent solar concentrator and light emitting diode color correction. Previously established modeling methods utilized a statistic-thermodynamic theory (Kenard-Stepnov etc.) that required a thorough understanding of the free energy landscape of the fluorophores. Some more recent work used an empirical approximation of the measured emission energy dispersion profile without considering anti-Stokes shifting during absorption and emission. In this work we present a technique for modeling fluorescence absorption and emission that utilizes the experimentally measured spectrum and approximates the observable Frank-Condon vibronic states as a continuum and takes into account thermodynamic energy relaxation by allowing thermal fluctuations. This new approximation method relaxes the requirement for knowledge of the fluorophore system and reduces demand on computing resources while still capturing the essence of physical process. We present simulation results of the energy distribution of emitted photons and compare them with experimental results with good agreement in terms of peak red-shift and intensity attenuation in a luminescent solar concentrator. This work is supported by the DOE `Light-Material Interactions in Energy Conversion' Energy Frontier Research Center under grant DE-SC0001293.

Coelenterazine-v ligated to Ca2+-triggered coelenterazine-binding protein is a stable and efficient substrate of the red-shifted mutant of Renilla muelleri luciferase.

PubMed

Stepanyuk, Galina A; Unch, James; Malikova, Natalia P; Markova, Svetlana V; Lee, John; Vysotski, Eugene S

2010-10-01

It has been shown that the coelenterazine analog, coelenterazine-v, is an efficient substrate for a reaction catalyzed by Renilla luciferase. The resulting bioluminescence emission maximum is shifted to a longer wavelength up to 40 nm, which allows the use of some "yellow" Renilla luciferase mutants for in vivo imaging. However, the utility of coelenterazine-v in small-animal imaging has been hampered by its instability in solution and in biological tissues. To overcome this drawback, we ligated coelenterazine-v to Ca(2+)-triggered coelenterazine-binding protein from Renilla muelleri, which apparently functions in the organism for stabilizing and protecting coelenterazine from oxidation. The coelenterazine-v bound within coelenterazine-binding protein has revealed a greater long-term stability at both 4 and 37 °C. In addition, the coelenterazine-binding protein ligated by coelenterazine-v yields twice the total light over free coelenterazine-v as a substrate for the red-shifted R. muelleri luciferase. These findings suggest the possibility for effective application of coelenterazine-v in various in vitro assays.

Bistetrazine-cyanines as double-clicking fluorogenic two-point binder or crosslinker probes.

PubMed

Kormos, Attila; Koehler, Christine; Fodor, Eszter; Rutkai, Zsófia; Martin, Maddison; Mező, Gábor; Lemke, Edward; Kele, Péter

2018-04-20

Fluorogenic probes are capable of minimizing background fluorescence of unreacted and non-specifically adsorbed reagents. The preceding years have brought substantial developments in the design and synthesis of bioorthogonally applicable fluorogenic systems mainly based on the quenching effects of azide and tetrazine moieties. The modulation power exerted by these bioorthogonal motifs typically becomes less efficient on more conjugated systems, i.e. on probes with red-shifted emission wavelength. In order to reach efficient quenching, i.e. fluorogenicity even in the red range of the spectrum, We present the synthesis, fluorogenic and conjugation characterization of bistetrazine-cyanine probes with emission maxima between 600-620 nm. The probes can bind to genetically altered proteins harboring an 11-amino acid peptide tag with two appending cyclooctyne motifs. Moreover, we also demonstrate the use of these bistetrazines as fluorogenic, covalent cross-linkers between monocyclooctynylated proteins. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The luciferin binding site residues C/T311 (S314) influence the bioluminescence color of beetle luciferases through main-chain interaction with oxyluciferin phenolate.

PubMed

Viviani, V R; Amaral, D T; Neves, D R; Simões, A; Arnoldi, F G C

2013-01-08

Beetle luciferases emit different bioluminescence colors from green to red; however, no clear relationship between the identity of the luciferin binding site residues and bioluminescence colors was found in different luciferases, and it is unclear whether critical interactions affecting emission spectra occur on the thiazolyl or on the benzothiazolyl sides of the luciferin binding site. Through homology modeling and site-directed mutagenesis using our multicolor set of beetle luciferases (Pyrearinus termitilluminans larval click beetle, Pte, λ(max) = 534 nm; Phrixothrix hirtus railroad worm red emitting, PxRE, λ(max) = 623 nm; and Macrolampis sp2 firefly, Mac, λ(max) = 564 nm), we show that the residues C/T311 (S314) play an important role in bioluminescence color determination. Modeling studies indicate that the main-chain carbonyls of these residues are close to both oxyluciferin phenolate and AMP, whereas the side chains pack against second-shell residues. The C311(S314)A mutation considerably red shifts the spectra of the green-yellow-emitting luciferases (Pte λ(max) = 534 to 590 nm; Mac λ(max) = 564 to 583/613 nm) and affects the K(M) values for luciferin and ATP, but not the spectrum of the red-emitting luciferase. On the other hand, whereas the exchange between C/T311 (S314) caused smaller effects on the emission spectra of green-yellow-emitting luciferases, the C311T substitution (naturally found in green-emitting railroad worm luciferases) resulted in the largest reported blue shift in P. hirtus red-emitting luciferase (λ(max) = 623 to 606 nm). Altogether, these results indicate that the stability of residues C/T311 (S314) and the size of the cavity around oxyluciferin phenolate affect bioluminescence colors and suggest, for the first time, the occurrence of a critical interaction between main-chain carbonyls of position 311 (314) residues and oxyluciferin phenolate.

Two colorimetric and ratiometric fluorescence probes for hydrogen sulfide based on AIE strategy of α-cyanostilbenes

NASA Astrophysics Data System (ADS)

Zhao, Baoying; Yang, Binsheng; Hu, Xiangquan; Liu, Bin

2018-06-01

Aggregation-induced emission (AIE) active fluorescent probes have attracted great potential in biological sensors. In this paper two cyanostilbene based fluorescence chemoprobe Cya-NO2 (1) and Cya-N3 (2) were developed and evaluated for the selective and sensitive detection of hydrogen sulfide (H2S). Both of these probes behave aggression-induced emission (AIE) activity which fluoresces in the red region with a large Stokes shift. They exhibit rapid response to H2S with enormous colorimetric and ratiometric fluorescent changes. They are readily employed for assessing intracellular H2S levels.

Phenylene bridged boron-nitrogen containing dendrimers.

PubMed

Proń, Agnieszka; Baumgarten, Martin; Müllen, Klaus

2010-10-01

The synthesis and characterization of novel phenylene bridged boron-nitrogen containing π-conjugated dendrimers N3B6 and N3B3, with peripheral boron atoms and 1,3,5-triaminobenzene moiety as a core, are presented. UV-vis absorption and emission measurements reveal that the optical properties of the resulting compounds can be controlled by changing the donor/acceptor ratio: a 1:1 ratio results in a more efficient charge transfer than the 1:2 ratio. This was proven by the red shift of the emission maxima and the stronger solvatochromic effect in N3B3 compared to N3B6.

[Ph-Sensor Properties of a Fluorescent Protein from Dendronephthya sp].

PubMed

Pakhomov, A A; Chertkova, R V; Martynov, V I

2015-01-01

Genetically encoded biosensors based on fluorescent proteins are now widely applicable for monitoring pH changes in live cells. Here, we have shown that a fluorescent protein from Dendronephthya sp. (DendFP) exhibits a pronounced pH-sensitivity. Unlike most of known genetically encoded pH-sensors, fluorescence of the protein is not quenched upon medium acidification, but is shifting from the red to green spectral range. Therefore, quantitative measurements of intracellular pH are feasible by ratiometric comparison of emission intensities in the red and green spectral ranges, which makes DendFP advantageous compared with other genetically encoded pH-sensors.

Competition Between Resonant Plasmonic Coupling and Electrostatic Interaction in Reduced Graphene Oxide Quantum Dots.

PubMed

Karna, Sanjay; Mahat, Meg; Choi, Tae-Youl; Shimada, Ryoko; Wang, Zhiming; Neogi, Arup

2016-11-22

The light emission from reduced graphene oxide quantum dots (rGO-QDs) exhibit a significant enhancement in photoluminescence (PL) due to localized surface plasmon (LSP) interactions. Silver and gold nanoparticles (NPs) coupled to rGO nanoparticles exhibit the effect of resonant LSP coupling on the emission processes. Enhancement of the radiative recombination rate in the presence of Ag-NPs induced LSP tuned to the emission energy results in a four-fold increase in PL intensity. The localized field due to the resonantly coupled LSP modes induces n-π* transitions that are not observed in the absence of the resonant interaction of the plasmons with the excitons. An increase in the density of the Ag-NPs result in a detuning of the LSP energy from the emission energy of the nanoparticles. The detuning is due to the cumulative effect of the red-shift in the LSP energy and the electrostatic field induced blue shift in the PL energy of the rGO-QDs. The detuning quenches the PL emission from rGO-QDs at higher concentration of Ag NPs due to non-dissipative effects unlike plasmon induced Joule heating that occurs under resonance conditions. An increase in Au nanoparticles concentration results in an enhancement of PL emission due to electrostatic image charge effect.

Luminescence and thermal stability tuning in (Ba,Mn)3(Gd,Y)Na(PO4)5F:Eu2+ phosphors via cation-substitution

NASA Astrophysics Data System (ADS)

Mei, Juan; Lv, Lemin; Gao, Junsong; Wei, Yi; Feng, Yuxin; Yan, Chunjie; Li, Guogang

2018-04-01

In this work, [Y3+-Gd3+] and [Mn2+-Ba2+] substitutions were designed in Ba3GdNa(PO4)5F:Eu2+ system, which were marked as BG1-xYxNPF:Eu2+ and B1-yMyGNPF:Eu2+, respectively. It is found that their luminescence properties and thermal stability could be obviously tuned. For BG1-xYxNPF:Eu2+ series, under 365 nm UV light, the emission spectra exhibited a continuous red-shift from 458 nm (x = 0) to 485 nm (x = 1) with the corresponding luminescence varying from blue light to cyan light. For B1-yMyGNPF:Eu2+ series, it was observed the coexistence of blue-green and enhanced red emission of Eu2+ and the appearance of Eu3+ emission when Mn2+ partly substituted Ba2+, resulting in a final white emission. In addition, the thermal stabilities of B1-yMyGNPF:Eu2+ were obviously improved with Mn2+ doping. The corresponding luminescence and thermal stability tuning mechanisms were investigated.

Study of Sequential Dexter Energy Transfer in High Efficient Phosphorescent White Organic Light-Emitting Diodes with Single Emissive Layer

NASA Astrophysics Data System (ADS)

Kim, Jin Wook; You, Seung Il; Kim, Nam Ho; Yoon, Ju-An; Cheah, Kok Wai; Zhu, Fu Rong; Kim, Woo Young

2014-11-01

In this study, we report our effort to realize high performance single emissive layer three color white phosphorescent organic light emitting diodes (PHOLEDs) through sequential Dexter energy transfer of blue, green and red dopants. The PHOLEDs had a structure of; ITO(1500 Å)/NPB(700 Å)/mCP:Firpic-x%:Ir(ppy)3-0.5%:Ir(piq)3-y%(300 Å)/TPBi(300 Å)/Liq(20 Å)/Al(1200 Å). The dopant concentrations of FIrpic, Ir(ppy)3 and Ir(piq)3 were adjusted and optimized to facilitate the preferred energy transfer processes attaining both the best luminous efficiency and CIE color coordinates. The presence of a deep trapping center for charge carriers in the emissive layer was confirmed by the observed red shift in electroluminescent spectra. White PHOLEDs, with phosphorescent dopant concentrations of FIrpic-8.0%:Ir(ppy)3-0.5%:Ir(piq)3-0.5% in the mCP host of the single emissive layer, had a maximum luminescence of 37,810 cd/m2 at 11 V and a luminous efficiency of 48.10 cd/A at 5 V with CIE color coordinates of (0.35, 0.41).

Raman scattering and red fluorescence in the photochemical transformation of dry tryptophan particles

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lai, Chih Wei; Schwab, Mark; Hill, Steven C.

Tryptophan is a fluorescent amino acid common in proteins. Its absorption is largest for wavelengths λ ≲ 290 nm and its fluorescence emissions peak around 300–350 nm, depending upon the local environment. Here we report the observation of red fluorescence near 600 nm emerging from 488-nm continuous-wave (CW) laser photoexcitation of dry tryptophan (Trp) particles. With an excitation intensity below 0.5 kW/cm 2, dry Trp particles yield distinctive Raman scattering peaks in the presence of relatively weak and spectrally broad emissions with λ ~500–700 nm, allowing estimation of particle temperature at low excitation intensities. When the photoexcitation intensity is increasedmore » to 1 kW/cm 2 or more for a few minutes, fluorescence intensity dramatically increases by more than two orders of magnitude. The fluorescence continues to increase in intensity and gradually shift to the red when photoexcitation intensity and the duration of exposure are increased. The resulting products absorb at visible wavelengths and generate red fluorescence with λ ~ 650–800 nm with 633-nm CW laser excitation. In conclusion, we attribute the emergence of orange and red fluorescence in the Trp products to a photochemical transformation that is instigated by weak optical transitions to triplet states in Trp with 488-nm excitation and which may be expedited by a photothermal effect.« less

Raman scattering and red fluorescence in the photochemical transformation of dry tryptophan particles

DOE PAGES

Lai, Chih Wei; Schwab, Mark; Hill, Steven C.; ...

2016-05-19

Tryptophan is a fluorescent amino acid common in proteins. Its absorption is largest for wavelengths λ ≲ 290 nm and its fluorescence emissions peak around 300–350 nm, depending upon the local environment. Here we report the observation of red fluorescence near 600 nm emerging from 488-nm continuous-wave (CW) laser photoexcitation of dry tryptophan (Trp) particles. With an excitation intensity below 0.5 kW/cm 2, dry Trp particles yield distinctive Raman scattering peaks in the presence of relatively weak and spectrally broad emissions with λ ~500–700 nm, allowing estimation of particle temperature at low excitation intensities. When the photoexcitation intensity is increasedmore » to 1 kW/cm 2 or more for a few minutes, fluorescence intensity dramatically increases by more than two orders of magnitude. The fluorescence continues to increase in intensity and gradually shift to the red when photoexcitation intensity and the duration of exposure are increased. The resulting products absorb at visible wavelengths and generate red fluorescence with λ ~ 650–800 nm with 633-nm CW laser excitation. In conclusion, we attribute the emergence of orange and red fluorescence in the Trp products to a photochemical transformation that is instigated by weak optical transitions to triplet states in Trp with 488-nm excitation and which may be expedited by a photothermal effect.« less

Raman scattering and red fluorescence in the photochemical transformation of dry tryptophan particles.

PubMed

Lai, Chih Wei; Schwab, Mark; Hill, Steven C; Santarpia, Joshua; Pan, Yong-Le

2016-05-30

Tryptophan is a fluorescent amino acid common in proteins. Its absorption is largest for wavelengths λ ≲ 290 nm and its fluorescence emissions peak around 300-350 nm, depending upon the local environment. Here we report the observation of red fluorescence near 600 nm emerging from 488-nm continuous-wave (CW) laser photoexcitation of dry tryptophan (Trp) particles. With an excitation intensity below 0.5 kW/cm², dry Trp particles yield distinctive Raman scattering peaks in the presence of relatively weak and spectrally broad emissions with λ ∼500-700 nm, allowing estimation of particle temperature at low excitation intensities. When the photoexcitation intensity is increased to 1 kW/cm² or more for a few minutes, fluorescence intensity dramatically increases by more than two orders of magnitude. The fluorescence continues to increase in intensity and gradually shift to the red when photoexcitation intensity and the duration of exposure are increased. The resulting products absorb at visible wavelengths and generate red fluorescence with λ ∼ 650-800 nm with 633-nm CW laser excitation. We attribute the emergence of orange and red fluorescence in the Trp products to a photochemical transformation that is instigated by weak optical transitions to triplet states in Trp with 488-nm excitation and which may be expedited by a photothermal effect.

Lipid chain saturation and the cholesterol in the phospholipid membrane affect the spectroscopic properties of lipophilic dye nile red

NASA Astrophysics Data System (ADS)

Halder, Animesh; Saha, Baishakhi; Maity, Pabitra; Kumar, Gopinatha Suresh; Sinha, Deepak Kumar; Karmakar, Sanat

2018-02-01

We have studied the effect of composition and the phase state of phospholipid membranes on the emission spectrum, anisotropy and lifetime of a lipophilic fluorescence probe nile red. Fluorescence spectrum of nile red in membranes containing cholesterol has also been investigated in order to get insights into the influence of cholesterol on the phospholipid membranes. Maximum emission wavelength (λem) of nile red in the fluid phase of saturated and unsaturated phospholipids was found to differ by 10 nm. The λem was also found to be independent of chain length and charge of the membrane. However, the λem is strongly dependent on the temperature in the gel phase. The λem and rotational diffusion rate decrease, whereas the anisotropy and lifetime increase markedly with increasing cholesterol concentration for saturated phosoholipids, such as, dimyristoyl phosphatidylcholine (DMPC) in the liquid ordered phase. However, these spectroscopic properties do not alter significantly in case of unsaturated phospholipids, such as, dioleoyl phosphatidylcholine (DOPC) in liquid disordered phase. Interestingly, red edge excitation shift (REES) in the presence of lipid-cholesterol membranes is the direct consequences of change in rotational diffusion due to motional restriction of lipids in the presence of cholesterol. This study provides correlations between the membrane compositions and fluorescence spectral features which can be utilized in a wide range of biophysical fields as well the cell biology.

Reconsidering Dark Matter

NASA Astrophysics Data System (ADS)

Aisenberg, Sol

2012-02-01

There is a difference between (a) distances of remote standard candles, SN Type Ia, and (b) distances based upon their red shifts. It was believed that these galaxies had accelerated and used Dark Energy. There are 2 assumptions not supported by observations. The first is that the red shifts for remote galaxies are due to the Doppler Effect associated with receding velocity. Hubble only observed red shifts as a function of distances of known stars, and never measured receding velocities. He suggested the Doppler Effect as a cause, but expressed doubt about the suggestion. There are other causes for a red shift - gravity red shift of light from the sun, and loss of photon energy by gravity interaction of photons with dust and gas in interstellar space. The second assumption is that Hubble's linear relationship between the observed red shift and the distance will be valid at very large distances. Increasing red shift corresponds to a decrease of photon energy towards zero, and cannot be used for very remote stars - where the photon energy approaches zero and the red shift dependence becomes nonlinear and asymptotic to a constant value. This predicts the difference between the galaxy distances and the distances determined from their observed red shifts. The recent Nobel Prize (to Schmidt, Reis, and Perlmutter) needs reexamination. Two basic assumptions that are the foundation of their work may not be accurate. Details are in my earlier essays in ``The Misunderstood Universe'', 2009. .

Site-Selective Benzannulation of N-Heterocycles in Bidentate Ligands Leads to Blue-Shifted Emission from [( P^N)Cu]2(μ-X)2 Dimers.

PubMed

Mondal, Rajarshi; Lozada, Issiah B; Davis, Rebecca L; Williams, J A Gareth; Herbert, David E

2018-05-07

Benzannulated bidentate pyridine/phosphine ( P^N) ligands bearing quinoline or phenanthridine (3,4-benzoquinoline) units have been prepared, along with their halide-bridged, dimeric Cu(I) complexes of the form [( P^N)Cu] 2 (μ-X) 2 . The copper complexes are phosphorescent in the orange-red region of the spectrum in the solid-state under ambient conditions. Structural characterization in solution and the solid-state reveals a flexible conformational landscape, with both diamond-like and butterfly motifs available to the Cu 2 X 2 cores. Comparing the photophysical properties of complexes of (quinolinyl)phosphine ligands with those of π-extended (phenanthridinyl)phosphines has revealed a counterintuitive impact of site-selective benzannulation. Contrary to conventional assumptions regarding π-extension and a bathochromic shift in the lowest energy absorption maxima, a blue shift of nearly 40 nm in the emission wavelength is observed for the complexes with larger ligand π-systems, which is assigned as phosphorescence on the basis of emission energies and lifetimes. Comparison of the ground-state and triplet excited state structures optimized from DFT and TD-DFT calculations allows attribution of this effect to a greater rigidity for the benzannulated complexes resulting in a higher energy emissive triplet state, rather than significant perturbation of orbital energies. This study reveals that ligand structure can impact photophysical properties for emissive molecules by influencing their structural rigidity, in addition to their electronic structure.

Chromatic shifts in the fluorescence emitted by murine thymocytes stained with Hoechst 33342.

PubMed

Petersen, Timothy W; Ibrahim, Sherrif F; Diercks, Alan H; van den Engh, Ger

2004-08-01

Many methods in flow cytometry rely on staining DNA with a fluorescent dye to gauge DNA content. From the relative intensity of the fluorescence signature, one can then infer position in cell cycle, amount of DNA (i.e., for sperm selection), or, as in the case of flow karyotyping, to distinguish individual chromosomes. This work examines the staining of murine thymocytes with a common DNA dye, Hoechst 33342, to investigate nonlinearities in the florescence intensity as well as chromatic shifts. Murine thymocytes were stained with Hoechst 33342 and measured in a flow cytometer at two fluorescence emission bands. In other measurements, cells were stained at different dye concentrations, and then centrifuged. The supernatant was then used for a second round of staining to test the amount of dye uptake. Finally, to test for resonant energy transfer, we measured fluorescence anisotropy at two different wavelengths. The fluorescence of cells stained with Hoechst 33342 is a nonlinear process that shows an overall decrease in intensity with increased dye uptake, and spectral shift to the red. Along with the spectral shift of the fluorescence to the longer wavelengths, we document decreases in the fluorescence anisotropy that may indicate resonant energy transfer. At low concentrations, Hoechst 33342 binds to the minor groove of DNA and shows an increase in fluorescence and a blue shift upon binding. At higher concentrations, at which the dye molecules can no longer bind without overlapping, the blue fluorescence decreases and the red fluorescence increases until there is approximately one dye molecule per DNA base pair. The ratio of the blue fluorescence to the red fluorescence is an accurate indicator of the cellular dye concentration.

Absorption and fluorescence emission spectroscopic characters of naphtho-homologated yy-DNA bases and effect of methanol solution and base pairing.

PubMed

Zhang, Laibin; Li, Huifang; Li, Jilai; Chen, Xiaohua; Bu, Yuxiang

2010-03-01

A comprehensive theoretical study of electronic transitions of naphtho-homologated base analogs, namely, yy-T, yy-C, yy-A, and yy-G, was performed. The nature of the low-lying excited states is discussed, and the results are compared with those from experiment and also with those of y-bases. Geometrical characteristics of the lowest excited singlet pipi* and npi* states were explored using the CIS method, and the effects of methanol solution and paring with their complementary natural bases on the relevant absorption and emission spectra of these modified bases were examined. The calculated excitation and emission energies agree well with the measured data, where experimental results are available. In methanol solution, the fluorescence from yy-A and yy-G would be expected to occur around 539 and 562 nm, respectively, suggesting that yy-A is a green-colored fluorophore, whereas yy-G is a yellow-colored fluorophore. The methanol solution was found to red-shift both the absorption and emission maxima of yy-A, yy-T, and yy-C, but blue-shift those for yy-G. Generally, though base pairing has no significant effects on the absorption and fluorescence maxima of yy-A, yy-C, and yy-T, it blue-shifts those for yy-G. (c) 2009 Wiley Periodicals, Inc.

Comprehensive investigation of the excited-state dynamics of push-pull triphenylamine dyes as models for photonic applications.

PubMed

Ishow, Eléna; Clavier, Gilles; Miomandre, Fabien; Rebarz, Mateusz; Buntinx, Guy; Poizat, Olivier

2013-09-07

A series of emitting push-pull triarylamine derivatives, models of their widely used homologues in photonics and organic electronics, was investigated by steady-state and time-resolved spectroscopy. Their structural originality stems from the sole change of the electron-withdrawing substituent X (-H: 1, -CN: 2, -NO2: 3, -CHC(CN)2: 4), giving rise to efficient emission tuning from blue to red upon increasing the X electron-withdrawing character. All compounds are highly fluorescent in alkanes. The more polar compounds 2-4 undergo considerable Stokes shift and emission quenching in polar solvents. Femtosecond transient absorption data allowed us to identify the nature of the emissive state which varies as a function of the compound and surrounding polarity. A long-lived ππ* excited state with weak charge transfer character was found for 1. This excited state evolves into a long-lived ICT state with red-shifted emission for 2 in polar solvents. For 3 and 4, the ICT state is directly populated in all solvents. Long-lived and emissive in n-hexane, it relaxes in toluene to a new ICT' conformation with stronger charge transfer character and enhanced Stokes shift. In more polar THF, ethanol, and nitrile solvents, ICT relaxes to a dark excited state ICT'' with viscosity-dependent kinetics (<10 ps). The ICT'' state lifetime drops with increasing solvent polarity (150 ps for 3 in THF, 8.5 ps in butyronitrile, 1.9 ps in acetonitrile), denoting an efficient radiationless deactivation to the ground state (back charge transfer). This result reveals a very small S0-S1 energy gap at the relaxed ICT'' geometry, with a possible close-lying S0-S1 conical intersection, which suggests that the ICT → ICT'' process results from a structural change involving a large-amplitude molecular distortion. This fast structural change can account for the strong fluorescence quenching observed for 3 and 4 in polar solvents. Finally, the magnitude of intersystem crossing between the singlet and triplet excited states largely depends on the electron-deficient X unit and the solvent itself. These observations help one conclude on the prevailing role played by the electron-withdrawing groups and the surrounding polarity in the photophysical performances of triphenylamine derivatives, largely employed in numerous emissive solid-state devices.

Sensitive red protein calcium indicators for imaging neural activity

PubMed Central

Dana, Hod; Mohar, Boaz; Sun, Yi; Narayan, Sujatha; Gordus, Andrew; Hasseman, Jeremy P; Tsegaye, Getahun; Holt, Graham T; Hu, Amy; Walpita, Deepika; Patel, Ronak; Macklin, John J; Bargmann, Cornelia I; Ahrens, Misha B; Schreiter, Eric R; Jayaraman, Vivek; Looger, Loren L; Svoboda, Karel; Kim, Douglas S

2016-01-01

Genetically encoded calcium indicators (GECIs) allow measurement of activity in large populations of neurons and in small neuronal compartments, over times of milliseconds to months. Although GFP-based GECIs are widely used for in vivo neurophysiology, GECIs with red-shifted excitation and emission spectra have advantages for in vivo imaging because of reduced scattering and absorption in tissue, and a consequent reduction in phototoxicity. However, current red GECIs are inferior to the state-of-the-art GFP-based GCaMP6 indicators for detecting and quantifying neural activity. Here we present improved red GECIs based on mRuby (jRCaMP1a, b) and mApple (jRGECO1a), with sensitivity comparable to GCaMP6. We characterized the performance of the new red GECIs in cultured neurons and in mouse, Drosophila, zebrafish and C. elegans in vivo. Red GECIs facilitate deep-tissue imaging, dual-color imaging together with GFP-based reporters, and the use of optogenetics in combination with calcium imaging. DOI: http://dx.doi.org/10.7554/eLife.12727.001 PMID:27011354

Communication: Broad manifold of excitonic states in light-harvesting complex 1 promotes efficient unidirectional energy transfer in vivo

NASA Astrophysics Data System (ADS)

Sohail, Sara H.; Dahlberg, Peter D.; Allodi, Marco A.; Massey, Sara C.; Ting, Po-Chieh; Martin, Elizabeth C.; Hunter, C. Neil; Engel, Gregory S.

2017-10-01

In photosynthetic organisms, the pigment-protein complexes that comprise the light-harvesting antenna exhibit complex electronic structures and ultrafast dynamics due to the coupling among the chromophores. Here, we present absorptive two-dimensional (2D) electronic spectra from living cultures of the purple bacterium, Rhodobacter sphaeroides, acquired using gradient assisted photon echo spectroscopy. Diagonal slices through the 2D lineshape of the LH1 stimulated emission/ground state bleach feature reveal a resolvable higher energy population within the B875 manifold. The waiting time evolution of diagonal, horizontal, and vertical slices through the 2D lineshape shows a sub-100 fs intra-complex relaxation as this higher energy population red shifts. The absorption (855 nm) of this higher lying sub-population of B875 before it has red shifted optimizes spectral overlap between the LH1 B875 band and the B850 band of LH2. Access to an energetically broad distribution of excitonic states within B875 offers a mechanism for efficient energy transfer from LH2 to LH1 during photosynthesis while limiting back transfer. Two-dimensional lineshapes reveal a rapid decay in the ground-state bleach/stimulated emission of B875. This signal, identified as a decrease in the dipole strength of a strong transition in LH1 on the red side of the B875 band, is assigned to the rapid localization of an initially delocalized exciton state, a dephasing process that frustrates back transfer from LH1 to LH2.

Pressure-induced photoluminescence of MgO

NASA Astrophysics Data System (ADS)

Li, Xin; Yuan, Ye; Zhang, Jinbo; Kim, Taehyun; Zhang, Dongzhou; Yang, Ke; Lee, Yongjae; Wang, Lin

2018-05-01

It is reported in this paper that pressure can promote strong photoluminescence (PL) in MgO. The PL measurements of MgO indicate that it has no obvious luminescence at pressures lower than 13 GPa. PL starts to appear upon further compression and reaches a maximum intensity at about 35 GPa. The center of the emission band shows a red shift at lower pressures and turns to a blue shift as pressure exceeds 25 GPa. The PL is preserved upon complete decompression. The defects and micro-strain due to the plastic deformation of MgO are likely responsible for the origin of the luminescence.

Blue emission in photoluminescence spectra of the red phosphor CaAlSiN3:Eu2+ at low Eu2+ concentration

NASA Astrophysics Data System (ADS)

Suda, Yoriko; Kamigaki, Yoshiaki; Yamamoto, Hajime

2018-04-01

In red phosphor CaAlSiN3:Eu2+, unintentional blue emission occurs with increasing intensity at low Eu2+ concentrations and also at low measurement temperatures. Time-resolved photoluminescence measurements were used to confirm the decrease in red emission and increase in blue emission with the decreasing Eu2+ concentration. The peak timing of blue emission occurred faster than that of red emission, and long lasting luminescence of red emission was observed as well as that of blue emission. The Eu2+ concentration dependences of the red and blue emissions were similar to those of the g values 4.75 (Eu2+) and 2.0025 (nitrogen vacancies), respectively, which were observed from electron spin resonance (ESR) measurements. The origin of the blue emission is proposed to be nitrogen vacancy defects, which had about the same ESR signal intensity as that of Eu2+ ions in CaAlSiN3:Eu2+ containing 0.01 at. % Eu2+. The possibility of red emission also arising from excited electron tunneling or thermal pathways via nitrogen vacancies is discussed. Long lasting red emission was observed, which is proposed to involve trapped electrons remaining at nitrogen vacancies, yielding blue emission and inducing red emission from Eu2+ ions.

Imaging with HST the Time Evolution of Eta Carinae's Colliding Winds

NASA Technical Reports Server (NTRS)

Gull, Theodore R.; Madura, Thomas I.; Groh, Jose H.; Corcoran, Michael F.

2011-01-01

We report new HST/STIS observations that map the high-ionization forbidden line emission in the inner arcsecond of Eta Car, the first that fully image the extended wind-wind interaction region of the massive colliding wind binary. These observations were obtained after the 2009.0 periastron at orbital phases 0.084, 0.163, and 0.323 of the 5.54-year spectroscopic cycle. We analyze the variations in brightness and morphology of the emission, and find that blue-shifted emission (-400 to -200 km/s is symmetric and elongated along the northeast-southwest axis, while the red-shifted emission (+ 100 to +200 km/s) is asymmetric and extends to the north-northwest. Comparison to synthetic images generated from a 3-D dynamical model strengthens the 3-D orbital orientation found by Madura et al. (2011), with an inclination i approx. 138deg, argument of periapsis omega approx. 270deg, and an orbital axis that is aligned at the same PA on the sky as the symmetry axis of the Homunculus, 312deg. We discuss the potential that these and future mappings have for constraining the stellar parameters of the companion star and the long-term variability of the system.

A new approach way for white organic light-emitting diodes based on single emitting layer and large stokes shift.

PubMed

Kim, Beomjin; Park, Youngil; Shin, Yunseop; Lee, Jiwon; Shin, Hwangyu; Park, Jongwook

2014-07-01

New red dopant, DPPZ based on porphyrin moiety was synthesized. DPPZ showed UV-Vis and PL maximum values of 412 and 638 nm, indicating the large stokes shift. New blue host compound, TATa was also synthesized and used for co-mixed white emission. TATa exhibited UV-Vis. and PL maximum values of 403 nm and 463 nm in film state. Thus, when two compounds are used as co-mixed emitter in OLED device, there is no energy transfer from blue emission of TATa to DPPZ due to large stokes shift of DPPZ. Based on the PL result, it is available to realize two-colored white in PL and EL spectra. As a result of this, two-mixed compounds showed vivid their own PL emission peaks of 466 and 638 nm in film state. Also, white OLED device using two-mixed compounds system was fabricated. EL spectrum shows 481 and 646 nm peaks and two separate EL peaks. As the operation voltage is increased from 8 to 11 V, EL spectrum does not change the peak shape and maximum wavelength values. EL performance of white device showed 0.041 cd/A, 0.018 Im/W, and CIE (0.457, 0.331) at 8 V.

Enhancement of the Ultraviolet Photoresponsivity of Al-doped ZnO Thin Films Prepared by using the Sol-gel Spin-coating Method

NASA Astrophysics Data System (ADS)

Lee, Wookbin; Leem, Jae-Young

2018-03-01

We report the structural, morphological, optical, and ultraviolet (UV) photoresponse properties of Al-doped ZnO (AZO) thin films prepared on silicon substrates with different Al doping concentrations by using the sol-gel spin-coating method. An analysis of the X-ray diffraction patterns of the AZO thin films revealed that the average grain size decreased and the c-axis lattice constant increased with Al content. The field-emission scanning electron microscopy images showed that with Al doping, the grain size decreased, but the film density increased with increasing Al doping concentration from 0% to 3%. These results indicate that the surface area of the film increased with increasing Al doping. The absorbance spectra revealed that the UV absorbance of the AZO thin films increased with increasing Al doping concentration and that the absorption onset shifted towards lower energies. The photoluminescence spectra revealed that with increasing Al doping, the intensity of the visible emission greatly decreased and the visible emission peak shifted forward lower energy (a red shift). The UV sensor based on the AZO thin films exhibited a higher responsivity than that based on the undoped ZnO thin film. Therefore, this study provides a facile method for improving the photoresponsivity of UV sensors.

Time evolution, Lamb shift, and emission spectra of spontaneous emission of two identical atoms

NASA Astrophysics Data System (ADS)

Wang, Da-Wei; Li, Zheng-Hong; Zheng, Hang; Zhu, Shi-Yao

2010-04-01

A unitary transformation method is used to investigate the dynamic evolution of two multilevel atoms, in the basis of symmetric and antisymmetric states, with one atom being initially prepared in the first excited state and the other in the ground state. The unitary transformation guarantees that our calculations are based on the ground state of the atom-field system and the self-energy is subtracted at the beginning. The total Lamb shifts of the symmetric and antisymmetric states are divided into transformed shift and dynamic shift. The transformed shift is due to emitting and reabsorbing of virtual photons, by a single atom (nondynamic single atomic shift) and between the two atoms (quasi-static shift). The dynamic shift is due to the emitting and reabsorbing of real photons, by a single atom (dynamic single atomic shift) and between the two atoms (dynamic interatomic shift). The emitting and reabsorbing of virtual and real photons between the two atoms result in the interatomic shift, which does not exist for the one-atom case. The spectra at the long-time limit are calculated. If the distance between the two atoms is shorter than or comparable to the wavelength, the strong coupling between the two atoms splits the spectrum into two peaks, one from the symmetric state and the other from the antisymmetric state. The origin of the red or blue shifts for the symmetric and antisymmetric states mainly lies in the negative or positive interaction energy between the two atoms. In the investigation of the short time evolution, we find the modification of the effective density of states by the interaction between two atoms can modulate the quantum Zeno and quantum anti-Zeno effects in the decays of the symmetric and antisymmetric states.

Supramolecular assembly of group 11 phosphorescent metal complexes for chemosensors of alcohol derivatives

NASA Astrophysics Data System (ADS)

Lintang, H. O.; Ghazalli, N. F.; Yuliati, L.

2018-04-01

We report on systematic study on vapochromic sensing of ethanol by using phosphorescent trinuclear metal pyrazolate complexes with supramolecular assembly of weak intermolecular metal-metal interactions using 4-(3,5-dimethoxybenzyl)-3,5-dimethyl pyrazole ligand (1) and group 11 metal ions (Cu(I), Ag(I), Au(I)). Upon excitation at 284, the resulting complexes showed emission bands with a peak centered at 616, 473 and 612 nm for 2(Cu), 2(Ag) and 2(Au), respectively. Chemosensor 2(Cu) showed positive response to ethanol vapors in 5 mins by blue-shifting its emission band from 616 to 555 nm and emitting bright orange to green. Otherwise 2(Au) gave shifting from its emission band centered at 612 to 587 nm with Δλ of 25 nm (41%) and color changes from red-orange to light green-orange while 2(Ag) showed quenching in its original emission intensity at 473 nm in 40% with color changes from dark green to less emissive. These results demonstrate that sensing capability of chemosensor 2(Cu) with suitable molecular design of ligand and metal ion in the complex is due to the formation of a weak intermolecular hydrogen bonding interaction of O atom at the methoxy of the benzyl ring with the OH of the vapors at the outside of the molecules.

J-aggregation in porphyrin nanoparticles induced by diphenylalanine

NASA Astrophysics Data System (ADS)

Li, Fengqing; Liu, Dongzhi; Wang, Tianyang; Hu, Jianxin; Meng, Fancui; Sun, Haiya; Shang, Zhi; Li, Pingan; Feng, Wenhui; Li, Wei; Zhou, Xueqin

2017-08-01

In this report, L-diphenylalanine-decorated tetraphenylporphyrin (TPPtFFC) was synthesized and self-assembled into regular nano-architechtures. The morphology of the assemblies varied with the concentration of TPPtFFC. The absorption spectra of the nanoparticles show the Soret band merges with the Q bands and redistributes with great red-shift, indicative of the formation of J-aggregates of the porphyrin molecules. The fluorescence emission of the nanoparticles is merged and red-shifted to near-infrared region. Studies of absorption and fluorescence spectra reveal an indispensible role of diphenylalanine group in the formation of J-aggregates. The Raman spectra disclose that diprotonation of the porphyrin core contributes to delocalized coherent excited states in the nanoparticles. The positive cotton effect in circular dichroism spectra corresponding to the Soret band of TPPtFFC in solution confirms the formation of J-aggregates with right-handed chirality of the dipole moment. This report will shed light on the rational design of porphyrin-peptide conjugates to mimic naturally light-harvesting complexes.

Lead selenide quantum dot polymer nanocomposites

NASA Astrophysics Data System (ADS)

Waldron, Dennis L.; Preske, Amanda; Zawodny, Joseph M.; Krauss, Todd D.; Gupta, Mool C.

2015-02-01

Optical absorption and fluorescence properties of PbSe quantum dots (QDs) in an Angstrom Bond AB9093 epoxy polymer matrix to form a nanocomposite were investigated. To the authors’ knowledge, this is the first reported use of AB9093 as a QD matrix material and it was shown to out-perform the more common poly(methyl methacrylate) matrix in terms of preserving the optical properties of the QD, resulting in the first reported quantum yield (QY) for PbSe QDs in a polymer matrix, 26%. The 1-s first excitonic absorption peak of the QDs in a polymer matrix red shifted 65 nm in wavelength compared to QDs in a hexane solution, while the emission peak in the polymer matrix red shifted by 38 nm. The fluorescence QY dropped from 55% in hexane to 26% in the polymer matrix. A time resolved fluorescence study of the QDs showed single exponential lifetimes of 2.34 and 1.34 μs in toluene solution and the polymer matrix respectively.

Safranine fluorescent staining of wood cell walls.

PubMed

Bond, J; Donaldson, L; Hill, S; Hitchcock, K

2008-06-01

Safranine is an azo dye commonly used for plant microscopy, especially as a stain for lignified tissues such as xylem. Safranine fluorescently labels the wood cell wall, producing green/yellow fluorescence in the secondary cell wall and red/orange fluorescence in the middle lamella (ML) region. We examined the fluorescence behavior of safranine under blue light excitation using a variety of wood- and fiber-based samples of known composition to interpret the observed color differentiation of different cell wall types. We also examined the basis for the differences in fluorescence emission using spectral confocal microscopy to examine lignin-rich and cellulose-rich cell walls including reaction wood and decayed wood compared to normal wood. Our results indicate that lignin-rich cell walls, such as the ML of tracheids, the secondary wall of compression wood tracheids, and wood decayed by brown rot, tend to fluoresce red or orange, while cellulose-rich cell walls such as resin canals, wood decayed by white rot, cotton fibers and the G-layer of tension wood fibers, tend to fluoresce green/yellow. This variation in fluorescence emission seems to be due to factors including an emission shift toward red wavelengths combined with dye quenching at shorter wavelengths in regions with high lignin content. Safranine fluorescence provides a useful way to differentiate lignin-rich and cellulose-rich cell walls without counterstaining as required for bright field microscopy.

Potential benefits of triethylamine as n-electron donor in the estimation of forskolin by electronic absorption and emission spectroscopy.

PubMed

Raju, Gajula; Ram Reddy, A

2016-02-05

Diterpenoid forskolin was isolated from Coleus forskolii. The electronic absorption and emission studies of forskolin were investigated in various solvents with an aim to improve its detection limits. The two chromophores present in the diterpenoid are not conjugated leading to the poor absorption and emission of UV light. The absorption and fluorescence spectra were solvent specific. In the presence of a monodentate ligand, triethylamine the detection of forskolin is improved by 3.63 times in ethanol with the fluorescence method and 3.36 times in DMSO by the absorption spectral method. The longer wavelength absorption maximum is blue shifted while the lower energy fluorescence maximum is red shifted in the presence of triethylamine. From the wavelength of fluorescence maxima of the exciplex formed between excited forskolin and triethylamine it is concluded that the order of reactivity of hydroxyl groups in the excited state forskolin is in the reverse order to that of the order of the reactivity of hydroxyl groups in its ground state. Copyright © 2015. Published by Elsevier B.V.

Interfacial exciplex formation in bilayers of conjugated polymers

NASA Astrophysics Data System (ADS)

Nobuyasu, R. S.; Araujo, K. A. S.; Cury, L. A.; Jarrosson, T.; Serein-Spirau, F.; Lère-Porte, J.-P.; Dias, F. B.; Monkman, A. P.

2013-10-01

The donor-acceptor interactions in sequential bilayer and blend films are investigated. Steady-state and time-resolved photoluminescence (PL) were measured to characterize the samples at different geometries of photoluminescence collection. At standard excitation, with the laser incidence at 45° of the normal direction of the sample surface, a band related to the aggregate states of donor molecules appears for both blend and bilayer at around 540 nm. For the PL spectra acquired from the edge of the bilayer, with the laser incidence made at normal direction of the sample surface (90° geometry), a new featureless band emission, red-shifted from donor and acceptor emission regions was observed and assigned as the emission from interfacial exciplex states. The conformational complexity coming from donor/acceptor interactions at the heterojunction interface of the bilayer is at the origin of this interfacial exciplex emission.

"CH"/N substituted mer-Gaq3 and mer-Alq3 derivatives: an effective approach for the tuning of emitting color.

PubMed

Gahungu, Godefroid; Zhang, Jingping

2005-09-22

Equilibrium geometry configurations of the "CH"/N substituted Alq3 and Gaq3 derivatives are calculated by density functional theory (B3LYP/6-31G). The frontier molecular orbital and gap energy calculations for all complexes have been performed at the HF/6-31G level. It was shown that, compared to the pristine molecules, the HOMO and LUMO are stabilized, the net effect being however an increasing/decreasing of the gap (Eg) depending on the position of the substituted group. On the basis of the equilibrium geometries, the effect of the substitution on the absorption and emission spectra was evaluated using TDB3LYP/3-21G. It was shown that the change of "CH"/N substituted position on 8-hydroxyquinoline ligand is a powerful approach for the tuning of emitting color. An important blue shift was predicted for 5-substituted 8-hydroxyquinoline derivatives, an important red one being observed for 4-substituted ones. Interestingly, relatively significant blue and red shifts were also predicted for the 7- and 2-substituted derivatives. In this work, the correlation between the spectrum shifts and the metal-ligand bonding is also discussed.

Femtosecond transient photoluminescence of the substituted poly(diphenylacetulene)s.

NASA Astrophysics Data System (ADS)

Piskun, N. V.; Wang, D. K.; Lim, H.; Epstein, A. J.; Vanwoerkom, L. D.; Gustafson, T. L.

2000-03-01

We present the results of a femtosecond transient photoluminescence (PL) study of solutions of two derivatives of substituted poly(diphenylacetylene) using an up-conversion technique. n-Butyl (nBu) and p-carbazole (Cz) substituted poly(diphenylacetylene), PDPA-nBu and PDPA-Cz respectively, have band gaps determined by maxima in the slope of absorption vs. energy of 2.75 eV and 2.63 eV. The steady state emission peaks are at 2.4 eV for PDPA-nBu and at 2.3 eV for PDPA-Cz respectively. The PL peak for PDPA-Cz is red shifted in comparison to the PL peak for PDPA-nBu. Roles of phenyl groups, electron donating effect of the carbazole side units and planarity of the backbone are discussed. Exciting at 3.1 eV, the fs PL shows a faster decay for PDPA-Cz than that for PDPA-nBu, in accord with the decrease of PL quantum efficiency of PDPA-Cz. The 200 fs - 80 ps PL(t) agrees with ~1 ns lifetime. The PDPA-Cz has larger red shift in the 0.2-20 ps time frame. The origin of that shift will be discussed. This work is supported in part by ONR.

Red emission enhancement from CaMoO4:Eu3+ by co-doping of Bi3+ for near UV/blue LED pumped white pcLEDs: Energy transfer studies

NASA Astrophysics Data System (ADS)

Wangkhem, Ranjoy; Yaba, Takhe; Shanta Singh, N.; Ningthoujam, R. S.

2018-03-01

CaMoO4:Eu3+ (3 at. %)/Bi3+ (x at. %) nanophosphors were synthesized hydrothermally. All the samples can be excited by 280, 320, 393, and 464 nm (blue) wavelengths for generation of red color emission. Enhancement in 5D0 → 7F2 (615 nm) emission (f-f transition) of Eu3+ is observed when Bi3+ is incorporated in CaMoO4:Eu3+. This is due to the efficient energy transfer from Bi3+ to Eu3+ ions. Introduction of Bi3+ in the system does not lead to the change of emission wavelength of Eu3+. However, Bi3+ incorporation in the system induces a shift in Mo-O charge transfer band absorption from 295 to 270 nm. This may be due to the increase in electronegativity between Mo and O bond in the presence of Bi3+ leading to change in crystal field environment of Mo6+ in MoO42-. At the optimal concentration of Bi3+, an enhancement in emission by a factor of ˜10 and 4.2 in the respective excitation at 393 (7F0 → 5L6) and 464 nm (7F0 → 5D2) is observed. The energy transfer efficiency from Bi3+ to Eu3+ increases from 75% to 96%. The energy transfer is observed to occur mainly via dipole-dipole interactions. Maximum quantum yield value of 55% is observed from annealed CaMoO4:Eu3+ (3 at. %) when sensitized with Bi3+ (15 at. %) under 464 nm excitation. From Commission International de I'Eclairage chromaticity coordinates, the color (red) saturation is observed to be nearly 100%.

Role of Ni2+(d8) ions in electrical, optical and magnetic properties of CdS nanowires for optoelectronic and spintronic applications

NASA Astrophysics Data System (ADS)

Arshad Kamran, Muhammad

2018-06-01

For the first time, 1D Ni ion doped CdS nanowires (NWs) were synthesized via chemical vapour deposition (CVD). The synthesized Cd0.886Ni0.114S NWs were single crystalline. We have reported here the investigation of optical, electrical and magnetic properties of prepared NWs for optoelectronic and spintronic applications. Successful incorporation of Ni ions in an individual CdS NW has been confirmed through several characterization tools: significantly higher angle and phonon mode shift were observed in the XRD and Raman spectra. SEM-EDX and XPS analysis also confirmed the presence of Ni2+ ions. Room temperature photoluminescence (RT-PL) showed multiple peaks: two emission peaks in the visible region centered at 517.1 nm (green), 579.2 nm (orange), and a broad-band near infra-red (NIR) emission centered at 759.9 nm. The first peak showed 5 nm red shift upon Ni2+ doping, hinting at the formation of exciton magnetic polarons (EMPs), and broad NIR emission was observed in both chlorides and bromides, which was assigned to d‑d transition of Ni ions whose energy levels lying at 749.51 nm (13 342 cm–1) and 750.98 nm (13 316 cm–1) are very close to NIR emission. Orange emission not only remained at same peak position—its PL intensity was also significantly enhanced at 78 K; this was assigned to d‑d transition (3A2g → 1Eg) of Ni2+ ions. It was observed that 11.4% Ni2+ ion doping enhanced the conductivity of our sample around 20 times, and saturation magnetization (Ms) increased from 7.2 × 10‑5 Am2/Kg to 1.17 × 10‑4 Am2/Kg, which shows promise for optoelectronic and spintronic applications.

Role of Ni2+(d8) ions in electrical, optical and magnetic properties of CdS nanowires for optoelectronic and spintronic applications.

PubMed

Kamran, Muhammad Arshad

2018-06-29

For the first time, 1D Ni ion doped CdS nanowires (NWs) were synthesized via chemical vapour deposition (CVD). The synthesized Cd 0.886 Ni 0.114 S NWs were single crystalline. We have reported here the investigation of optical, electrical and magnetic properties of prepared NWs for optoelectronic and spintronic applications. Successful incorporation of Ni ions in an individual CdS NW has been confirmed through several characterization tools: significantly higher angle and phonon mode shift were observed in the XRD and Raman spectra. SEM-EDX and XPS analysis also confirmed the presence of Ni 2+ ions. Room temperature photoluminescence (RT-PL) showed multiple peaks: two emission peaks in the visible region centered at 517.1 nm (green), 579.2 nm (orange), and a broad-band near infra-red (NIR) emission centered at 759.9 nm. The first peak showed 5 nm red shift upon Ni 2+ doping, hinting at the formation of exciton magnetic polarons (EMPs), and broad NIR emission was observed in both chlorides and bromides, which was assigned to d-d transition of Ni ions whose energy levels lying at 749.51 nm (13 342 cm -1 ) and 750.98 nm (13 316 cm -1 ) are very close to NIR emission. Orange emission not only remained at same peak position-its PL intensity was also significantly enhanced at 78 K; this was assigned to d-d transition ( 3 A 2g  →  1 E g ) of Ni 2+ ions. It was observed that 11.4% Ni 2+ ion doping enhanced the conductivity of our sample around 20 times, and saturation magnetization (M s ) increased from 7.2 × 10 -5 Am 2 /Kg to 1.17 × 10 -4 Am 2 /Kg, which shows promise for optoelectronic and spintronic applications.

Excited-State Conformational/Electronic Responses of Saddle-Shaped N,N'-Disubstituted-Dihydrodibenzo[a,c]phenazines: Wide-Tuning Emission from Red to Deep Blue and White Light Combination.

PubMed

Zhang, Zhiyun; Wu, Yu-Sin; Tang, Kuo-Chun; Chen, Chi-Lin; Ho, Jr-Wei; Su, Jianhua; Tian, He; Chou, Pi-Tai

2015-07-08

A tailored strategy is utilized to modify 5,10-dimethylphenazine (DMP) to donor-acceptor type N,N'-disubstituted-dihydrodibenzo[a,c]phenazines. The representative compounds DMAC (N,N'-dimethyl), DPAC (N,N'-diphenyl), and FlPAC (N-phenyl-N'-fluorenyl) reveal significant nonplanar distortions (i.e., a saddle shape) and remarkably large Stokes-shifted emission independent of the solvent polarity. For DPAC and FlPAC with higher steric hindrance on the N,N'-substituents, normal Stokes-shifted emission also appears, for which the peak wavelength reveals solvent-polarity dependence. These unique photophysical behaviors are rationalized by electronic configuration coupled conformation changes en route to the geometry planarization in the excited state. This proposed mechanism is different from the symmetry rule imposed to explain the anomalously long-wavelength emission for DMP and is firmly supported by polarity-, viscosity-, and temperature-dependent steady-state and nanosecond time-resolved spectroscopy. Together with femtosecond early dynamics and computational simulation of the reaction energy surfaces, the results lead us to establish a sequential, three-step kinetics. Upon electronic excitation of N,N'-disubstituted-dihydrodibenzo[a,c]phenazines, intramolecular charge-transfer takes place, followed by the combination of polarization stabilization and skeletal motion toward the planarization, i.e., elongation of the π-delocalization over the benzo[a,c]phenazines moiety. Along the planarization, DPAC and FlPAC encounter steric hindrance raised by the N,N'-disubstitutes, resulting in a local minimum state, i.e., the intermediate. The combination of initial charge-transfer state, intermediate, and the final planarization state renders the full spectrum of interest and significance in their anomalous photophysics. Depending on rigidity, the N,N'-disubstituted-dihydrodibenzo[a,c]phenazines exhibit multiple emissions, which can be widely tuned from red to deep blue and even to white light generation upon optimization of the surrounding media.

NH3-free growth of GaN nanostructure on n-Si (1 1 1) substrate using a conventional thermal evaporation technique

NASA Astrophysics Data System (ADS)

Saron, K. M. A.; Hashim, M. R.; Farrukh, M. A.

2012-06-01

We have investigated the influence of carrier gas on grown gallium nitride (GaN) epitaxial layers deposited on n-Si (1 1 1) by a physical vapour deposition (PVD) via thermal evaporation of GaN powder at 1150 °C. The GaN nanostructures were grown at a temperature of 1050 °C for 60 min under various gases (N2, H2 mixed with N2, and Ar2) with absence of NH3. The morphology, structure, and optical properties (SEM) images showed that the morphology of GaN displayed various shapes of nanostructured depending on the type of carrier gas. X-ray diffraction (XRD) pattern showed that the GaN polycrystalline reveals a wurtzite-hexagonal structure with [0 0 1] crystal orientation. Raman spectra exhibited a red shift in peaks of E2 (high) as a result of tensile stress. Photoluminescence (PL) measurements showed two band emissions aside from the UV emission. The ultraviolet band gap of GaN nanostructure displayed a red shift as compared with the bulk GaN; this might be attributed to an increase in the defect and stress present in the GaN nanostructure. In addition, the observed blue and green-yellow emissions indicated defects due to the N vacancy and C impurity of the supplied gas. These results clearly indicated that the carrier gas, similar to the growth temperature, is one of the important parameters to control the quality of thermal evaporation (TE)-GaN epilayers.

Differential fluorescence EEMs can be used to assess treatability of DOM during drinking water production

NASA Astrophysics Data System (ADS)

Lavonen, Elin; Kothawala, Dolly; Tranvik, Lars; Köhler, Stephan

2014-05-01

Fluorescence spectroscopy has been widely used to characterize fluorescent dissolved organic matter (FDOM) in various waters including during drinking water production. Commonly used techniques for data treatment include peak picking, indexes calculated from 2D emission spectra and modelling of fluorescence components using parallel factor analysis (PARAFAC). However, peak picking and indexes only use limited information from the fluorescence EEMs and PARAFAC requires a larger dataset and experience to perform. Because DOM is a major issue in drinking water production, and personnel at water treatment plants usually have limited time for advanced analysis we have developed a simple way of assessing the treatability of DOM in different waters using differential fluorescence. With this approach the removed fraction of FDOM is calculated from samples taken before and after a particular treatment process and the percentage of removed material assessed. Samples have been collected from four large water treatment plants in Sweden and analyzed for 3Dfluorescence, absorbance and DOC. The selective removal of DOM during e.g. flocculation and slow sand filtration as well as differences in experienced treatability between the treatment plants was described with differential fluorescence. Chemical flocculation is selective towards FDOM with red-shifted emission across the entire EEM. Red-shift has earlier been connected to condensation (i.e. decrease in H/C) and positively correlated to molecular size indicating that larger, humified molecules are being preferentially removed. During the biological process of slow sand filtration compounds with blue-shifted emission are targeted demonstrating selective removal of more freshly produced, microbial material. Disinfection with UV/NH2Cl and NaOCl was found to only target material with protein-like fluorescence suggesting that FDOM of this nature could be responsible for unwanted consumption of disinfection agent. Targeted removal of this fraction prior to disinfection should optimize the process. Furthermore, the main process at all studied WTPs is flocculation and their experienced treatability could easily be explained through the percentage of FDOM with emission above 450 nm (p<0.0001).

Diagnostics of red-shifted H-alpha line emission from a C-class flare with full non-LTE radiative and hydrodynamic approach

NASA Astrophysics Data System (ADS)

Druett, M. K.; Zharkova, V. V.; Scullion, E.; Zharkov, S.; Matthews, S. A.

2016-12-01

We analyse H-alpha line profiles with strong redshifts during the C1.8 flare on 1st July 2012 obtained from the Swedish Solar Telescope (SST) closely resembling the previous observations (Wuelser and Marti, 1989). The flare has a magnetic field configuration with two levels of loop structures. The kernels with red shifts are observed in one of the H-alpha ribbons in the south-west location formed after the main impulse recorded in the north-east. The locations of H-alpha kernels with red shifts reveal close temporal and spatial correlation with weaker HXR signatures and coincide with the locations of coronal jets observed with AIA/SDO. For interpretation we apply a revised 1D hydrodynamic and non-LTE (NLTE) radiative model for 5 level plus continuum model hydrogen atom (Druett & Zharkova, 2016) considering radiative, thermal and non-thermal excitation and ionisation by beam electrons with the updated beam densities (Zharkova & Dobranskis, 2016) and analytical excitation/ionisation rates (Zharkova& Kobylinskijj, 1993). We find the simultaneous solutions of steady state and radiative transfer equations in all optically-thick lines and continua. The electron and ion temperatures, ambient density and macrovelocity of the ambient plasma are derived from a 1D hydrodynamic model with initial condition of the pre-flaring photosphere for the two fluid ambient plasma heated by beam electrons (Zharkova & Zharkov, 2007). We simulate distributions over precipitation depth of ionisation and departure coefficients for all the hydrogen atom transitions including the deviation of ionisation from Saha equation affected by non-thermal electron beams. We show that in the very first seconds after the beam onset Balmer line profiles are sensitive to the effect of beam electrons. The combination of the additional ionisation caused by beam electrons leading to a very strong Stark effect in Balmer lines with the hydrodynamic heating and formation of a low temperature shock in the chromosphere is shown to closely account for the visible asymmetric H-alpha line profiles with strong red shifts observed now and in the past. The interplay between the ambient plasma heating and non-thermal collisional excitation and ionisation rates by beam electrons is shown to define the Balmer line red shifts and continuum enhancements.

Design of cadmium-free colloidal II-VI semiconductor quantum dots exhibiting RGB emission

NASA Astrophysics Data System (ADS)

Asano, Hiroshi; Omata, Takahisa

2017-04-01

The size and composition dependence of the optical gap of colloidal alloyed quantum dots (QDs) of Zn(Te1-xSex) and Zn(Te1-xSx) were calculated by the finite-depth-well effective mass approximation method. QDs that exhibited red, green and blue emission were explored to develop cadmium-free II-VI chalcogenide-based QD-phosphors. We considered that highly monodisperse colloidal QDs with diameters of 3-6 nm are easy to synthesize and II-VI semiconductor QDs usually exhibit a Stokes shift ranging between 50 and 150 meV. We showed that Zn(Te1-xSex) QDs with 0.02≤x≤0.68, and 0≤x≤0.06, and 0.66≤x≤0.9 may be expected to exhibit green, and blue emission, respectively. Zn(Te1-xSx) QDs with 0.26≤x≤0.37, 0.01≤x≤0.2 and 0.45≤x≤0.61, 0≤x≤0.02, and 0.63≤x≤0.72, should give red, green and blue emission respectively. On the basis of our calculations, we showed that Zn(Te,Se) and Zn(Te,S) QDs are very promising cadmium-free II-VI chalcogenide semiconductor QD phosphors.

Doppler interpretation of quasar red shifts.

PubMed

Zapolsky, H S

1966-08-05

The hypothesis that the quasistellar sources (quasars) are local objects moving with velocities close to the speed of light is examined. Provided there is no observational cutoff on apparent bolometric magnitude for the quasars, the transverse Doppler effect leads to the expectation of fewer blue shifts than red shifts for an isotropic distribution of velocities. Such a distribution also yields a function N(z), the number of objects with red shift less than z which is not inconsistent with the present data. On the basis of two extreme assumptions concerning the origin of such rapidly moving sources, we computed curves of red shift plotted against magnitude. In particular, the curve obtained on the assumption that the quasars originated from an explosion in or nearby our own galaxy is in as good agreement with the observations as the curve of cosmological red shift plotted against magnitude.

Cephalopod-INspired Adaptive Photonic SystEms (CINAPSE)

DTIC Science & Technology

2013-09-13

2013 19.00 L. M. Mathger, G. R. R. Bell, A. M. Kuzirian, J. J. Allen, R. T. Hanlon. How does the blue - ringed octopus (Hapalochlaena lunulata) flash...its blue rings ?, Journal of Experimental Biology, (10 2012): 3752. doi: 10.1242/jeb.076869 08/28/2013 20.00 T. J. Wardill, P. T. Gonzalez-Bellido, R...distinct fluorescent emission spectrum shift into the near-red wavelengths (610-630 ¿) when excited by a 514 ¿ ( blue -green) laser beam. The

Impact of the wetting layer thickness on the emission wavelength of direct band gap GeSn/Ge quantum dots

NASA Astrophysics Data System (ADS)

Ilahi, Bouraoui; Al-Saigh, Reem; Salem, Bassem

2017-07-01

The effects of the wetting layer thickness (t WL) on the electronic properties of direct band gap type-I strained dome shaped Ge(1-x)Sn x quantum dot (QD) embedded in Ge matrix is numerically studied. The emission wavelength and the energy difference between S and P electron levels have been evaluated as a function of t WL for different QD size and composition with constant height to diameter ratio. The emission wavelength is found to be red shifted by increasing the wetting layer thickness, with smaller size QD being more sensitive to the variation of t WL. Furthermore, the minimum Sn composition required to fit the directness criteria is found to reduce by increasing the wetting layer thickness.

Palette of fluorinated voltage-sensitive hemicyanine dyes

PubMed Central

Yan, Ping; Acker, Corey D.; Zhou, Wen-Liang; Lee, Peter; Bollensdorff, Christian; Negrean, Adrian; Lotti, Jacopo; Sacconi, Leonardo; Antic, Srdjan D.; Kohl, Peter; Mansvelder, Huibert D.; Pavone, Francesco S.; Loew, Leslie M.

2012-01-01

Optical recording of membrane potential permits spatially resolved measurement of electrical activity in subcellular regions of single cells, which would be inaccessible to electrodes, and imaging of spatiotemporal patterns of action potential propagation in excitable tissues, such as the brain or heart. However, the available voltage-sensitive dyes (VSDs) are not always spectrally compatible with newly available optical technologies for sensing or manipulating the physiological state of a system. Here, we describe a series of 19 fluorinated VSDs based on the hemicyanine class of chromophores. Strategic placement of the fluorine atoms on the chromophores can result in either blue or red shifts in the absorbance and emission spectra. The range of one-photon excitation wavelengths afforded by these new VSDs spans 440–670 nm; the two-photon excitation range is 900–1,340 nm. The emission of each VSD is shifted by at least 100 nm to the red of its one-photon excitation spectrum. The set of VSDs, thus, affords an extended toolkit for optical recording to match a broad range of experimental requirements. We show the sensitivity to voltage and the photostability of the new VSDs in a series of experimental preparations ranging in scale from single dendritic spines to whole heart. Among the advances shown in these applications are simultaneous recording of voltage and calcium in single dendritic spines and optical electrophysiology recordings using two-photon excitation above 1,100 nm. PMID:23169660

LINER galaxy properties and the local environment

NASA Astrophysics Data System (ADS)

Coldwell, Georgina V.; Alonso, Sol; Duplancic, Fernanda; Mesa, Valeria

2018-05-01

We analyse the properties of a sample of 5560 low-ionization nuclear emission-line region (LINER) galaxies selected from SDSS-DR12 at low red shift, for a complete range of local density environments. The host LINER galaxies were studied and compared with a well-defined control sample of 5553 non-LINER galaxies matched in red shift, luminosity, morphology and local density. By studying the distributions of galaxy colours and the stellar age population, we find that LINERs are redder and older than the control sample over a wide range of densities. In addition, LINERs are older than the control sample, at a given galaxy colour, indicating that some external process could have accelerated the evolution of the stellar population. The analysis of the host properties shows that the control sample exhibits a strong relation between colours, ages and the local density, while more than 90 per cent of the LINERs are redder and older than the mean values, independently of the neighbourhood density. Furthermore, a detailed study in three local density ranges shows that, while control sample galaxies are redder and older as a function of stellar mass and density, LINER galaxies mismatch the known morphology-density relation of galaxies without low-ionization features. The results support the contribution of hot and old stars to the low-ionization emission although the contribution of nuclear activity is not discarded.

Analytical methods to determine the comparative DNA binding studies of curcumin-Cu(II) complexes

NASA Astrophysics Data System (ADS)

Rajesh, Jegathalaprathaban; Rajasekaran, Marichamy; Rajagopal, Gurusamy; Athappan, Periakaruppan

2012-11-01

DNA interaction studies of two mononuclear [1:1(1); 1:2(2)] copper(II) complexes of curcumin have been studied. The interaction of these complexes with CT-DNA has been explored by physical methods to propose modes of DNA binding of the complexes. Absorption spectral titrations of complex 1 with CT-DNA shows a red-shift of 3 nm with the DNA binding affinity of Kb, 5.21 × 104 M-1 that are higher than that obtained for 2 (red-shift, 2 nm; Kb, 1.73 × 104 M-1) reveal that the binding occurs in grooves as a result of the interaction is via exterior phosphates. The CD spectra of these Cu(II) complexes show a red shift of 3-10 nm in the positive band with increase in intensities. This spectral change of induced CD due to the hydrophobic interaction of copper complexes with DNA is the characteristic of B to A conformational change. The EB displacement assay also reveals the same trend as observed in UV-Vis spectral titration. The addition of complexes 1 and 2 to the DNA bound ethidium bromide (EB) solutions causes an obvious reduction in emission intensities indicating that these complexes competitively bind to DNA with EB. The positive shift of both the Epc and E0' accompanied by reduction of peak currents in differential pulse voltammogram (DPV), upon adding different concentrations of DNA to the metal complexes, are obviously in favor of strong binding to DNA. The super coiled plasmid pUC18 DNA cleavage ability of Cu(II) complexes in the presence of reducing agent reveals the single strand DNA cleavage (ssDNA) is observed. The hydroxyl radical (HOrad ) and the singlet oxygen are believed to be the reactive species responsible for the cleavage.

Dendron-functionalized perylenes for red luminescent materials

NASA Astrophysics Data System (ADS)

Pan, Jianfeng; Zhu, Weihong; Li, Shangfeng; Tian, He

2005-01-01

This paper presents a novel series of dendrimers containing perylene diimide cores, Fréchet-type poly(arylether) dendrons, and peripheral functional units such as hole-transporting groups (carbazole) via a convergent synthetic approach with three generation. The higher generation dendrimer has an obvious site-isolation effect or dilution effect of dendrons, which results in a relatively small red-shift of absorption and emission spectra when they form a solid thin film for applications. The interactions between peripheral units and perylene diimide core in the dendrimers are studied by fluorescence spectra. The steady-state fluorescence shows there is no effective Förster intramolecular energy transfer. DSC results indicate that the incorporation of Fréchet-type poly(arylether) dendrons can improve the amorphous property and increase glass transition temperature (Tg). The preliminary EL results with a single-layer architecture demonstrate that these dendrimers could be utilized as a promising kind of active red luminescent emitters.

Hue-shifted monomeric variants of Clavularia cyan fluorescent protein: identification of the molecular determinants of color and applications in fluorescence imaging

PubMed Central

Ai, Hui-wang; Olenych, Scott G; Wong, Peter; Davidson, Michael W; Campbell, Robert E

2008-01-01

Background In the 15 years that have passed since the cloning of Aequorea victoria green fluorescent protein (avGFP), the expanding set of fluorescent protein (FP) variants has become entrenched as an indispensable toolkit for cell biology research. One of the latest additions to the toolkit is monomeric teal FP (mTFP1), a bright and photostable FP derived from Clavularia cyan FP. To gain insight into the molecular basis for the blue-shifted fluorescence emission we undertook a mutagenesis-based study of residues in the immediate environment of the chromophore. We also employed site-directed and random mutagenesis in combination with library screening to create new hues of mTFP1-derived variants with wavelength-shifted excitation and emission spectra. Results Our results demonstrate that the protein-chromophore interactions responsible for blue-shifting the absorbance and emission maxima of mTFP1 operate independently of the chromophore structure. This conclusion is supported by the observation that the Tyr67Trp and Tyr67His mutants of mTFP1 retain a blue-shifted fluorescence emission relative to their avGFP counterparts (that is, Tyr66Trp and Tyr66His). Based on previous work with close homologs, His197 and His163 are likely to be the residues with the greatest contribution towards blue-shifting the fluorescence emission. Indeed we have identified the substitutions His163Met and Thr73Ala that abolish or disrupt the interactions of these residues with the chromophore. The mTFP1-Thr73Ala/His163Met double mutant has an emission peak that is 23 nm red-shifted from that of mTFP1 itself. Directed evolution of this double mutant resulted in the development of mWasabi, a new green fluorescing protein that offers certain advantages over enhanced avGFP (EGFP). To assess the usefulness of mTFP1 and mWasabi in live cell imaging applications, we constructed and imaged more than 20 different fusion proteins. Conclusion Based on the results of our mutagenesis study, we conclude that the two histidine residues in close proximity to the chromophore are approximately equal determinants of the blue-shifted fluorescence emission of mTFP1. With respect to live cell imaging applications, the mTFP1-derived mWasabi should be particularly useful in two-color imaging in conjunction with a Sapphire-type variant or as a fluorescence resonance energy transfer acceptor with a blue FP donor. In all fusions attempted, both mTFP1 and mWasabi give patterns of fluorescent localization indistinguishable from that of well-established avGFP variants. PMID:18325109

Conformational study of red kidney bean (Phaseolus vulgaris L.) protein isolate (KPI) by tryptophan fluorescence and differential scanning calorimetry.

PubMed

Yin, Shou-Wei; Tang, Chuan-He; Yang, Xiao-Quan; Wen, Qi-Biao

2011-01-12

Fluorescence and differential scanning calorimetry (DSC) were used to study changes in the conformation of red kidney bean (Phaseolus vulgaris L.) protein isolate (KPI) under various environmental conditions. The possible relationship between fluorescence data and DSC characteristics was also discussed. Tryptophan fluorescence and fluorescence quenching analyses indicated that the tryptophan residues in KPI, exhibiting multiple fluorophores with different accessibilities to acrylamide, are largely buried in the hydrophobic core of the protein matrix, with positively charged side chains close to at least some of the tryptophan residues. GdnHCl was more effective than urea and SDS in denaturing KPI. SDS and urea caused variable red shifts, 2-5 nm, in the emission λ(max), suggesting the conformational compactness of KPI. The result was further supported by DSC characteristics that a discernible endothermic peak was still detected up to 8 M urea or 30 mM SDS, also evidenced by the absence of any shift in emission maximum (λ(max)) at different pH conditions. Marked decreases in T(d) and enthalpy (ΔH) were observed at extreme alkaline and/or acidic pH, whereas the presence of NaCl resulted in higher T(d) and ΔH, along with greater cooperativity of the transition. Decreases in T(d) and ΔH were observed in the presence of protein perturbants, for example, SDS and urea, indicating partial denaturation and decrease in thermal stability. Dithiothreitol and N-ethylmaleimide have a slight effect on the thermal properties of KPI. Interestingly, a close linear relationship between the T(d) (or ΔH) and the λ(max) was observed for KPI in the presence of 0-6 M urea.

Interfacial exciplex formation in bilayers of conjugated polymers.

PubMed

Nobuyasu, R S; Araujo, K A S; Cury, L A; Jarrosson, T; Serein-Spirau, F; Lère-Porte, J-P; Dias, F B; Monkman, A P

2013-10-28

The donor-acceptor interactions in sequential bilayer and blend films are investigated. Steady-state and time-resolved photoluminescence (PL) were measured to characterize the samples at different geometries of photoluminescence collection. At standard excitation, with the laser incidence at 45° of the normal direction of the sample surface, a band related to the aggregate states of donor molecules appears for both blend and bilayer at around 540 nm. For the PL spectra acquired from the edge of the bilayer, with the laser incidence made at normal direction of the sample surface (90° geometry), a new featureless band emission, red-shifted from donor and acceptor emission regions was observed and assigned as the emission from interfacial exciplex states. The conformational complexity coming from donor/acceptor interactions at the heterojunction interface of the bilayer is at the origin of this interfacial exciplex emission.

Bichromophoric dyes for wavelength shifting of dye-protein fluoromodules.

PubMed

Pham, Ha H; Szent-Gyorgyi, Christopher; Brotherton, Wendy L; Schmidt, Brigitte F; Zanotti, Kimberly J; Waggoner, Alan S; Armitage, Bruce A

2015-03-28

Dye-protein fluoromodules consist of fluorogenic dyes and single chain antibody fragments that form brightly fluorescent noncovalent complexes. This report describes two new bichromophoric dyes that extend the range of wavelengths of excitation or emission of existing fluoromodules. In one case, a fluorogenic thiazole orange (TO) was attached to an energy acceptor dye, Cy5. Upon binding to a protein that recognizes TO, red emission due to efficient energy transfer from TO to Cy5 replaces the green emission observed for monochromophoric TO bound to the same protein. Separately, TO was attached to a coumarin that serves as an energy donor. The same green emission is observed for coumarin-TO and TO bound to a protein, but efficient energy transfer allows violet excitation of coumarin-TO, versus longer wavelength, blue excitation of monochromophoric TO. Both bichromophores exhibit low nanomolar KD values for their respective proteins, >95% energy transfer efficiency and high fluorescence quantum yields.

Bichromophoric Dyes for Wavelength Shifting of Dye-Protein Fluoromodules

PubMed Central

Pham, Ha H.; Szent-Gyorgyi, Christopher; Brotherton, Wendy L.; Schmidt, Brigitte F.; Zanotti, Kimberly J.; Waggoner, Alan S.

2015-01-01

Dye-protein fluoromodules consist of fluorogenic dyes and single chain antibody fragments that form brightly fluorescent noncovalent complexes. This report describes two new bichromophoric dyes that extend the range of wavelengths of excitation or emission of existing fluoromodules. In one case, a fluorogenic thiazole orange (TO) was attached to an energy acceptor dye, Cy5. Upon binding to a protein that recognizes TO, red emission due to efficient energy transfer from TO to Cy5 replaces the green emission observed for monochromophoric TO bound to the same protein. Separately, TO was attached to a coumarin that serves as an energy donor. The same green emission is observed for coumarin-TO and TO bound to a protein, but efficient energy transfer allows violet excitation of coumarin-TO, versus longer wavelength, blue excitation of monochromophoric TO. Both bichromophores exhibit low nanomolar KD values for their respective proteins, >95% energy transfer efficiency and high fluorescence quantum yields. PMID:25679477

Luminescence of the elpasolite series MI2MIIMCl6 (MI=Cs, Rb; MII=Li, Na; M=Lu, Y, Sc, In) doped with europium using synchrotron radiation excitation

NASA Astrophysics Data System (ADS)

Tanner, Peter A.; Duan, Chang-Kui; Jia, Guohua; Cheng, Bing-Ming

2012-04-01

The excitation and emission spectra of a series of cubic hexachloroelpasolites doped with europium have been investigated using synchrotron radiation at 10 K. Besides the Eu3+ emission from 5DJ (J=0-3) multiplets, emission from 5H3 is also observed for Cs2NaIn0.995Eu0.005Cl6, since the gap to the next lowest level is spanned by seven phonons. The excitation spectra of samples indicate impurities due to oxygen and divalent europium. Broad band emission from Eu2+ is reported from the crystalline samples grown in vacuum by the Bridgman process, with the maximum wavelength shifting to the red with increasing lattice parameter for the series Cs2NaMCl6:Eu2+ (M=Lu, Y, Eu).

Hydrothermal synthesis infrared to visible upconversion luminescence of SrMoO4: Er3+/Yb3+ phosphor

NASA Astrophysics Data System (ADS)

Sinha, Shriya; Kumar, Kaushal

2018-04-01

The upconversion emission properties in Er3+/Yb3+ doped SrMoO4 phosphor synthesized via hydrothermal method is investigated upon 980 nm laser light excitation. The crystal structure and morphology of the synthesized phosphor are characterized by X-ray diffraction and field emission scanning electron microscopy. The X-ray diffraction pattern suggests that SrMoO4 phosphor has tetragonal phase structure. The phosphor emits strong green (525 and 552 nm) and red (665 nm) UC emissions along with weak blue (410 and 488 nm) and near infrared (798 nm) emission bands. The color emitted from the phosphor is shifted from yellow to green region with increasing the power density from 15 to 65 W/cm2. The result indicates that the present material is suitable for making infrared to visible up-converts and display devices.

Laser induced fluorescence of dental caries

NASA Technical Reports Server (NTRS)

Albin, S.; Byvik, C. E.; Buoncristiani, A. M.

1988-01-01

Significant differences between the optical spectra taken from sound regions of teeth and carious regions have been observed. These differences appear both in absorption and in laser induced fluorescence spectra. Excitation by the 488 nm line of an argon ion laser beam showed a peak in the emission intensity around 553 nm for the sound dental material while the emission peak from the carious region was red-shifted by approximately 40 nm. The relative absorption of carious region was significantly higher at 488 nm; however its fluorescence intensity peak was lower by an order of magnitude compared to the sound tooth. Implications of these results for a safe, reliable and early detection of dental caries are discussed.

Fluorosilicate and fluorophosphate superfluorescent multicore optical fibers co-doped with Nd3+/Yb3+

NASA Astrophysics Data System (ADS)

Kochanowicz, M.; Zmojda, J.; Dorosz, D.

2014-06-01

In the paper spectroscopic properties of two fluorosilicate and fluorophosphate glass systems co-doped with Nd3+/Yb3+ ions are investigated. As a result of optical excitation at the wavelength of 808 nm strong and wide emission in the 1 μm region corresponding to the superposition of optical transitions 4F3/2 → 4I11/2 (Nd3+) and 2F5/2 → 2F7/2 (Yb3+) can be observed. The optimization of Nd3+ → Yb3+ energy transfer in both glasses allows to manufacture multicore optical fibers with narrowing and red-shifting of amplified spontaneous emission (ASE) at 1.1 μm.

Excitation-resolved wide-field fluorescence imaging of indocyanine green visualizes the microenvironment properties in vivo via solvatochromic shift (Conference Presentation)

NASA Astrophysics Data System (ADS)

Cho, Jaedu; Kim, Chang-Seok; Gulsen, Gultekin

2016-03-01

Near-infrared fluorescence imaging (NIRF) is a powerful wide-field optical imaging tool that has a potential to visualize molecular-specific exogenous fluorescence agents, such as FDA approved Indocyanine Green (ICG), in thick tissue. Indeed, ICG is sensitive to biochemical environment such that it can be used to detect micro- or macroscopic environmental changes in tissue by solvatochromic shift that is defined by the dependence of absorption and emission spectra with the solvent polarity. For example, dimethyl sulfoxide (DMSO) is a very powerful drug carrier that can penetrate biological barriers such as the skin, the membranes, and the blood-brain-barrier. In presence of DMSO, ICG in tissue shows the excitation blue shift. However, NIRF imaging of microenvironment dependent changes of ICG has been challenging for the following reasons. First, the Stoke's shift of ICG is too small to separate the excitation and emission spectra easily. Second, the solvatochromic shift of ICG is too small to be detected by conventional NIRF techniques. Last but not least, the multiple scattering in tissue degrades not only the spatial information but also the spectral contents by the red-shift. We developed a wavelength-swept laser-based NIRF system that can resolve the excitation shift of ICG in tissue such that DMSO can be indirectly visualized. We plan to conduct an in-vivo lymph-node drug-delivery study in a mouse model to show feasibility of the indirect imaging of the drug-carrier with the wavelength-swept-laser based NIRF system.

C-shaped diastereomers containing cofacial thiophene-substituted quinoxaline rings: synthesis, photophysical properties, and X-ray crystallography.

PubMed

DeBlase, Catherine R; Finke, Ryan T; Porras, Jonathan A; Tanski, Joseph M; Nadeau, Jocelyn M

2014-05-16

Synthesis and characterization of two diastereomeric C-shaped molecules containing cofacial thiophene-substituted quinoxaline rings are described. A previously known bis-α-diketone was condensed with an excess of 4-bromo-1,2-diaminobenzene in the presence of zinc acetate to give a mixture of two C-shaped diastereomers with cofacial bromine-substituted quinoxaline rings. After chromatographic separation, thiophene rings were installed by a microwave-assisted Suzuki coupling reaction, resulting in highly emissive diastereomeric compounds that were studied by UV-vis, fluorescence, and NMR spectroscopy, as well as X-ray crystallography. The unique symmetry of each diastereomer was confirmed by NMR spectroscopy. NMR data indicated that the syn isomer has restricted rotation about the bond connecting the thiophene and quinoxaline rings, which was also observed in the solid state. The spectroscopic properties of the C-shaped diastereomers were compared to a model compound containing only a single thiophene-substituted quinoxaline ring. Ground state intramolecular π-π interactions in solution were detected by NMR and UV-vis spectroscopy. Red-shifted emission bands, band broadening, and large Stokes shifts were observed, which collectively suggest excited state π-π interactions that produce excimer-like emissions, as well as a remarkable positive emission solvatochromism, indicating charge-transfer character in the excited state.

Multicolor fluorescence of a styrylquinoline dye tuned by metal cations.

PubMed

Shiraishi, Yasuhiro; Ichimura, Chizuru; Sumiya, Shigehiro; Hirai, Takayuki

2011-07-18

A styrylquinoline dye with a dipicolylamine (DPA) moiety (1) has been synthesized. The dye 1 in acetonitrile demonstrates multicolor fluorescence upon addition of different metal cations. Compound 1 shows a green fluorescence without cations. Coordination of 1 with Cd(2+) shows a blue emission, while with Hg(2+) and Pb(2+) exhibits yellow and orange emissions, respectively. The different fluorescence spectra are due to the change in intramolecular charge transfer (ICT) properties of 1 upon coordination with different cations. The DPA and quinoline moieties of 1 behave as the electron donor and acceptor units, respectively, and both units act as the coordination site for metal cations. Cd(2+) coordinates with the DPA unit. This reduces the donor ability of the unit and decreases the energy level of HOMO. This results in an increase in HOMO-LUMO gap and blue shifts the emission. Hg(2+) or Pb(2+) coordinate with both DPA and quinoline units. The coordination with the quinoline unit decreases the energy level of LUMO. This results in a decrease in HOMO-LUMO gap and red shifts the emission. Addition of two different metal cations successfully creates intermediate colors; in particular, the addition of Cd(2+) and Pb(2+) at once creates a bright white fluorescence. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

High pressure luminescence of Nd3+ in YAlO3 perovskite nanocrystals: A crystal-field analysis

NASA Astrophysics Data System (ADS)

Hernández-Rodríguez, Miguel A.; Muñoz-Santiuste, Juan E.; Lavín, Víctor; Lozano-Gorrín, Antonio D.; Rodríguez-Hernández, Plácida; Muñoz, Alfonso; Venkatramu, Vemula; Martín, Inocencio R.; Rodríguez-Mendoza, Ulises R.

2018-01-01

Pressure-induced energy blue- and red-shifts of the 4F3/2 → 4I9/2,11/2 near-infrared emission lines of Nd3+ ions in YAlO3 perovskite nano-particles have been measured from ambient conditions up to 29 GPa. Different positive and negative linear pressure coefficients have been calibrated for the emission lines and related to pressure-induced changes in the interactions between those Nd3+ ions and their twelve oxygen ligands at the yttrium site. Potentiality of the simple overlap model, combined with ab initio structural calculations, in the description of the effects of these interactions on the energy levels and luminescence properties of the optically active Nd3+ ion is emphasized. Simulations show how the energies of the 4f3 ground configuration and the barycenters of the multiplets increase with pressure, whereas the Coulomb interaction between f-electrons decreases and the crystal-field strength increases. All these effects combined explain the wavelength blue-shifts of some near-infrared emission lines of Nd3+ ions. Large pressure rates of various emission lines suggest that a YAlO3 perovskite nano-crystal can be a potential candidate for near-infrared optical pressure sensors.

CdS quantum dots in a novel glass with a very low activation energy and its variation of diffusivity with temperature

NASA Astrophysics Data System (ADS)

Nagpal, Swati

2011-07-01

CdS quantum dots of different average sizes in the range 2 to 3.8 nm were grown by diffusion-limited growth process in indigenously made silicate glass. The absorption spectra showed a strong quantum confinement effect with a blue shift of the order of 500 meV depending on the average size. Critical radius of quantum dots was found to be 1.8 nm. The size dispersion decreased from 15.2 to 12.5% with a 20% increase in the particle size. The activation energy for diffusion was found to be very low i.e. 193 kJ mol-1 and the diffusion coefficient increased by 60% for 10 K rise in temperature. The PL emission spectra showed the presence of only deep traps around 600 nm with a red shift of 200 nm. No shallow traps or band edge emission was observed. The PL peak position changed from 560 to 640 nm with a 35 K increase in annealing temperature.

Chemoselective Alteration of Fluorophore Scaffolds as a Strategy for the Development of Ratiometric Chemodosimeters.

PubMed

Zhou, Xinqi; Lesiak, Lauren; Lai, Rui; Beck, Jon R; Zhao, Jia; Elowsky, Christian G; Li, Hui; Stains, Cliff I

2017-04-03

Ratiometric sensors generally couple binding events or chemical reactions at a distal site to changes in the fluorescence of a core fluorophore scaffold. However, such approaches are often hindered by spectral overlap of the product and reactant species. We provide a strategy to design ratiometric sensors that display dramatic spectral shifts by leveraging the chemoselective reactivity of novel functional groups inserted within fluorophore scaffolds. As a proof-of-principle, fluorophores containing a borinate (RF 620 ) or silanediol (SiOH2R) functionality at the bridging position of the xanthene ring system are developed as endogenous H 2 O 2 sensors. Both these fluorophores display far-red to near-infrared excitation and emission prior to reaction. Upon oxidation by H 2 O 2 both sensors are chemically converted to tetramethylrhodamine, producing significant (≥66 nm) blue-shifts in excitation and emission maxima. This work provides a new concept for the development of ratiometric probes. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Solvatochromic fluorescence characteristics of cinnamoyl pyrone derivatives

NASA Astrophysics Data System (ADS)

Benosmane, Nadjib; Boutemeur, Baya; Hamdi, Safouane M.; Hamdi, Maamar; Silva, Artur S. M.

2017-12-01

The solvatochromic fluorescence behavior of cinnamoyl pyrone derivatives has been studied in several polar and non-polar solvents. The fluorescence spectra of these compounds exhibit red shift from its absorption spectra and present an excellent correlation with solvent polarity. Cinnamoyl pyrones show a significant spectral shift in fluorescence emission as a function of water composition in binary aqueous solutions mixture. This change is due to the specific intermolecular hydrogen bonding of cinnamoyl pyrones with a molecules of water, due to the deactivation of the lowest excited singlet state of these compounds. The relative quantum yields are calculated. It is found that the quantum yields of the cinnamoyl pyrones vary with the change in the solvent polarity indicating the dependency of fluorescence properties on the solvent nature. It has been observed that the addition of water and pH medium can affect the fluorescence properties of cinnamoyl pyrones in ethanol. This study exhibited that due to the solvent sensitive emission, cinnamoyl pyrone derivatives are a good compound to be used as fluorescence probes.

Quantitative phase imaging of human red blood cells using phase-shifting white light interference microscopy with colour fringe analysis

NASA Astrophysics Data System (ADS)

Singh Mehta, Dalip; Srivastava, Vishal

2012-11-01

We report quantitative phase imaging of human red blood cells (RBCs) using phase-shifting interference microscopy. Five phase-shifted white light interferograms are recorded using colour charge coupled device camera. White light interferograms were decomposed into red, green, and blue colour components. The phase-shifted interferograms of each colour were then processed by phase-shifting analysis and phase maps for red, green, and blue colours were reconstructed. Wavelength dependent refractive index profiles of RBCs were computed from the single set of white light interferogram. The present technique has great potential for non-invasive determination of refractive index variation and morphological features of cells and tissues.

Contour shape analysis of hollow ion x-ray emission

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rosmej, F. B.; Angelo, P.; Ecole Polytechnique, Laboratoire pour Utilisation des Lasers Intenses, Physique Atomique dans les Plasmas Denses, 91128 Palaiseau Cedex

2008-10-22

Hollow ion x-ray transitions originating from the configurations K{sup 0}L{sup N} have been studied via relativistic atomic structure and Stark broadening calculations. The broadening of the total contour is largely influenced by the oscillator strengths distribution over wavelengths rather than by Stark broadening alone. Interference effects between the upper and lower levels are shown to result in a considerable contour narrowing as well as in a shift of the total contour which could be either red or blue.

Noninvasive in vivo plasma volume and hematocrit in humans: observing long-term baseline behavior to establish homeostasis for intravascular volume and composition

NASA Astrophysics Data System (ADS)

Dent, Paul; Deng, Bin; Goodisman, Jerry; Peterson, Charles M.; Narsipur, Sriram; Chaiken, J.

2016-04-01

A new device incorporating a new algorithm and measurement process allows simultaneous noninvasive in vivo monitoring of intravascular plasma volume and red blood cell volume. The purely optical technique involves probing fingertip skin with near infrared laser light and collecting the wavelength shifted light, that is, the inelastic emission (IE) which includes the unresolved Raman and fluorescence, and the un-shifted emission, that is, the elastic emission (EE) which includes both the Rayleigh and Mie scattered light. Our excitation and detection geometry is designed so that from these two simultaneous measurements we can calculate two parameters within the single scattering regime using radiation transfer theory, the intravascular plasma volume fraction and the red blood cell volume fraction. Previously calibrated against a gold standard FDA approved device, 2 hour monitoring sessions on three separate occasions over a three week span for a specific, motionless, and mostly sleeping individual produced 3 records containing a total of 5706 paired measurements of hematocrit and plasma volume. The average over the three runs, relative to the initial plasma volume taken as 100%, of the plasma volume±1σ was 97.56+/-0.55 or 0.56%.For the same three runs, the average relative hematocrit (Hct), referenced to an assumed initial value of 28.35 was 29.37+/-0.12 or stable to +/-0.4%.We observe local deterministic circulation effects apparently associated with the pressure applied by the finger probe as well as longer timescale behavior due to normal ebb and flow of internal fluids due to posture changes and tilt table induced gravity gradients.

Method Of Signal Amplification In Multi-Chromophore Luminescence Sensors

DOEpatents

Levitsky, Igor A.; Krivoshlykov, Sergei G.

2004-02-03

A fluorescence-based method for highly sensitive and selective detection of analyte molecules is proposed. The method employs the energy transfer between two or more fluorescent chromophores in a carefully selected polymer matrix. In one preferred embodiment, signal amplification has been achieved in the fluorescent sensing of dimethyl methylphosphonate (DMMP) using two dyes, 3-aminofluoranthene (AM) and Nile Red (NR), in a hydrogen bond acidic polymer matrix. The selected polymer matrix quenches the fluorescence of both dyes and shifts dye emission and absorption spectra relative to more inert matrices. Upon DMMP sorption, the AM fluorescence shifts to the red at the same time the NR absorption shifts to the blue, resulting in better band overlap and increased energy transfer between chromophores. In another preferred embodiment, the sensitive material is incorporated into an optical fiber system enabling efficient excitation of the dye and collecting the fluorescent signal form the sensitive material on the remote end of the system. The proposed method can be applied to multichromophore luminescence sensor systems incorporating N-chromophores leading to N-fold signal amplification and improved selectivity. The method can be used in all applications where highly sensitive detection of basic gases, such as dimethyl methylphosphonate (DMMP), Sarin, Soman and other chemical warfare agents having basic properties, is required, including environmental monitoring, chemical industry and medicine.

Bluish-green BMes2-functionalized Pt(II) complexes for high efficiency PhOLEDs: impact of the BMes2 location on emission color.

PubMed

Rao, Ying-Li; Schoenmakers, Dylan; Chang, Yi-Lu; Lu, Jia-Sheng; Lu, Zheng-Hong; Kang, Youngjin; Wang, Suning

2012-09-03

New phosphorescent Pt(II) compounds based on dimesitylboron (BMes(2))-functionalized 2-phenylpyridyl (ppy) N,C-chelate ligands and an acetylacetonato ancillary ligand have been achieved. We have found that BMes(2) substitution at the 4'-position of the phenyl ring can blue-shift the phosphorescent emission energy of the Pt(II) compound by approximately 50 nm, compared to the 5'-BMes(2) substituted analogue, without substantial loss of luminescent quantum efficiencies. The emission color of the 4'-BMes(2) substituted Pt(II) compound, Pt(Bppy)(acac) (1) can be further tuned by the introduction of a substituent group at the 3'-position of the phenyl ring. A methyl substituent red-shifts the emission energy of 1 by approximately 10 nm whereas a fluoro substituent blue-shifts the emission energy by about 6 nm. Using this strategy, three bright blue-green phosphorescent Pt(II) compounds 1, 2 and 3 with emission energy at 481, 492, and 475 nm and Φ(PL)=0.43, 0.26 and 0.25, respectively, have been achieved. In addition, we have examined the impact of BMes(2) substitution on 3,5-dipyridylbenzene (dpb) N,C,N-chelate Pt(II) compounds by synthesizing compound 4, Pt(Bdpb)Cl, which has a BMes(2) group at the 4'-position of the benzene ring. Compound 4 has a phosphorescent emission band at 485 nm and Φ(PL)=0.70. Highly efficient blue-green electroluminescent (EL) devices with a double-layer structure and compounds 1, 3 or 4 as the phosphorescent dopant have been fabricated. At 100 cd m(-2) luminance, EL devices based on 1, 3 and 4 with an external quantum efficiency of 4.7, 6.5 and 13.4%, respectively, have been achieved. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Photoluminescence Spectra From The Direct Energy Gap of a-SiQDs

NASA Astrophysics Data System (ADS)

Abdul-Ameer, Nidhal M.; Abdulrida, Moafak C.; Abdul-Hakeem, Shatha M.

2018-05-01

A theoretical model for radiative recombination in amorphous silicon quantum dots (a-SiQDs) was developed. In this model, for the first time, the coexistence of both spatial and quantum confinements were considered. Also, it is found that the photoluminescence exhibits significant size dependence in the range (1-4) nm of the quantum dots. a-SiQDs show visible light emission peak energies and high radiative quantum efficiency at room temperature,in contrast to bulk a-Si structures. The quantum efficiency is sensitive to any change in defect density (the volume nonradiative centers density and/or the surface nonradiative centers density) but, with small dots sizes, the quantum efficiency is insensitive to such defects. Our analysis shows that the photoluminescence intensity increases or decreases by the effect of radiative quantum efficiency. By controlling the size of a-SiQDs, we note that the energy of emission can be tuned. The blue shift is attributed to quantum confinement effect. Meanwhile, the spatial confinement effect is clearly observed in red shift in emission spectra. we found a good agreement with the experimental published data. Therefore, we assert that a-SiQDs material is a promising candidate for visible, tunable, and high performance devices of light emitting.

Photoluminescence and structural properties of unintentional single and double InGaSb/GaSb quantum wells grown by MOVPE

NASA Astrophysics Data System (ADS)

Ahia, Chinedu Christian; Tile, Ngcali; Botha, Johannes R.; Olivier, E. J.

2018-04-01

The structural and photoluminescence (PL) characterization of InGaSb quantum well (QW) structures grown on GaSb substrate (100) using atmospheric pressure Metalorganic Vapor Phase Epitaxy (MOVPE) is presented. Both structures (single and double-InGaSb QWs) were inadvertently formed during an attempt to grow capped InSb/GaSb quantum dots (QDs). In this work, 10 K PL peak energies at 735 meV and 740 meV are suggested to be emissions from the single and double QWs, respectively. These lines exhibit red shifts, accompanied by a reduction in their full-widths at half-maximum (FWHM) as the excitation power decreases. The presence of a GaSb spacer in the double QW was found to increase the strength of the PL emission, which consequently gives rise to a reduced blue-shift and broadening of the PL emission line observed for the double QW with an increase in laser power, while the low thermal activation energy for the quenching of the PL from the double QW is attributed to the existence of threading dislocations, as seen in the bright field TEM image for this sample.

Band gap enhancement of glancing angle deposited TiO2 nanowire array

NASA Astrophysics Data System (ADS)

Chinnamuthu, P.; Mondal, A.; Singh, N. K.; Dhar, J. C.; Chattopadhyay, K. K.; Bhattacharya, Sekhar

2012-09-01

Vertically oriented TiO2 nanowire (NW) arrays were fabricated by glancing angle deposition technique. Field emission-scanning electron microscopy shows the formation of two different diameters ˜80 nm and ˜40 nm TiO2 NW for 120 and 460 rpm azimuthal rotation of the substrate. The x-ray diffraction and Raman scattering depicted the presence of rutile and anatase phase TiO2. The overall Raman scattering intensity decreased with nanowire diameter. The role of phonon confinement in anatase and rutile peaks has been discussed. The red (7.9 cm-1 of anatase Eg) and blue (7.4 cm-1 of rutile Eg, 7.8 cm-1 of rutile A1g) shifts of Raman frequencies were observed. UV-vis absorption measurements show the main band absorption at 3.42 eV, 3.48 eV, and ˜3.51 eV for thin film and NW prepared at 120 and 460 rpm, respectively. Three fold enhance photon absorption and intense light emission were observed for NW assembly. The photoluminescence emission from the NW assembly revealed blue shift in main band transition due to quantum confinement in NW structures.

Role of Mn2+ concentration in the linear and nonlinear optical properties of Ni1-xMnxSe nanoparticles

NASA Astrophysics Data System (ADS)

Anugop, B.; Prasanth, S.; Rithesh Raj, D.; Vineeshkumar, T. V.; Pranitha, S.; Mahadevan Pillai, V. P.; Sudarsanakumar, C.

2016-12-01

Ni1-xMnxSe nanoparticles (x = 0.1, 0.3, 0.5, 0.7, 0.9) were successfully synthesized by chemical co-precipitation method and their structural and optical properties were studied using X-ray diffraction, transmission electron microscopy, UV-Visible absorption and photo luminescence spectroscopy. XRD pattern reveals the hexagonal structure of the particles and the peak positions were shifted to higher 2θ values with increase in Mn2+ concentration. The average particle size determined from XRD varies from 6 to 11 nm. The UV-Visible absorption spectrum shows absorption edge around the blue region and is red-shifted with increasing Mn2+ concentration consequently the optical bandgap energy is decreasing. The PL emission spectrum shows a broad emission around 380 nm, and the intensity of the emission decreases with increase in Mn2+ concentration. The nonlinear optical properties of the samples were analysed using Z-scan technique and the samples show optical limiting behaviour and the 2 PA coefficient increases with increasing Mn2+ concentration. Overall, manganese concentration influences the linear and nonlinear optical properties of Ni1-xMnxSe nanoparticles.

Red-ultraviolet photoluminescence tuning by Ni nanocrystals in epitaxial SrTiO3 matrix

NASA Astrophysics Data System (ADS)

Xiong, Z. W.; Cao, L. H.

2018-07-01

In this work, the self-organized Ni nanocrystals (NCs) were embedded in the epitaxial SrTiO3 matrix using pulsed laser deposition method. With the in-situ monitoring of reflection high-energy electron diffraction, both matrix and NCs could be precisely engineered with desired qualities by regulating the growth conditions according to the full release of stress energy at the interfaces of Ni NCs and SrTiO3. We achieved a controllable strained system according to the transformation of growth modes from three dimensional (3D) islands of Ni NCs to 2D layer-by-layer of SrTiO3, corresponding to the (1 1 1) and (0 0 l) orientation for Ni and SrTiO3, respectively. With the increase of Ni NCs concentration, the absorption intensity is increasing in the regions of 190-300 nm, and the band gap is gradually decreased. Besides, photoluminescence (PL) spectra reveal that the energy levels of Ni 3d bands contribute to the different PL colors, further inducing the enhancement of PL intensity and red-shift of emission peaks. Compared with the pure SrTiO3 published in the literature, much wider ranges of PL emission from red to ultraviolet can be tuned by the Ni NCs.

Tuning Ag29 nanocluster light emission from red to blue with one and two-photon excitation.

PubMed

Russier-Antoine, Isabelle; Bertorelle, Franck; Hamouda, Ramzi; Rayane, Driss; Dugourd, Philippe; Sanader, Željka; Bonačić-Koutecký, Vlasta; Brevet, Pierre-François; Antoine, Rodolphe

2016-02-07

We demonstrate that the tuning of the light emission from red to blue in dihydrolipoic acid (DHLA) capped Ag29 nanoclusters can be trigged with one and two photon excitations. The cluster stoichiometry was determined with mass spectrometry and found to be Ag29(DHLA)12. In a detailed optical investigation, we show that these silver nanoclusters exhibit a strong red photoluminescence visible to the naked eye and characterized by a quantum yield of nearly ∼2% upon one-photon excitation. In the nonlinear optical (NLO) study of the properties of the clusters, the two-photon excited fluorescence spectra were recorded and their first hyperpolarizability obtained. The two-photon absorption cross-section at ∼800 nm for Ag29(DHLA)12 is higher than 10(4) GM and the hyperpolarizability is 106 × 10(-30) esu at the same excitation wavelength. The two-photon excited fluorescence spectrum appears strongly blue-shifted as compared to the one-photon excited spectrum, displaying a broad band between 400 and 700 nm. The density functional theory (DFT) provides insight into the structural and electronic properties of Ag29(DHLA)12 as well as into interplay between metallic subunit or core and ligands which is responsible for unique optical properties.

Synthesis and effect of Sr substitution on fluorescence of new Ba 2-xSr xZnS 3: Eu 2+ red phosphor: Considerable enhancement of emission intensity

NASA Astrophysics Data System (ADS)

Lee, Chi-Woo; Petrykin, Valery; Kakihana, Masato

2009-01-01

A series of 0.5 mol% Eu 2+-activated Ba 2-xSr xZnS 3 phosphor materials were synthesized using precursors prepared by the polymerizable complex method and their fluorescent properties were studied for the first time. It was found that Sr substitution for Ba leads to the considerable improvement of internal quantum efficiency and emission intensity in these materials compared to Ba 2ZnS 3, while emission peak wavelength exhibits a blue shift from 680 to 660 nm. Rietveld refinement of crystal structure of sample with x=0.7 suggests that Sr ions preferentially occupy one of two Ba sites in this compound. Such a structural re-arrangement might be responsible for the observed quantum efficiency dependence on Sr concentration.

Electroluminescence from single-wall carbon nanotube network transistors.

PubMed

Adam, E; Aguirre, C M; Marty, L; St-Antoine, B C; Meunier, F; Desjardins, P; Ménard, D; Martel, R

2008-08-01

The electroluminescence (EL) properties from single-wall carbon nanotube network field-effect transistors (NNFETs) and small bundle carbon nanotube field effect transistors (CNFETs) are studied using spectroscopy and imaging in the near-infrared (NIR). At room temperature, NNFETs produce broad (approximately 180 meV) and structured NIR spectra, while they are narrower (approximately 80 meV) for CNFETs. EL emission from NNFETs is located in the vicinity of the minority carrier injecting contact (drain) and the spectrum of the emission is red shifted with respect to the corresponding absorption spectrum. A phenomenological model based on a Fermi-Dirac distribution of carriers in the nanotube network reproduces the spectral features observed. This work supports bipolar (electron-hole) current recombination as the main mechanism of emission and highlights the drastic influence of carrier distribution on the optoelectronic properties of carbon nanotube films.

New insights into the molecular characteristics behind the function of Renilla luciferase.

PubMed

Fanaei-Kahrani, Zahra; Ganjalikhany, Mohamad Reza; Rasa, Seyed Mohammad Mahdi; Emamzadeh, Rahman

2018-02-01

Renilla Luciferase (RLuc) is a blue light emitter protein which can be applied as a valuable tool in medical diagnosis. But due to lack of the crystal structure of RLuc-ligand complex, the functional motions and catalytic mechanism of this enzyme remain largely unknown. In the present study, the active site properties and the ligand-receptor interactions of the native RLuc and its red-shifted light emitting variant (Super RLuc 8) were investigated using molecular docking approach, molecular dynamics (MD) analysis, and MM-PBSA method. The detailed analysis of the main clusters led to identifying a lid-like structure and its functional motions. Furthermore, an induced-fit mechanism is proposed where ligand-binding induces conformational changes of the active site. Our findings give an insight into the deeper understanding of RLuc conformational changes during binding steps and ligand-receptor pattern. Moreover, our work broaden our understanding of how active site geometry is adjusted to support the catalytic activity and red-shifted light emission in Super RLuc 8. © 2017 Wiley Periodicals, Inc.

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

PubMed

Chen, Chih-Yen; Hsieh, Chieh; Liao, Che-Hao; Chung, Wei-Lun; Chen, Hao-Tsung; Cao, Wenyu; Chang, Wen-Ming; Chen, Horng-Shyang; Yao, Yu-Feng; Ting, Shao-Ying; Kiang, Yean-Woei; Yang, Chih-Chung C C; Hu, Xiaodong

2012-05-07

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.

Fluorescent biosensor for the detection of hyaluronidase: intensity-based ratiometric sensing and fluorescence lifetime-based sensing using a long lifetime azadioxatriangulenium (ADOTA) fluorophore.

PubMed

Chib, Rahul; Mummert, Mark; Bora, Ilkay; Laursen, Bo W; Shah, Sunil; Pendry, Robert; Gryczynski, Ignacy; Borejdo, Julian; Gryczynski, Zygmunt; Fudala, Rafal

2016-05-01

In this report, we have designed a rapid and sensitive, intensity-based ratiometric sensing as well as lifetime-based sensing probe for the detection of hyaluronidase activity. Hyaluronidase expression is known to be upregulated in various pathological conditions. We have developed a fluorescent probe by heavy labeling of hyaluronic acid with a new orange/red-emitting organic azadioxatriangulenium (ADOTA) fluorophore, which exhibits a long fluorescence lifetime (∼20 ns). The ADOTA fluorophore in water has a peak fluorescence lifetime of ∼20 ns and emission spectra centered at 560 nm. The heavily ADOTA-labeled hyaluronic acid (HA-ADOTA) shows a red shift in the peak emission wavelength (605 nm), a weak fluorescence signal, and a shorter fluorescence lifetime (∼4 ns) due to efficient self-quenching and formation of aggregates. In the presence of hyaluronidase, the brightness and fluorescence lifetime of the sample increase with a blue shift in the peak emission to its original wavelength at 560 nm. The ratio of the fluorescence intensity of the HA-ADOTA probe at 560 and 605 nm can be used as the sensing method for the detection of hyaluronidase. The cleavage of the hyaluronic acid macromolecule reduces the energy migration between ADOTA molecules, as well as the degree of self-quenching and aggregation. This probe can be efficiently used for both intensity-based ratiometric sensing as well as fluorescence lifetime-based sensing of hyaluronidase. The proposed method makes it a rapid and sensitive assay, useful for analyzing levels of hyaluronidase in relevant clinical samples like urine or plasma. Graphical Abstract Scheme showing cleavage of HA-ADOTA probe by hyaluronidase and the change in the emission spectrum of HA-ADOTA probe before and after cleavage by hyaluronidase.

Electron Shuttling by Dissolved Humic Substances: Using Fluorescence Spectroscopy to Move Beyond the Laboratory to Natural Lakes, Streams and Groundwaters

NASA Astrophysics Data System (ADS)

McKnight, D. M.

2017-12-01

Humic substances are an important class of reactive chemical species in natural waters, and one important role is their capacity to as an electron acceptor and/or electron shuttle to ferric iron present as solid phase ferric oxides. Several lines of evidence point to quinone-like moieties being the main redox active moieties that can be used by microbes in respiration. Concomitantly, the humic fraction of dissolved organic mater (DOM) contains the dominant fluorophores in many natural waters. Examination of excitation emission matrices (EEMs) across redox gradients in diverse aquatic systems show that the EEMs are generally red-shifted under reducing conditions, such as anoxic bottom waters in lakes and hypoxic waters in riparian wetlands. Furthermore, there is striking similarity between the humic fluorophores that are resolved by statistical analysis and the fluorescence spectra of model quinone compounds, with the more reduced species having red-shifted fluorescence spectra. This apparent red-shift can be quantified based on the distribution of apparently "quinone-like", "semi-quinone-like" and "hydroquinone-like" fluorophores determined by the PARAFAC statistical analysis. Because fluorescence spectroscopy can be applied at ambient DOM concentrations for samples that have been maintained in an anoxic condition, fluorescence spectroscopy can provide insight into the role of humic electron shuttling in natural systems. Examples are presented demosntrating the changing EEMs in anoxic bottomwaters in a lake in the McMurdo Dry Valleys following a major flood event and the role of organic material in the mobilization of arsenic in shallow groundwater in South East Asia.

Influence of functional groups on the photophysical properties of dimethylamino chalcones as laser dyes

NASA Astrophysics Data System (ADS)

Ibnaouf, K. H.; Elzupir, A. O.; AlSalhi, M. S.; Alaamer, Abdulaziz S.

2018-02-01

In this report, a series of 3-(4-(Dimethylamino) phenyl)-1-(4,3 di-substituted phenyl)-(2E) - propen -1-one chalcones was synthesised and examined as optical materials. The influence of functional groups (FG) and solvents on their photophysical properties was investigated. These include absorption, fluorescence, Stokes shift, and amplified spontaneous emission (ASE). The absorption spectra of all compounds showed a wavelength band in the range 404-429 nm, whereas the fluorescence spectra exhibited a band at 470-535 nm. We found that the fluorescence intensity was inversely proportional to the concentration of chalcones. The FGs and solvents had an amazing effect on the photophysical properties of the synthesised materials. Unexpectedly, the electron withdrawing group showed a highly red shift, whereas the electron donating group exhibited a blue shift. Further, these compounds showed large Stokes shifts (up to 5800 cm-1). ASE was observed under pump pulse laser excitation, and the wavelengths were tuned from 509 to 566 nm.

Photoluminescence light-up detection of zinc ion and imaging in living cells based on the aggregation induced emission enhancement of glutathione-capped copper nanoclusters.

PubMed

Lin, Liyun; Hu, Yuefang; Zhang, Liangliang; Huang, Yong; Zhao, Shulin

2017-08-15

In this work, we prepared glutathione (GSH)-capped copper nanoclusters (Cu NCs) with red emission by simply adjusting the pH of GSH/Cu 2+ mixture at room temperature. A photoluminescence light-up method for detecting Zn 2+ was then developed based on the aggregation induced emission enhancement of GSH-capped Cu NCs. Zn 2+ could trigger the aggregation of Cu NCs, inducing the enhancement of luminescence and the increase of absolute quantum yield from 1.3% to 6.2%. GSH-capped Cu NCs and the formed aggregates were characterized, and the possible mechanism was also discussed. The prepared GSH-capped Cu NCs exhibited a fast response towards Zn 2+ and a wider detection range from 4.68 to 2240μM. The detection limit (1.17μM) is much lower than that of the World Health Organization permitted in drinking water. Furthermore, taking advantages of the low cytotoxicity, large Stokes shift, red emission and light-up detection mode, we explored the use of the prepared GSH-capped Cu NCs in the imaging of Zn 2+ in living cells. The developed luminescence light-up nanoprobe may hold the potentials for Zn 2+ -related drinking water safety and biological applications. Copyright © 2017 Elsevier B.V. All rights reserved.

Diamines as auxiliary ligands for tuning photophysical and electrochemical properties of Ruthenium(II) polypyridyl complexes

NASA Astrophysics Data System (ADS)

Al-Rashdi, Kamelah S.; Babgi, Bandar A.; Sahin, Cigdem; Eltayeb, Naser E.; Moxey, Graeme J.; Humphrey, Mark G.; Basaleh, Amal S.

2018-04-01

The complex with the formula [Ru(bpy)2(2,3-diaminonaphthalene)][PF6] (5) was synthesized and characterized by 1H NMR spectroscopy, mass spectrometry and elemental analysis. A set of previously reported complexes with the formula [Ru(bpy)2(diamine)][PF6]{diamine = 1,2-diaminoethane (2), o-phenylenediamine (3), 1,2-diaminocyclohexane (4) } was synthesized and crystal structures were obtained for complexes 3 and 4. UV-vis absorption spectra of the complexes 2-5 were collected and compared to that of [Ru(bpy)3][PF6]2 (1), showing that the MLCT band is red-shifted upon introducing the diamine ligands in place of bipyridine. Emission spectra, excited-state lifetimes and emission quantum yields were collected at room temperature for the complexes 1-5, showing considerable changes in the photophysical characteristics upon the introductions of the diamine. The emission spectrum of 5 exhibits an intense emission in the far red-NIR region when excited at 510 nm. The cyclic voltammograms of the complexes 1-5 show one oxidation peak between 0.98 V and 1.15 V which is attributed to the Ru(II)/Ru(III) oxidation couple. Calculated HOMO and LUMO energy levels from both electrochemical data and theoretical calculations suggest a lower HOMO energy level for complex 1 than the diamino-containing complexes, presumably due to the stronger ligand field of the bipyridine.

Multiexcitation Fluorogenic Labeling of Surface, Intracellular, and Total Protein Pools in Living Cells

PubMed Central

2016-01-01

Malachite green (MG) is a fluorogenic dye that shows fluorescence enhancement upon binding to its engineered cognate protein, a fluorogen activating protein (FAP). Energy transfer donors such as cyanine and rhodamine dyes have been conjugated with MG to modify the spectral properties of the fluorescent complexes, where the donor dyes transfer energy through Förster resonance energy transfer to the MG complex resulting in binding-conditional fluorescence emission in the far-red region. In this article, we use a violet-excitable dye as a donor to sensitize the far-red emission of the MG-FAP complex. Two blue emitting fluorescent coumarin dyes were coupled to MG and evaluated for energy transfer to the MG-FAP complex via its secondary excitation band. 6,8-Difluoro-7-hydroxycoumarin-3-carboxylic acid (Pacific blue, PB) showed the most efficient energy transfer and maximum brightness in the far-red region upon violet (405 nm) excitation. These blue-red (BluR) tandem dyes are spectrally varied from other tandem dyes and are able to produce fluorescence images of the MG-FAP complex with a large Stokes shift (>250 nm). These dyes are cell-permeable and are used to label intracellular proteins. Used together with a cell-impermeable hexa-Cy3-MG (HCM) dye that labels extracellular proteins, we are able to visualize extracellular, intracellular, and total pools of cellular protein using one fluorogenic tag that combines with distinct dyes to effect different spectral characteristics. PMID:27159569

Bright blue-shifted fluorescent proteins with Cys in the GAF domain engineered from bacterial phytochromes: fluorescence mechanisms and excited-state dynamics.

PubMed

Hontani, Yusaku; Shcherbakova, Daria M; Baloban, Mikhail; Zhu, Jingyi; Verkhusha, Vladislav V; Kennis, John T M

2016-11-18

Near-infrared fluorescent proteins (NIR FPs) engineered from bacterial phytochromes (BphPs) are of great interest for in vivo imaging. They utilize biliverdin (BV) as a chromophore, which is a heme degradation product, and therefore they are straightforward to use in mammalian tissues. Here, we report on fluorescence properties of NIR FPs with key alterations in their BV binding sites. BphP1-FP, iRFP670 and iRFP682 have Cys residues in both PAS and GAF domains, rather than in the PAS domain alone as in wild-type BphPs. We found that NIR FP variants with Cys in the GAF or with Cys in both PAS and GAF show blue-shifted emission with long fluorescence lifetimes. In contrast, mutants with Cys in the PAS only or no Cys residues at all exhibit red-shifted emission with shorter lifetimes. Combining these results with previous biochemical and BphP1-FP structural data, we conclude that BV adducts bound to Cys in the GAF are the origin of bright blue-shifted fluorescence. We propose that the long fluorescence lifetime follows from (i) a sterically more constrained thioether linkage, leaving less mobility for ring A than in canonical BphPs, and (ii) that π-electron conjugation does not extend on ring A, making excited-state deactivation less sensitive to ring A mobility.

Plasmon excitations in doped square-lattice atomic clusters

NASA Astrophysics Data System (ADS)

Wang, Yaxin; Yu, Ya-Bin

2017-12-01

Employing the tight-binding model, we theoretically study the properties of the plasmon excitations in doped square-lattice atomic clusters. The results show that the dopant atoms would blur the absorption spectra, and give rise to extra plasmon resonant peaks as reported in the literature; however, our calculated external-field induced oscillating charge density shows that no obvious evidences indicate the so-called local mode of plasmon appearing in two-dimensional-doped atomic clusters, but the dopants may change the symmetry of the charge distribution. Furthermore, we show that the disorder of the energy level due to dopant makes the absorption spectrum has a red- or blue-shift, which depends on the position of impurities; disorder of hopping due to dopant makes a blue- or red-shift, a larger (smaller) hopping gives a blue-shift (red-shift); and a larger (smaller) host-dopant and dopant-dopant intersite coulomb repulsion induces a blue-shift (red-shift).

Photoluminescence and cathodoluminescence of Mn doped zinc silicate nanophosphors for green and yellow field emissions displays

NASA Astrophysics Data System (ADS)

Omri, K.; Alyamani, A.; Mir, L. El

2018-02-01

Mn2+-doped Zn2SiO4 (ZSM2+) was synthesized by a facile sol-gel technique. The obtained samples were characterized by X-ray diffraction (XRD), Raman spectroscopy, photoluminescence (PL) and cathodoluminescence (CL) techniques. Under UV excitation, spectra showed that the α-ZSM2+ phosphor exhibited a strong green emission around 525 nm and reached the highest luminescence intensity with the Mn doping concentration of 5 at.%. However, for the β-ZSM2+ phase, an interesting yellow emission band centered at 575 nm of Mn2+ at the Zn2+ tetrahedral sites was observed. In addition, an unusual red shift with increasing Mn2+ content was also found and attributed to an exchange interaction between Mn2+. Both PL and CL spectra exhibit an intense green and yellow emission centered at 525 and 573 nm, respectively, due to the 4T1 (4G)-6A1 (6S) transition of Mn2+. Furthermore, these results indicated that the Mn2+-doped zinc silicate phosphors may have potential applications in green and yellow emissions displays like field emission displays (FEDs).

Sensitive spectroscopic detection of large and denatured protein aggregates in solution by use of the fluorescent dye Nile red.

PubMed

Sutter, Marc; Oliveira, Sabrina; Sanders, Niek N; Lucas, Bart; van Hoek, Arie; Hink, Mark A; Visser, Antonie J W G; De Smedt, Stefaan C; Hennink, Wim E; Jiskoot, Wim

2007-03-01

The fluorescent dye Nile red was used as a probe for the sensitive detection of large, denatured aggregates of the model protein beta-galactosidase (E. coli) in solution. Aggregates were formed by irreversible heat denaturation of beta-galactosidase below and above the protein's unfolding temperature of 57.4 degrees C, and the presence of aggregates in heated solutions was confirmed by static light scattering. Interaction of Nile red with beta-galactosidase aggregates led to a shift of the emission maximum (lambda (max)) from 660 to 611 nm, and to an increase of fluorescence intensity. Time-resolved fluorescence and fluorescence correlation spectroscopy (FCS) measurements showed that Nile red detected large aggregates with hydrodynamic radii around 130 nm. By steady-state fluorescence measurements, it was possible to detect 1 nM of denatured and aggregated beta-galactosidase in solution. The comparison with size exclusion chromatography (SEC) showed that native beta-galactosidase and small aggregates thereof had no substantial effect on the fluorescence of Nile red. Large aggregates were not detected by SEC, because they were excluded from the column. The results with beta-galactosidase demonstrate the potential of Nile red for developing complementary analytical methods that overcome the size limitations of SEC, and can detect the formation of large protein aggregates at early stages.

Tuning exciton energy and fine-structure splitting in single InAs quantum dots by applying uniaxial stress

DOE Office of Scientific and Technical Information (OSTI.GOV)

Su, Dan; Dou, Xiuming; Wu, Xuefei

2016-04-15

Exciton and biexciton emission energies as well as excitonic fine-structure splitting (FSS) in single InAs/GaAs quantum dots (QDs) have been continuously tuned in situ in an optical cryostat using a developed uniaxial stress device. With increasing tensile stress, the red shift of excitonic emission is up to 5 nm; FSS decreases firstly and then increases monotonically, reaching a minimum value of approximately 10 μeV; biexciton binding energy decreases from 460 to 106 μeV. This technique provides a simple and convenient means to tune QD structural symmetry, exciton energy and biexciton binding energy and can be used for generating entangled andmore » indistinguishable photons.« less

Influence of thermally induced structural and morphological changes, and UV irradiation on photoluminescence and optical absorption behavior of CdS nanoparticles

NASA Astrophysics Data System (ADS)

Osman, M. A.; El-Said, Waleed A.; Othman, A. A.; Abd-Elrahim, A. G.

2016-04-01

Polycrystalline cubic CdS nanoparticles (NPs) with a crystallite size ({{D}\\text{Sch}} ) ~3 nm were synthesized by chemical precipitation method at room temperature. Thermal induced structural and morphological changes have been investigated using x-ray diffraction, high-resolution transmission electron microscope, x-ray fluorescence, Fourier transform infrared and Raman spectroscopy. The influence of these changes on optical absorption and photoluminescence (PL) characteristics have been studied. It was found that increasing annealing temperature (T a), results in structural phase transitions at 300 and 700 °C, increasing {{D}\\text{Sch}} and red shift of the optical band gap (E\\text{g}\\text{opt} ) due to the improvement in crystallinity. The photoluminescence emission spectrum of nonstoichiometric CdS (Cd-rich) nanopowder reveals emission bands at 365, 397, and 434 nm. Furthermore, PL spectrum of colloidal solution exhibits additional green and red emission bands at 535, 570 and 622 nm. To explain the mechanism of PL emission in CdS NPs, trapping and radiative recombination levels have been identified and the corresponding energy band diagrams are suggested. Annealing process results in an overall enhancement in PL intensity due to the improvement in crystallinity associated with the reduction of nonradiative surface state defects. Irradiation of CdS NPs colloidal solution at UV irradiation dose  <13 J cm-2 leads to the enhancement of PL quantum efficiency and blue shift of E\\text{g}\\text{opt} (i.e. photo-brightening) due to the decrease in the particle size deduced from Brus equation ≤ft({{D}\\text{Brus}}\\right) , This behavior is due to UV irradiation effects such as photopolymerization, the formation of CdSO4 passivation layers due to photooxidation and the reduction in {{D}\\text{Brus}} by photocorrosion process. At UV irradiation dose  <13 J cm-2, PL emission intensity continuously enhances without any change in both E\\text{g}\\text{opt} and {{D}\\text{Brus}} . This behavior is discussed in terms of electron filling model. Boltzmann curve fitting successfully describes the dependence of both {{D}\\text{Brus}} and E\\text{g}\\text{opt} on UV irradiation dose.

PARABIOTIC INTOXICATION. II. THE DISTRIBUTION AND SURVIVAL OF Cr$sup 51$- LABELED RED BLOOD CELLS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tokuda, S.; MacGillivray, M.H.

1962-04-01

The anemia and polycythemia in parent-to-F/sub 1/ parabiotic intoxication in mice were studied using Cr/sup 51/- and Fe/sup 59/ labeled red blood cells. It was observed that the anemia and polycythemia result from a shift in red cell mass from the hybrid into its parent strain partner. Because crosscirculation was observed between the parabionts during the anemia and polycythemia, the shift is attributed to unequal cross transfusion between the parabionts. There was neither preferential selection nor preferential destruction of either parental or hybrid red cells during the shift in red cell mass. (auth)

Structural, morphological and steady state photoluminescence spectroscopy studies of red Eu(3+)-doped Y2O3 nanophosphors prepared by the sol-gel method.

PubMed

Lamiri, Lyes; Guerbous, Lakhdar; Samah, Madani; Boukerika, Allaoua; Ouhenia, Salim

2015-12-01

Europium trivalent (Eu(3+))-doped Y2O3 nanopowders of different concentrations (0.5, 2.5, 5 or 7 at.%) were synthesized by the sol-gel method, at different pH values (pH 2, 5 or 8) and annealing temperatures (600 °C, 800 °C or 1000 °C). The nanopowders samples were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), Fourier transform infrared spectroscopy (FT-IR) and steady state photoluminescence spectroscopy. The effect of pH of solution and annealing temperatures on structural, morphological and photoluminescence properties of Eu(3+)-doped Y2O3 were studied and are discussed. It was found that the average crystallite size of the nanopowders increased with increasing pH and annealing temperature values. The Y2O3:Eu(3+) material presented different morphology and its evolution depended on the pH value and the annealing temperature. Activation energies at different pH values were determined and are discussed. Under ultraviolet (UV) light excitation, Y2O3:Eu(3+) showed narrow emission peaks corresponding to the (5)D0- (7) FJ (J = 0, 1, 2 and 3) transitions of the Eu(3+) ion, with the most intense red emission at 611 assigned to forced electric dipole (5)D0 → (7)F2. The emission intensity became more intense with increasing annealing temperature and pH values, related to the improvement of crystalline quality. For the 1000 °C annealing temperature, the emission intensity presented a maximum at pH 5 related to the uniform cubic-shaped particles. It was found that for lower annealing temperatures (small crystallite size) the CTB (charge transfer band) position presented a red shift. Copyright © 2015 John Wiley & Sons, Ltd.

Energy transfer by way of an exciplex intermediate in flexible boron dipyrromethene-based allosteric architectures.

PubMed

Mula, Soumyaditya; Elliott, Kristopher; Harriman, Anthony; Ziessel, Raymond

2010-10-07

We have designed and synthesized a series of modular, dual-color dyes comprising a conventional boron dipyrromethene (Bodipy) dye, as a yellow emitter, and a Bodipy dye possessing extended conjugation that functions as a red emitter. A flexible tether of variable length, built from ethylene glycol residues, connects the terminal dyes. A critical design element of this type of dyad relates to a secondary amine linkage interposed between the conventional Bodipy and the tether. Cyclic voltammetry shows both Bodipy dyes to be electroactive and indicates that the secondary amine is quite easily oxidized. The ensuing fluorescence quenching is best explained in terms of the rapid formation of an intermediate charge-transfer state. In fact, exciplex-type emission is observed in weakly polar solvents and over a critical temperature range. In the dual-color dyes, direct excitation of the yellow emitter results in the appearance of red fluorescence, indicating that the exciplex is likely involved in the energy-transfer event, and provides for a virtual Stokes shift of 5000 cm(-1). Replacing the red emitter with a higher energy absorber (namely, pyrene) facilitates the collection of near-UV light and extends the virtual Stokes shift to 8000 cm(-1). Modulation of the efficacy of intramolecular energy transfer is achieved by preorganization of the connector in the presence of certain cations. This latter behavior, which is fully reversible, corresponds to an artificial allosteric effect.

Electronic and optical properties of novel carbazole-based donor-acceptor compounds for applications in blue-emitting organic light-emitting diodes

DOE PAGES

Legaspi, Christian M.; Stubbs, Regan E.; Yaron, David J.; ...

2015-08-20

We report that organic light-emitting diodes (OLEDs) have received a significant attention over the past decade due to their energy-saving potential. We have recently synthesized two novel carbazole-based donor-acceptor compounds and analyzed their optical properties to determine their suitability for use as blue emitters in OLEDs. These compounds show remarkable photo-stability and high quantum yields in the blue region of the spectrum. In addition, they have highly solvatochromic emission. In non-polar solvents, bright, blue-shifted (λmax ≈ 398 nm), and highly structured emission is seen. With increasing solvent dielectric constant, the emission becomes weaker, red-shifted (λmax ≈ 507 nm), and broad.more » We aim to determine the underlying cause of these changes. Electronic structure calculations indicate the presence of multiple excited states with comparable oscillator strength. These states are of interest because there are several with charge-transfer (CT) character, and others centered on the donor moiety. We theorize that CT states play a role in the observed changes in emission lineshape and may promote charge mobility for electrofluorescence in OLEDs. In the future, we plan to use Stark spectroscopy to analyze the polarity of excited states and transient absorption spectroscopy to observe the dynamics in the excited state.« less

Electronic and optical properties of novel carbazole-based donor-acceptor compounds for applications in blue-emitting organic light-emitting diodes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Legaspi, Christian M.; Stubbs, Regan E.; Yaron, David J.

We report that organic light-emitting diodes (OLEDs) have received a significant attention over the past decade due to their energy-saving potential. We have recently synthesized two novel carbazole-based donor-acceptor compounds and analyzed their optical properties to determine their suitability for use as blue emitters in OLEDs. These compounds show remarkable photo-stability and high quantum yields in the blue region of the spectrum. In addition, they have highly solvatochromic emission. In non-polar solvents, bright, blue-shifted (λmax ≈ 398 nm), and highly structured emission is seen. With increasing solvent dielectric constant, the emission becomes weaker, red-shifted (λmax ≈ 507 nm), and broad.more » We aim to determine the underlying cause of these changes. Electronic structure calculations indicate the presence of multiple excited states with comparable oscillator strength. These states are of interest because there are several with charge-transfer (CT) character, and others centered on the donor moiety. We theorize that CT states play a role in the observed changes in emission lineshape and may promote charge mobility for electrofluorescence in OLEDs. In the future, we plan to use Stark spectroscopy to analyze the polarity of excited states and transient absorption spectroscopy to observe the dynamics in the excited state.« less

ZnO nanowires for tunable near-UV/blue LED

NASA Astrophysics Data System (ADS)

Pauporté, Thierry; Lupan, Oleg; Viana, Bruno

2012-02-01

Nanowires (NWs)-based light emitting diodes (LEDs) have drawn large interest due to many advantages compared to thin film based devices. Markedly improved performances are expected from nanostructured active layers for light emission. Nanowires can act as direct waveguides and favor light extraction without the use of lenses and reflectors. Moreover, the use of wires avoids the presence of grain boundaries and then the emission efficiency should be boosted by the absence of non-radiative recombinations at the joint defects. Electrochemical deposition technique was used for the preparation of ZnO-NWs based light emitters. Nanowires of high structural and optical quality have been epitaxially grown on p-GaN single crystalline films substrates. We have shown that the emission is directional with a wavelength that was tuned and red-shifted toward the visible region by doping with Cu in ZnO NWs.

Constraining the red shifts of TeV BL Lac objects

NASA Astrophysics Data System (ADS)

Qin, Longhua; Wang, Jiancheng; Yan, Dahai; Yang, Chuyuan; Yuan, Zunli; Zhou, Ming

2018-01-01

We present a model-dependent method to estimate the red shifts of three TeV BL Lac objects (BL Lacs) through fitting their (quasi-)simultaneous multi-waveband spectral energy distributions (SEDs) with a one-zone leptonic synchrotron self-Compton model. Considering the impact of electron energy distributions (EEDs) on the results, we use three types of EEDs to fit the SEDs: a power-law EED with exponential cut-off (PLC), a log-parabola (PLLP) EED and the broken power-law (BPL) EED. We also use a parameter α to describe the uncertainties of the extragalactic background light models, as in Abdo et al. We then use a Markov chain Monte Carlo method to explore the multi-dimensional parameter space and obtain the uncertainties of the model parameters based on the observational data. We apply our method to obtain the red shifts of three TeV BL Lac objects in the marginalized 68 per cent confidence, and find that the PLC EED does not fit the SEDs. For 3C66A, the red shift is 0.14-0.31 and 0.16-0.32 in the BPL and PLLP EEDs. For PKS1424+240, the red shift is 0.55-0.68 and 0.55-0.67 in the BPL and PLLP EEDs. For PG1553+113, the red shift is 0.22-0.48 and 0.22-0.39 in the BPL and PLLP EEDs. We also estimate the red shift of PKS1424+240 in the high stage to be 0.46-0.67 in the PLLP EED, roughly consistent with that in the low stage.

HYDRO2GEN: Non-thermal hydrogen Balmer and Paschen emission in solar flares generated by electron beams

NASA Astrophysics Data System (ADS)

Druett, M. K.; Zharkova, V. V.

2018-03-01

Aim. Sharp rises of hard X-ray (HXR) emission accompanied by Hα line profiles with strong red-shifts up to 4 Å from the central wavelength, often observed at the onset of flares with the Specola Solare Ticinese Telescope (STT) and the Swedish Solar Telescope (SST), are not fully explained by existing radiative models. Moreover, observations of white light (WL) and Balmer continuum emission with the Interface Region Imaging Spectrograph (IRISH) reveal strong co-temporal enhancements and are often nearly co-spatial with HXR emission. These effects indicate a fast effective source of excitation and ionisation of hydrogen atoms in flaring atmospheres associated with HXR emission. In this paper, we investigate electron beams as the agents accounting for the observed hydrogen line and continuum emission. Methods: Flaring atmospheres are considered to be produced by a 1D hydrodynamic response to the injection of an electron beam defining their kinetic temperatures, densities, and macro velocities. We simulated a radiative response in these atmospheres using a fully non-local thermodynamic equilibrium (NLTE) approach for a 5-level plus continuum hydrogen atom model, considering its excitation and ionisation by spontaneous, external, and internal diffusive radiation and by inelastic collisions with thermal and beam electrons. Simultaneous steady-state and integral radiative transfer equations in all optically thick transitions (Lyman and Balmer series) were solved iteratively for all the transitions to define their source functions with the relative accuracy of 10-5. The solutions of the radiative transfer equations were found using the L2 approximation. Resulting intensities of hydrogen line and continuum emission were also calculated for Balmer and Paschen series. Results: We find that inelastic collisions with beam electrons strongly increase excitation and ionisation of hydrogen atoms from the chromosphere to photosphere. This leads to an increase in Lyman continuum radiation, which has high optical thickness, and after the beam is off it governs hydrogen ionisation and leads to the long lasting orders of magnitude enhancement of emission in Balmer and Paschen continua. The ratio of Balmer-to-other-continuum head intensities are found to be correlated with the initial flux of the beam. The height distribution of contribution functions for Paschen continuum emission indicate a close correlation with the observations of heights of WL and HXR emission reported for limb flares. This process also leads to a strong increase of wing emission (Stark's wings) in Balmer and Paschen lines, which is superimposed on large red-shifted enhancements of Hα-Hγ line emission resulting from a downward motion by hydrodynamic shocks. The simulated line profiles are shown to fit closely the observations for various flaring events.

Absorption and Emission of the Apigenin and Luteolin Flavonoids: A TDDFT Investigation

NASA Astrophysics Data System (ADS)

Amat, Anna; Clementi, Catia; de Angelis, Filippo; Sgamellotti, Antonio; Fantacci, Simona

2009-09-01

The absorption and emission properties of the two components of the yellow color extracted from weld (Reseda luteola L.), apigenin and luteolin, have been extensively investigated by means of DFT and TDDFT calculations. Our calculations reproduce the absorption spectra of both flavonoids in good agreement with the experimental data and allow us to assign the transitions giving rise to the main spectral features. For apigenin, we have also computed the electronic spectrum of the monodeprotonated species, providing a rationale for the red-shift of the experimental spectrum with increasing pH. The fluorescence emission of both apigenin and luteolin has then been investigated. Excited-state TDDFT geometry optimizations have highlighted an excited-state intramolecular proton transfer (ESIPT) from the 5-hydroxyl to the 4-carbonyl oxygen of the substituted benzopyrone moiety. By computing the potential energy curves at the ground and excited states as a function of an approximate proton transfer coordinate for apigenin, we have been able to trace an ESIPT pathway and thus explain the double emission observed experimentally.

Blue upconversion in Yb3+/Tm3+ co-doped silica fiber based on glass phase-separation technology

NASA Astrophysics Data System (ADS)

Yang, Yu; Chu, Yingbo; Chen, Zhangru; Xing, Yingbin; Hu, Xionwei; Li, Haiqing; Peng, Jinggang; Dai, Nengli; Li, Jinyan; Yang, Luyun

2018-02-01

Yb3+/Tm3+ co-doped silica fiber was prepared successfully by glass phase-separation technology. The measured refractive index profile indicated that the active fiber core had an excellent uniformity. The highest emission intensity was obtained in a sample with a Yb3+ concentration of 0.3 mol/L and a Tm3+ concentration of 0.1 mol/L. Under the excitation at 976 nm, intense blue upconversion emission of Tm3+ at 474 nm was observed due to energy transfer from Yb3+ to Tm3+. A three-photon process was responsible for the blue emission. Due to re-absorption resulted from the Tm3+:3H6→1G4 transition, the blue emission peak was red-shifted. It is suggested that the fiber preparation technology based on glass phase-separation technology can be a potential candidate for preparing active fibers with large core or complex fiber structure.

Photophysical processes of some benzimidazole derivatives

NASA Astrophysics Data System (ADS)

Chen, Zhaobin; Zhang, Caihong; Feng, Liheng

2005-11-01

The photophysical properties of N-(α-naphthyl)-benzimidazole (α-NABI), N-(β-naphthyl)-benzimidazole (β-NABI) and N-(α-pyridyl)-benzimidazole (α-PYBI) were studied and α-NYBI exhibit intramolecular charge transfer fluorescence in polar solvents. The fluorescence of benzimidazoles can be quenched by acetic acid and the existence of exciplexes was observed between the benzimidazole derivatives and acetic acid. Particularly, the maximum emission peak of solution of α-PYBI in mixed solvent, ether and acetic acid, presents obvious red-shift with the increase of concentration of acetic acid in the mixed solvent.

Satellite Studies of Storm-Time Thermospheric Winds

NASA Technical Reports Server (NTRS)

Fejer, Bela G.

2005-01-01

In this project we have studied the climatology and storm-time dependence of longitude-averaged mid- and low-latitude thermospheric neutral winds observed by the WINDII instrument on board the UARS satellite. This satellite is in a circular, 57 deg inclination orbit at a height of 585 km; the orbit precesses at a rate of 5 deg per day. WINDII is a Michelson interferometer that measures Doppler shifts of the green line (557.7 nm) and red line (630.0 nm) airglow emissions at the Earth's limb, covering latitudes up to 72 deg.

Fluorescence from polystyrene - Photochemical processes in polymeric systems, 7

NASA Technical Reports Server (NTRS)

Gupta, M. C.; Gupta, A.

1983-01-01

Results are presented for measurements of the fluorescence spectra of polystyrene in dilute solution and in pure solid films. It is determined that a major potential source of experimental error is the concurrent photooxidative degradation in air which may obscure fluorescence emission from monomeric sites in solid films at 25 C. The fluorescence spectra of oriented films are evaluated in terms of the monomer to excimer fluorescence intensity ratio and the excimer 'red shift'. The monomer to excimer fluorescence intensity ratio is determined to be significantly higher in fluid solution than in solid film.

Structure of the red fluorescent protein from a lancelet (Branchiostoma lanceolatum): a novel GYG chromophore covalently bound to a nearby tyrosine

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pletnev, Vladimir Z., E-mail: vzpletnev@gmail.com; Pletneva, Nadya V.; Lukyanov, Konstantin A.

The crystal structure of the novel red emitting fluorescent protein from lancelet Branchiostoma lanceolatum (Chordata) revealed an unusual five residues cyclic unit comprising Gly58-Tyr59-Gly60 chromophore, the following Phe61 and Tyr62 covalently bound to chromophore Tyr59. A key property of proteins of the green fluorescent protein (GFP) family is their ability to form a chromophore group by post-translational modifications of internal amino acids, e.g. Ser65-Tyr66-Gly67 in GFP from the jellyfish Aequorea victoria (Cnidaria). Numerous structural studies have demonstrated that the green GFP-like chromophore represents the ‘core’ structure, which can be extended in red-shifted proteins owing to modifications of the protein backbonemore » at the first chromophore-forming position. Here, the three-dimensional structures of green laGFP (λ{sub ex}/λ{sub em} = 502/511 nm) and red laRFP (λ{sub ex}/λ{sub em} ≃ 521/592 nm), which are fluorescent proteins (FPs) from the lancelet Branchiostoma lanceolatum (Chordata), were determined together with the structure of a red variant laRFP-ΔS83 (deletion of Ser83) with improved folding. Lancelet FPs are evolutionarily distant and share only ∼20% sequence identity with cnidarian FPs, which have been extensively characterized and widely used as genetically encoded probes. The structure of red-emitting laRFP revealed three exceptional features that have not been observed in wild-type fluorescent proteins from Cnidaria reported to date: (i) an unusual chromophore-forming sequence Gly58-Tyr59-Gly60, (ii) the presence of Gln211 at the position of the conserved catalytic Glu (Glu222 in Aequorea GFP), which proved to be crucial for chromophore formation, and (iii) the absence of modifications typical of known red chromophores and the presence of an extremely unusual covalent bond between the Tyr59 C{sup β} atom and the hydroxyl of the proximal Tyr62. The impact of this covalent bond on the red emission and the large Stokes shift (∼70 nm) of laRFP was verified by extensive structure-based site-directed mutagenesis.« less

Confining metal-halide perovskites in nanoporous thin films

PubMed Central

Demchyshyn, Stepan; Roemer, Janina Melanie; Groiß, Heiko; Heilbrunner, Herwig; Ulbricht, Christoph; Apaydin, Dogukan; Böhm, Anton; Rütt, Uta; Bertram, Florian; Hesser, Günter; Scharber, Markus Clark; Sariciftci, Niyazi Serdar; Nickel, Bert; Bauer, Siegfried; Głowacki, Eric Daniel; Kaltenbrunner, Martin

2017-01-01

Controlling the size and shape of semiconducting nanocrystals advances nanoelectronics and photonics. Quantum-confined, inexpensive, solution-derived metal halide perovskites offer narrowband, color-pure emitters as integral parts of next-generation displays and optoelectronic devices. We use nanoporous silicon and alumina thin films as templates for the growth of perovskite nanocrystallites directly within device-relevant architectures without the use of colloidal stabilization. We find significantly blue-shifted photoluminescence emission by reducing the pore size; normally infrared-emitting materials become visibly red, and green-emitting materials become cyan and blue. Confining perovskite nanocrystals within porous oxide thin films drastically increases photoluminescence stability because the templates auspiciously serve as encapsulation. We quantify the template-induced size of the perovskite crystals in nanoporous silicon with microfocus high-energy x-ray depth profiling in transmission geometry, verifying the growth of perovskite nanocrystals throughout the entire thickness of the nanoporous films. Low-voltage electroluminescent diodes with narrow, blue-shifted emission fabricated from nanocrystalline perovskites grown in embedded nanoporous alumina thin films substantiate our general concept for next-generation photonic devices. PMID:28798959

Excited state luminescence of multi-(5-phenyl-1,3,4-oxadiazo-2-yl)benzenes in an electron-donating matrix: exciplex or electroplex?

PubMed

Yang, Chih-Chiang; Hsu, Chia-Jung; Chou, Pi-Tai; Cheng, Hsu Chun; Su, Yuhlong Oliver; Leung, Man-kit

2010-01-21

Multi-(5-phenyl-1,3,4-oxadiazo-2-yl)benzenes show emission in organic solvents from ultraviolet to blue (339-447 nm). The reduction potentials E(1/2)(red) cover a large range of -2.11 V for 2,5-diphenyl-1,3,4-oxadiazole to -0.76 V for 1,2,3,4,5,6-hexa(5-phenyl-1,3,4-oxadiazo-2-yl)benzene. An unexpectedly wide spectral range of the oxadiazole (OXD) exciplex emissions in PVK is observed, ranging from 406 to 603 nm. The OXDs also exhibit similar electroluminescence (EL) when blended into polyvinylcarbazole (PVK). A linear correlation between the lambda(max) of the electroluminescence and photoluminescence is observed, implying that the emission mechanisms in both processes are similar. In addition, the linear correlation between the E(1/2)(red) versus lambda(max) of EL (eV) reflected that the term of the charge-transfer configuration of the contact electron-hole pair plays a major role in the exciplex emission. The exciplex EL of 1,2,5-tri(5-phenyl-1,3,4-oxadiazo-2-yl)benzene (5) could be as high as 1.0 cd/A. Since the exciplex emission usually has a large Stokes shift, this provides a window for us to generate duo emissions for near white light EL with high efficiency. Among the devices we tried, the device of PVK/2-tert-butylphenyl-5-biphenyl-1,3,4-oxadiazole/5/2,5,8,11-tetra-tert-butylperylene (100:40:40:4) gave EL with good current efficiency of 1.63 cd/A.

Three-terminal RGB full-color OLED pixels for ultrahigh density displays.

PubMed

Fröbel, Markus; Fries, Felix; Schwab, Tobias; Lenk, Simone; Leo, Karl; Gather, Malte C; Reineke, Sebastian

2018-06-26

In recent years, the organic light-emitting diode (OLED) technology has been a rapidly evolving field of research, successfully making the transition to commercial applications such as mobile phones and other small portable devices. OLEDs provide efficient generation of light, excellent color quality, and allow for innovative display designs, e.g., curved shapes, mechanically flexible and/or transparent devices. Especially their self emissive nature is a highly desirable feature for display applications. In this work, we demonstrate an approach for full-color OLED pixels that are fabricated by vertical stacking of a red-, green-, and blue-emitting unit. Each unit can be addressed separately which allows for efficient generation of every color that is accessible by superpositioning the spectra of the individual emission units. Here, we use a combination of time division multiplexing and pulse width modulation to achieve efficient color mixing. The presented device design requires only three independently addressable electrodes, simplifying both fabrication and electrical driving. The device is built in a top-emission geometry, which is highly desirable for display fabrication as the pixel can be directly deposited onto back-plane electronics. Despite the top-emission design and the application of three silver layers within the device, there is only a minor color shift even for large viewing angles. The color space spanned by the three emission sub-units exceeds the sRGB space, providing more saturated green/yellow/red colors. Furthermore, the electrical performance of each individual unit is on par with standard single emission unit OLEDs, showing very low leakage currents and achieving brightness levels above 1000 cd/m 2 at moderate voltages of around 3-4 V.

Luminescence and scintillation characteristics of (GdxY3-x)Al2Ga3O12:Ce (x = 1,2,3) single crystals

NASA Astrophysics Data System (ADS)

Chewpraditkul, Warut; Pattanaboonmee, Nakarin; Sakthong, Ongsa; Chewpraditkul, Weerapong; Szczesniak, Tomasz; Moszynski, Marek; Kamada, Kei; Yoshikawa, Akira; Nikl, Martin

2018-02-01

The luminescence and scintillation characteristics of Czochralski-grown (GdxY3-x)Al2Ga3O12:Ce (x = 1,2,3) single crystals are presented. With increasing Gd content in this garnet host, the 5d2 absorption band was blue-shifted while the 5d1 absorption and 5d1 → 4f emission bands were red-shifted due to an increase in the crystal field splitting of the 5d levels. In addition, the luminescence quenching temperature of the Ce3+emission and activation energy for thermal quenching decreased with increasing Gd content. The Gd3+ → Ce3+ energy transfer was evidenced by photoluminescence excitation spectra of Ce3+ emission. At 662 keV γ - rays, the light yield (LY) of 48,600 ph/MeV and energy resolution of 6.5% was measured for a Gd3Al2Ga3O12:Ce crystal. Scintillation decay measurements were performed using the time-correlated single photon counting technique. Superior time resolution of Gd3Al2Ga3O12:Ce is due to its high LY and fast scintillation response. The total mass attenuation coefficients at 60 and 662 keV γ - rays were also determined.

Influence of the Doppler effect on radiative transfer in a spherical plasma under macroscopic motion of substance

NASA Astrophysics Data System (ADS)

Kosarev, N. I.

2018-03-01

The non-LTE radiative transfer in spherical plasma containing resonantly absorbing light ions has been studied numerically under conditions of macroscopic motion of substance. Two types of macroscopic motion were simulated: radial expansion and compression (pulsation) of spherical plasma; rotation of plasma relative to an axis of symmetry. The calculations of absorption line profile of transmitted broadband radiation and the emission line profile were performed for the optically dense plasma of calcium ions on the resonance transition with wavelength 397 nm. Numerical results predict frequency shifts in the emission line profile to red wing of the spectrum for radial expansion of the plasma and to blue wing of the spectrum for the plasma compression at an average velocity of ions along the ray of sight equal to zero. The width of the emission line profile of a rotating plasma considerably exceeds the width of the profile of the static plasma, and the shift of the central frequency of resonance transition from the resonance frequency of the static plasma gives a linear velocity of ion motion along a given ray trajectory in units of thermal velocity. Knowledge of the linear radial velocity of ions can be useful for diagnostic purposes in determining the frequency and period of rotation of optically dense plasmas.

Enhancement of red upconversion emission of cubic phase NaLuF{sub 4}: Yb{sup 3+}/Ho{sup 3+}/Ce{sup 3+} nanocrystals

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gao, Wei, E-mail: gaowei@xupt.edu.com; Dong, Jun, E-mail: dongjun@xupt.edu.cn; Liu, Jihong

Highlights: • The upconversion emission of Ho{sup 3+} ions was tuned from green to red. • The upconversion mechanism of Ho{sup 3+} ions was discussed based on emission spectrum. • The conversion efficiency between Ho{sup 3+} and Ce{sup 3+} were studied and calculated. - Abstract: The red upconversion emission of lanthanide-doped fluoride nanocrystals have great potential applications in color display and anticounterfeiting applications, especially for biological imaging and biomedical. In this work, a significant enhancement of red upconversion emission of Ho{sup 3+} ions was successfully obtained in the cubic phase NaLuF{sub 4} nanocrystals through codoping Ce{sup 3+} ions under NIRmore » 980 nm excitation. The ratio of red-to-green emission of Ho{sup 3+} ions was enhanced about 10-fold, which is due to two efficient cross relaxation processes derived from Ho{sup 3+} and Ce{sup 3+} ions promoted the red emission and quenched the green emission. The upconversion emission and luminescent colors of NaLuF{sub 4}: Yb{sup 3+}/Ho{sup 3+} nanocrystals were carefully investigated by a confocal microscopy setup. The possible upconversion emission mechanism and conversion efficiency of cross relaxation between Ho{sup 3+} and Ce{sup 3+} ions were discussed in detail. The current study suggests that strong red emission of NaLuF{sub 4}: Yb{sup 3+}/Ho{sup 3+}/Ce{sup 3+} nanomaterials can be used for color display and anticounterfeiting techniques.« less

Dual emissive manganese and copper Co-doped Zn-In-S quantum dots as a single color-converter for high color rendering white-light-emitting diodes.

PubMed

Yuan, Xi; Ma, Ruixin; Zhang, Wenjin; Hua, Jie; Meng, Xiangdong; Zhong, Xinhua; Zhang, Jiahua; Zhao, Jialong; Li, Haibo

2015-04-29

Novel white light emitting diodes (LEDs) with environmentally friendly dual emissive quantum dots (QDs) as single color-converters are one of the most promising high-quality solid-state lighting sources for meeting the growing global demand for resource sustainability. A facile method was developed for the synthesis of the bright green-red-emitting Mn and Cu codoped Zn-In-S QDs with an absorption bangdgap of 2.56 eV (485 nm), a large Stokes shift of 150 nm, and high emission quantum yield up to 75%, which were suitable for warm white LEDs based on blue GaN chips. The wide photoluminescence (PL) spectra composed of Cu-related green and Mn-related red emissions in the codoped QDs could be controlled by varying the doping concentrations of Mn and Cu ions. The energy transfer processes in Mn and Cu codoped QDs were proposed on the basis of the changes in PL intensity and lifetime measured by means of steady-state and time-resolved PL spectra. By integrating these bicolor QDs with commercial GaN-based blue LEDs, the as-fabricated tricolor white LEDs showed bright natural white light with a color rendering index of 95, luminous efficacy of 73.2 lm/W, and color temperature of 5092 K. These results indicated that (Mn,Cu):Zn-In-S/ZnS QDs could be used as a single color-converting material for the next generation of solid-state lighting.

Long-lived exciplex formation and delayed exciton emission in bulk heterojunction blends of silole derivative and polyfluorene copolymer: the role of morphology on exciplex formation and charge separation.

PubMed

Benson-Smith, Jessica J; Wilson, Joanne; Dyer-Smith, Clare; Mouri, Kazuhiro; Yamaguchi, Shigehiro; Murata, Hideyuki; Nelson, Jenny

2009-06-04

Long-lived exciplex emission is observed in blend films of poly[9,9-dioctylfluorene-co-N-(4-methoxy-phenyl)diphenylamine] (TFMO) and the soluble silole derivative 2,5-bis-(2,2-bipyridin-6-yl)-1,1-dimethyl-3,4-diphenylsilacyclopentadiene (PyPySPyPy). The exciplex is characterized by a long-lived (approximately 40-90 ns) component in both the photoluminescence and electroluminescence spectra, which is red-shifted relative to the emission of the pristine materials. In addition to exciplex emission, delayed fluorescence from the TFMO singlet state is observed and is attributed to exciton regeneration through the interfacial exciplex state. Comparing blend films made using chlorobenzene and p-xylene solvents, we find that exciplex lifetime and exciton regeneration in the blend film are sensitive to the choice of solvent and the resulting morphology of the blend film. The exciplex emissive lifetime can be correlated to changes in photoluminescence quenching and efficiency of light-emitting diodes.

Conversion of the luminescence of laser dyes in opal matrices to stimulated emission

DOE Office of Scientific and Technical Information (OSTI.GOV)

Alimov, O K; Basiev, T T; Orlovskii, Yu V

The luminescence and laser characteristics of a synthetic opal matrix filled with organic dyes are studied upon excitation by nanosecond laser pulses. The appearance of stimulated emission in a partially ordered scattering medium is investigated. It is shown that if the luminescence spectrum of a dye (oxazine-17) is located far outside the photonic bandgap of the opal matrix, stimulated emission along a preferential direction in the (111) plane is observed when pumping exceeds a threshold even without an external optical cavity. The stimulated emission spectrum is considerably narrower than the luminescence spectrum and consists of several narrow lines located withinmore » the dye luminescence band. If the luminescence spectrum of a dye (rhodamine 6G) overlaps with the photonic bandgap of the opal matrix, a different picture is observed. The loss of radiation in the matrix leads to the red shift of the luminescence spectrum, while the stimulated emission as in the case of oxazine-17 lies is observed within the luminescence band. (active media, lasers, and amplifiers)« less

Comparison of Refractive Error Changes in Retinopathy of Prematurity Patients Treated with Diode and Red Lasers.

PubMed

Roohipoor, Ramak; Karkhaneh, Reza; Riazi Esfahani, Mohammad; Alipour, Fateme; Haghighat, Mahtab; Ebrahimiadib, Nazanin; Zarei, Mohammad; Mehrdad, Ramin

2016-01-01

To compare refractive error changes in retinopathy of prematurity (ROP) patients treated with diode and red lasers. A randomized double-masked clinical trial was performed, and infants with threshold or prethreshold type 1 ROP were assigned to red or diode laser groups. Gestational age, birth weight, pretreatment cycloplegic refraction, time of treatment, disease stage, zone and disease severity were recorded. Patients received either red or diode laser treatment and were regularly followed up for retina assessment and refraction. The information at month 12 of corrected age was considered for comparison. One hundred and fifty eyes of 75 infants were enrolled in the study. Seventy-four eyes received diode and 76 red laser therapy. The mean gestational age and birth weight of the infants were 28.6 ± 3.2 weeks and 1,441 ± 491 g, respectively. The mean baseline refractive error was +2.3 ± 1.7 dpt. Posttreatment refraction showed a significant myopic shift (mean 2.6 ± 2.0 dpt) with significant difference between the two groups (p < 0.001). There was a greater myopic shift among children with zone I and diode laser treatment (mean 6.00 dpt) and a lesser shift among children with zone II and red laser treatment (mean 1.12 dpt). The linear regression model, using the generalized estimating equation method, showed that the type of laser used has a significant effect on myopic shift even after adjustment for other variables. Myopic shift in laser-treated ROP patients is related to the type of laser used and the involved zone. Red laser seems to cause less myopic shift than diode laser, and those with zone I involvement have a greater myopic shift than those with ROP in zone II. © 2016 S. Karger AG, Basel.

Photophysical Characterization and BSA Interaction of Direct Ring Carboxy Functionalized Symmetrical squaraine Dyes

NASA Astrophysics Data System (ADS)

Saikiran, Maryala; Pandey, Shyam S.; Hayase, Shuzi; Kato, Tamaki

2017-11-01

A series of far-red sensitive symmetrical squaraine dyes bearing direct -COOH functionalized indole ring were synthesized, characterized and subjected to photophysical investigations. These symmetrical squaraine dyes were then subjected to investigate their interaction with bovine serum albumin (BSA) in Phosphate buffer solutions. All the squaraine dyes under investigation exhibit intense and sharp optical absorption mainly in the far-red wavelength region from 550 nm -700 nm having very high molar extinction coefficients from 1.3 × 105 dm3.mol-1.cm-1. A very small Stokes shift of 10-17 nm indicates the rigid conformational structure of squaraine chromophore. Interaction of these dyes with BSA leads to not only enhanced emission intensity but also bathochromically shifted absorption maximum due to formation of dye-BSA conjugate. These dyes bind strongly with BSA having about an order of magnitude higher binding constant as compared to the reported squaraine dyes. Amongst the symmetrical squaraine dyes investigated in this work one bearing substituents like trifluorobutyl as alkyl chain at N-position of indole ring and carboxylic acid on benzene ring at the terminal (SQ-26) exhibited highest association with the BSA having very high binding constant 8.01 × 106 M-1.

Fluorescent labeling of proteins with amine-specific 1,3,2-(2H)-dioxaborine polymethine dye.

PubMed

Gerasov, Andriy; Shandura, Mykola; Kovtun, Yuriy; Losytskyy, Mykhaylo; Negrutska, Valentyna; Dubey, Igor

2012-01-15

A novel water-soluble amine-reactive dioxaborine trimethine dye was synthesized in a good yield and characterized. The potential of the dye as a specific reagent for protein labeling was demonstrated with bovine serum albumin and lysozyme. Its interaction with proteins was studied by fluorescence spectroscopy and gel electrophoresis. The covalent binding of this almost nonfluorescent dye to proteins results in a 75- to 78-fold increase of its emission intensity accompanied by a red shift of the fluorescence emission maximum by 27 to 45 nm, with fluorescence wavelengths of labeled biomolecules being more than 600 nm. The dye does not require activation for the labeling reaction and can be used in a variety of bioassay applications. Copyright © 2011 Elsevier Inc. All rights reserved.

High luminescent L-cysteine capped CdTe quantum dots prepared at different reaction times

NASA Astrophysics Data System (ADS)

Kiprotich, Sharon; Onani, Martin O.; Dejene, Francis B.

2018-04-01

This paper reports a facile synthesis route of high luminescent L-cysteine capped CdTe quantum dots (QDs). The effect of reaction time on the growth mechanism, optical and physical properties of the CdTe QDs was investigated in order to find the suitability of them towards optical and medical applications. The representative high-resolution transmission microscopy (HRTEM) analysis showed that the as-obtained CdTe QDs appeared as spherical particles with excellent monodispersity. The images exhibited clear lattice fringes which are indicative of good crystallinity. The X-ray diffraction (XRD) pattern displayed polycrystalline nature of the QDs which correspond well to zinc blende phase of bulk CdTe. The crystallite sizes calculated from the Scherrer equation were less than 10 nm for different reaction times which were in close agreement with the values estimated from HRTEM. An increase in reaction time improved crystallinity of the sample as explained by highest peak intensity of the XRD supported by the photoluminescence emission spectra which showed high intensity at a longer growth time. It was observed that for prolonged growth time the emission bands were red shifted from about 517-557 nm for 5-180 min of reaction time due to increase in particle sizes. Ultraviolet and visible analysis displayed well-resolved absorption bands which were red shifted upon an increase in reaction time. There was an inverse relation between the band gap and reaction time. Optical band gap decreases from 3.98 to 2.59 eV with the increase in reaction time from 15 to 180 min.

Photophysical Properties of Organoplatinum(II) Compounds and Derived Self-Assembled Metallacycles and Metallacages: Fluorescence and its Applications.

PubMed

Saha, Manik Lal; Yan, Xuzhou; Stang, Peter J

2016-11-15

Over the past couple of decades, coordination-driven self-assembly has evolved as a broad multidisciplinary domain that not only covers the syntheses of aesthetically pleasing supramolecular architectures but also emerges as a method to form new optical materials, chemical sensors, theranostic agents, and compounds with light-harvesting and emissive properties. The majority of these applications depend upon investigations that reveal the photophysical nature and electronic structure of supramolecular coordination complexes (SCCs), including two-dimensional (2D) metallacycles and three-dimensional (3D) metallacages. As such, well-defined absorption and emission spectra are important for a given SCC to be used for sensing, bioimaging, and other applications with molecular fluorescence being an important component. In this Account, we summarize the photophysical properties of some bis(phosphine)organoplatinum(II) compounds and their discrete SCCs. The platinum(II) based organometallic precursors typically display spectral red-shifts and have low fluorescence quantum yields and short fluorescence lifetimes compared to their organic counterparts because the introduction of metal centers enhances both intersystem crossing (ISC) and intramolecular charge transfer (ICT) processes, which can compete with the fluorescence emissions. Likewise ligands with conjugation can also increase the ICT process; hence the corresponding organoplatinum(II) compounds undergo a further decrease in fluorescence lifetimes. The use of endohedral amine functionalized 120°-bispyridyl ligands can dramatically enhance the emission properties of the resultant organoplatinum(II) based SCCs. As such these SCCs display emissions in the visible region (ca. 400-500 nm) and are significantly red-shifted (ca. 80-100 nm) compared to the ligands. This key feature makes them suitable as supramolecular theranostic agents wherein these unique emission properties provide diagnostic spectroscopic handles and the organoplatinum(II) centers act as potential anticancer agents. Using steady state and time-resolved-spectroscopic techniques and quantum computations in concert, we have determined that the emissive properties stem from the ligand-centered transitions involving π-type molecular orbitals with modest contributions from the metal-based orbitals. The self-assembly and the photophysics of organoplatinum(II) ← 3-substituted pyridyl based SCCs are highly diverse. Subtle changes in the ligands' structures can form molecular congener systems with distinct conformational and photophysical properties. Furthermore, the heterometallic SCCs described herein possess rich photophysical properties and can be used for sensing based applications. Tetraphenylethylene (TPE) based SCCs display emissions in the aggregated state as well as in dilute solutions. This is a unique phenomenon that bridges the aggregation caused quenching (ACQ) and aggregation induced emission (AIE) effects. Moreover, a TPE based metallacage exhibits solvatoluminescence, including white light emission in THF solvent, and can act as a fluorescence-sensor for structurally similar ester compounds.

Controlling reabsorption effect of bi-color CdSe quantum dots-based white light-emitting diodes

NASA Astrophysics Data System (ADS)

Siao, Cyuan-Bin; Chung, Shu-Ru; Wang, Kuan-Wen

2017-08-01

The colloidal semiconductor quantum dots (QDs) have the potentials to be used in white light-emitting diode (WLED) as a down-converting component to replace incandescent lamps, because the traditional WLED composed of Y3Al5O12:Ce3+ (YAG:Ce) phosphor lack of red color emissions and shows low color quality. Among various QDs, CdSe has been extensively studied because it possesses attractive characteristics such as high quantum yields (QYs), narrow emission spectral bandwidth, as well as size-tunable optical characteristics. However, in order to enhance the color rendering index (CRI) of WLED, blending materials with different emission wavelengths has been used frequently. Unfortunately, these procedures are complex and time-consuming, and the emission energy of smaller QDs can be reabsorbed by larger QDs, resulting in decreasing the excitation intensity in yellowish-green region. Therefore, in this study, in order to decrease the reabsorption effect and to simplify the procedures, we have demonstrated a facile thermal pyrolyzed route to prepare bicolor CdSe QDs with dual-wavelengths. The emission wavelengths, particle sizes, and QYs of QDs can be tuned from 537/595 to 537/602 nm, 2.59/3.92 to 2.59/4.01 nm, and 27 to 40 %, for GR1 to 3 samples, respectively when the amount of Se precursor is decreased from 1.5 to 0.75 mmol. Meanwhile, the area ratio of green to red (Ag/Ar) in fluorescence spectra is gradually increased, due to the increase in growth rate, and decrease in nuclei formation in red emission. The GR1, GR2, and GR3 QDs are then encapsulated by convert types to form the LED, in which the QDs are deposited on the blue-emitting InGaN LED chip (λem = 450 nm). After encapsulation, the devices properties of Commission International d'Eclairage (CIE) chromaticity and Ag/Ar area ratio are (0.40, 0.24), 0.28/1, (0.40, 0.31), 0.52/1, and (0.40, 0.38), 1.02/1, respectively for GR1, GR2, and GR3. The results show that the green emission intensity are strongly reabsorbed by red emission, as the Ag/Ar area ratios are gradually increased and the CIEs are dramatically shift to white light region, suggesting that the Se amount not only can tune the red emission intensity but also can decrease the reabsorption effect. Based on the above results, the GR3 is suitable to be applied for WLED against the reabsorption effect. Besides, when the GR3 is blended with UV resin of 30 wt. % to prepare the WLED, the CIE located at (0.35, 0.34) is applied as backlight source, providing 126 % color gamut in sRGB standard. As a result, by simply adjusting the concentration of Se precursor, QDs with dual-wavelengths can be prepared and the reabsorption effect can be avoided to show promising lighting properties for the application in WLED.

Blue and red shifted temperature dependence of implicit phonon shifts in graphene

NASA Astrophysics Data System (ADS)

Mann, Sarita; Jindal, V. K.

2017-07-01

We have calculated the implicit shift for various modes of frequency in a pure graphene sheet. Thermal expansion and Grüneisen parameter which are required for implicit shift calculation have already been studied and reported. For this calculation, phonon frequencies are obtained using force constants derived from dynamical matrix calculated using VASP code where the density functional perturbation theory (DFPT) is used in interface with phonopy software. The implicit phonon shift shows an unusual behavior as compared to the bulk materials. The frequency shift is large negative (red shift) for ZA and ZO modes and the value of negative shift increases with increase in temperature. On the other hand, blue shift arises for all other longitudinal and transverse modes with a similar trend of increase with increase in temperature. The q dependence of phonon shifts has also been studied. Such simultaneous red and blue shifts in transverse or out plane modes and surface modes, respectively leads to speculation of surface softening in out of plane direction in preference to surface melting.

Computational study of red- and blue-shifted Csbnd H⋯Se hydrogen bond in Q3Csbnd H⋯SeH2 (Q = Cl, F, H) complexes

NASA Astrophysics Data System (ADS)

Chopra, Pragya; Chakraborty, Shamik

2018-01-01

This work presents Csbnd H⋯Se hydrogen bonding interaction at the MP2 level of theory. The system Q3Csbnd H⋯SeH2 (Q = Cl, F, and H) provides an opportunity to investigate red- and blue-shifted hydrogen bonds. The origin of the red- and blue-shift in Csbnd H stretching frequency has been investigated using Natural Bond Orbital analysis. A large amount of electron density is being transferred to the σ∗Csbnd H orbital in red-shifted Cl3Csbnd H⋯SeH2. Electron density transfer in the blue-shifted F3Csbnd H⋯SeH2 is primarily to the remote fluorine atoms. Further, due to polarization of the Csbnd H bond, the contradicting effects of rehybridization and hyperconjugation are important. The extent of hyperconjugation reigns predominant in explaining the nature of the Csbnd H⋯Se hydrogen bond in Q3Csbnd H⋯SeH2 complexes as the hydrogen bond acceptor remain same in this investigation. Red- and blue-shift in Q3Csbnd H⋯SeH2 (Q = Cl and F) complexes is best described by pro-improper hydrogen bond donor concept.

Mg II Chromospheric Emission Line Bisectors Of HD39801 And Its Relation With The Activity Cycle

NASA Astrophysics Data System (ADS)

García García, Leonardo Enrique; Pérez Martínez, M. Isabel

2016-07-01

Betelgeuse is a cool star of spectral type M and luminosity class I. In the present work, the activity cycle of Betelgeuse was obtained from the integrated emission flux of the Mg II H and K lines, using more than 250 spectra taken from the International Ultraviolet Explorer (IUE) online database. Of which it was found, based on a Lomb Scargle periodogram, a cycle of 16 years, along with 2 sub-cycles with a period of the order of 0.60 and 0.65 years, which may be due to turbulence or possible stellar flares. In addition, an analysis of line asymmetry was made by means of the chromospheric emission line bisectors, due to the strong self-absorption observed in this lines, the blue and red wings were analyzed independently. In order to measure such asymmetry, a "line shift" was calculated, from which several cycles of variability were obtained from a Lomb Scargle periodogram, spanning from few months to 4 years. In the sense, the most significant cycle is about 0.44 and 0.33 years in the blue and red wing respectively. It is worth noting, that the rotation period of the star doesn't play an important role in the variability of the Mg II lines. This technique provides us with a new way to study activity cycles of evolved stars.

QSO Broad Emission Line Asymmetries: Evidence of Gravitational Redshift?

NASA Astrophysics Data System (ADS)

Corbin, Michael R.

1995-07-01

The broad optical and ultraviolet emission lines of QSOs and active galactic nuclei (AGNs) display both redward and blueward asymmetries. This result is particularly well established for Hβ and C IV λ1549, and it has been found that Hβ becomes increasingly redward asymmetric with increasing soft X-ray luminosity. Two models for the origin of these asymmetries are investigated: (1) Anisotropic line emission from an ensemble of radially moving clouds, and (2) Two-component profiles consisting of a core of intermediate (˜1000-4000 km s-1) velocity width and a very broad (˜5000-20,000 km s-1) base, in which the asymmetries arise due to a velocity difference between the centroids of the components. The second model is motivated by the evidence that the traditional broad-line region is actually composed of an intermediate-line region (ILR) of optically thick clouds and a very broad line region (VBLR) of optically thin clouds lying closer to the central continuum source. Line profiles produced by model (1) are found to be inconsistent with those observed, being asymmetric mainly in their cores, whereas the asymmetries of actual profiles arise mainly from excess emission in their wings. By contrast, numerical fitting to actual Hβ and C IV λ1549 line profiles reveals that the majority can be accurately modeled by two components, either two Gaussians or the combination of a Gaussian base and a logarithmic core. The profile asymmetries in Hβ can be interpreted as arising from a shift of the base component over a range ˜6300 km s-1 relative to systemic velocity as defined by the position of the [O III] λ5007 line. A similar model appears to apply to C IV λ1549. The correlation between Hβ asymmetry and X-ray luminosity may thus be interpreted as a progressive red- shift of the VBLR velocity centroid relative to systemic velocity with increasing X-ray luminosity. This in turn suggests that the underlying effect is gravitational red shift, as soft X-ray emission arises from a region ˜ light-minutes in size and arguably traces the mass of the putative supermassive black hole. Depending on the size of the VBLR and the exact amount of its profile centroid shift, central masses in the range 109-10 Msun are implied for the objects displaying the strongest redward profile asymmetries, consistent with other estimates. The largest VBLR velocity dispersions measured from the two-component modeling are ˜20,000 km s-1, which also yields a virial mass ˜109 Msun for a VBLR size 0.1 pc. The gravitational redshift model does not explain the origin of the blueshift of the VBLR emission among low X-ray luminosity sources, however. This must be interpreted as arising from a competing effect such as electron scattering of line photons in the vicinity of the VBLR. On average, radio-loud objects have redward asymmetric broad-line profiles and stronger intermediate- and narrow-line emission than radio-quiet objects of comparable optical luminosity. Under the gravitational redshift model these differences may be interpreted as the result of black hole and host galaxy masses that are larger on average among the former class, consistent with the evidence that they are merger products.

Ultra-bright red-emitting photostable perylene bisimide dyes: new indicators for ratiometric sensing of high pH or carbon dioxide.

PubMed

Pfeifer, David; Klimant, Ingo; Borisov, Sergey M

2018-05-08

New pH sensitive perylene bisimide indicator dyes were synthesised and used for fabrication of optical sensors. The highly photostable dyes show absorption/emission bands in the red/near-infrared (NIR) region of the electromagnetic spectrum, high molar absorption coefficients (up to 100 000 M-1 cm-1) and fluorescence quantum yields close to unity. The absorption and emission spectra show strong bathochromic shift upon deprotonation of imidazole nitrogen which makes the dyes promising as ratiometric fluorescent indicators. Physical entrapment of the indicators into polyurethane hydrogel enables pH determination in alkaline pH. It is also shown that plastic carbon dioxide solid state sensor can be manufactured via immobilization of the pH indicator in a hydrophilic polymer, along with a quaternary ammonium base. The influence of plasticizer, different lipophilic bases and humidity on the sensitivity of the sensor material were systematically investigated. The disubstituted perylene, particularly, features two deprotonation equilibria enabling sensing over a very broad range from 0.5 to 1000 hPa pCO2. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The flares of August 1972. [solar flare characteristics and spectra

NASA Technical Reports Server (NTRS)

Zirin, H.; Tanaka, K.

1973-01-01

Observations of the August, 1972 flares at Big Bear and Tel Aviv, involving monochromatic movies, magnetograms, and spectra, are analyzed. The region (McMath 11976) showed inverted polarity from its inception on July 11; the great activity was due to extremely high shear and gradients in the magnetic field, as well as a constant invasion of one polarity into the opposite; observations in lambda 3835 show remarkable fast flashes in the impulsive flare of 18:38 UT on Aug. 2 with lifetimes of 5 sec, which may be due to dumping of particles in the lower chromosphere. Flare loops show evolutionary increases of their tilts to the neutral line in the flares of Aug. 4 and 7. Spectroscopic observations show red asymmetry and red shift of the H alpha emission in the flash phase of the Aug. 7 flare, as well as substantial velocity shear in the photosphere during the flare, somewhat like earthquake movement along a fault. Finally the total H alpha emission of the Aug. 7 flare could be measured accurately as about 2.5 x 10 to the 30th power erg, considerably less than coarser previous estimates for great flares.

Cesium lead halide perovskite quantum dot-based warm white light-emitting diodes with high color rendering index

NASA Astrophysics Data System (ADS)

Bi, Ke; Wang, Dan; Wang, Peng; Duan, Bin; Zhang, Tieqiang; Wang, Yinghui; Zhang, Hanzhuang; Zhang, Yu

2017-05-01

White light-emitting diodes (WLEDs) were fabricated by employing a combination of a commercial yellow emission Ce3+-doped Y3Al5O12 (YAG:Ce)-based phosphor and all-inorganic perovskite quantum dots pumped with blue LED chip. Perovskite quantum dot solution was used as the color conversion layer with liquid-type structure. Red-emitting materials based on cesium lead halide (CsPb(X)3) perovskite quantum dots were introduced to generate WLEDs with high efficacy and high color rendering index through compensating the red emission of the YAG:Ce phosphor-based commercialized WLEDs. The experimental results suggested that the luminous efficiency and color rendering index of the as-prepared WLED device could reach up to 84.7 lm/W and 89, respectively. The characteristics of those devices including correlated color temperature (CCT), color rendering index (CRI), and color coordinates were observed under different forward currents. The as-fabricated warm WLEDs showed excellent color stability against the increasing current, while the color coordinates shifted slightly from (0.3837, 0.3635) at 20 mA to (0.3772, 0.3592) at 120 mA and color temperature tuned from 3803 to 3953 K.

Assessment of spectroscopic parameters of solvated Eu(dmh)3 phen organometallic complex in various basic and acidic solvents.

PubMed

Chitnis, Dipti; Kalyani, N Thejo; Dhoble, Sanjay

2018-05-31

We report on the comprehension of novel europium activated hybrid organic Eu(dmh) 3 phen (Eu: europium, dmh: 2,6-dimethyl-3,5-heptanedione, phen: 1,10 phenanthroline) organo-metallic complexes, synthesized at different pH values by the solution technique. Photo physical properties of these complexes in various basic and acidic solvents were probed by UV-vis optical absorption and photoluminescence (PL) spectra. Minute differences in optical absorption peaks with variable optical densities were encountered with the variation in solvent from basic (chloroform, toluene, tetrahydrofuran) to acidic (acetic acid) media, revealing bathochromic shift in the absorption peaks. The PL spectra of the complex in various acidic and basic organic solvents revealed the position of the emission peak at 613 nm irrespective of the changes in solvents whereas the excitation spectrum almost matched with that of the UV-vis absorption data. The optical density was found to be maximum for the complex with pH 7.0 whereas it gradually decreased when pH was lowered to 6.0 or raised to 8.0 at an interval of 0.5, demonstrating its pH sensitive nature. Several spectroscopic parameters related to probability of transition such as absorbance A(λ), Napierian absorption coefficient α(λ), molecular absorption cross-section σ(λ), radiative lifetime (τ 0 ) and oscillator strength (f) were calculated from UV-vis spectra. The relative intensity ratio (R-ratio), calculated from the emission spectra was found to be almost the same in all the organic solvents. The optical energy gap, calculated for the designed complexes were found to be well in accordance with the ideal acceptance value of energy gap of the emissive materials used for fabrication of red organic light-emitting diode (OLED). The relation between Stoke's shift and solvent polarity function was established by Lippert-Mataga plot. This remarkable independence of the electronic absorption spectra of Eu complexes on the nature of the solvent with unique emission wavelength furnishes its potential to serve as a red light emitter for solution processed OLEDs, display panels and solid-state lighting. Copyright © 2018 John Wiley & Sons, Ltd.

The Time Evolution of Eta Carinae's Colliding Winds

NASA Technical Reports Server (NTRS)

Gull, Theodore R.; Madura, T. I.; Grobe, J. H.; Corcoran, M. F.

2011-01-01

We report new HST/STIS observations that map the high-ionization forbidden line emission in the inner arc second of Eta Car, the first that fully image the extended wind-wind interaction region of the massive colliding wind binary. These observations were obtained after the 2009.0 periastron at orbital phases 0.084, 0.163, and 0.323 of the 5.54-year spectroscopic cycle. We analyze the variations in brightness and morphology of the emission, and find that blue-shifted emission (-400 to -200 km/s is symmetric and elongated along the northeast-southwest axis, while the red-shifted emission (+ 100 to +200 km/s) is asymmetric and extends to the north-northwest. Comparison to synthetic images generated from a 3-D dynamical model strengthens the 3-D orbital orientation found by Madura et al. (2011), with an inclination i = 138 deg, argument of periapsis w = 270 deg, and an orbital axis that is aligned at the same P A on the sky as the symmetry axis of the Homunculus, 312 deg. We discuss the potential that these and future mappings have for constraining the stellar parameters of the companion star and the long-term variability of the system. Plain-Language Abstract: With HST, we resolved the interacting winds of the binary, Eta Carinae. With a 3-D model, we find the binary orbit axis is aligned to the Homunculus axis. This suggests a connection between the binary and Homunculus ejection mechanism.

Construction of energy transfer pathways self-assembled from DNA-templated stacks of anthracene.

PubMed

Iwaura, Rika; Yui, Hiroharu; Someya, Yuu; Ohnishi-Kameyama, Mayumi

2014-01-05

We describe optical properties of anthracene stacks formed from single-component self-assembly of thymidylic acid-appended anthracene 2,6-bis[5-(3'-thymidylic acid)pentyloxy] anthracene (TACT) and the binary self-assembly of TACT and complementary 20-meric oligoadenylic acid (TACT/dA20) in an aqueous buffer. UV-Vis and emission spectra for the single-component self-assembly of TACT and the binary self-assembly of TACT/dA20 were very consistent with stacked acene moieties in both self-assemblies. Interestingly, time-resolved fluorescence spectra from anthracene stacks exhibited very different features of the single-component and binary self-assemblies. In the single-component self-assembly of TACT, a dynamic Stokes shift (DSS) and relatively short fluorescence lifetime (τ=0.35ns) observed at around 450nm suggested that the anthracene moieties were flexible. Moreover, a broad emission at 530nm suggested the formation of an excited dimer (excimer). In the binary self-assembly of TACT/dA20, we detected a broad, red-shifted emission component at 534nm with a lifetime (τ=0.4ns) shorter than that observed in the TACT single-component self-assembly. Combining these results with the emission spectrum of the binary self-assembly of TACT/5'-HEX dA20, we concluded that the energy transfer pathway was constructed by columnar anthracene stacks formed from the DNA-templated self-assembly of TACT. Copyright © 2013 Elsevier B.V. All rights reserved.

First-principle study of phosphors for white-LED applications : absorption and emission energies for Ce- and Eu-doped hosts.

NASA Astrophysics Data System (ADS)

Gonze, Xavier; Jia, Yongchao; Miglio, Anna; Giantomassi, Matteo; Ponce, Samuel; Mikami, Masayoshi

After the invasion of compact fluorescent lamps, white LED lighting is becoming a major contender in ecofriendly light sources, with a combination of yellow-, green- and/or red-emitting phosphors partly absorbing the blue light emitted by an InGaN LED. After introducing the semi-empirical Dorenbos model for 4f' 5d transition energies of rare earth ions, I present a first-principle study of two dozen compounds, pristine as well as doped with Ce3+ or Eu2+ ions, in view of explaining their different emission color. The neutral excitation of the ions is simulated through a constrained density functional theory method coupled with a delta SCF analysis of total energies, yielding absorption energies. Then, atomic positions in the excited state are relaxed, yielding emission energies and Stokes shifts, and identification of luminescent centers. In case of the Ce doped materials, the first-principle approach matches experimental data within 0.3 eV for both absorption and emission energies, covering a range of values between 2.0 eV and 5.0 eV, and provides Stokes shifts within 30%, with two exceptions. This is significantly better than the semi-empirical Dorenbos model. A similar analysis is performed for Eu-doped materials, also examining the thermal quenching of two oxynitride hosts. The work was supported by the FRS-FNRS Belgium (PDR Grant T.0238.13 - AIXPHO).

Facile Atmospheric Pressure Synthesis of High Thermal Stability and Narrow-Band Red-Emitting SrLiAl3N4:Eu(2+) Phosphor for High Color Rendering Index White Light-Emitting Diodes.

PubMed

Zhang, Xuejie; Tsai, Yi-Ting; Wu, Shin-Mou; Lin, Yin-Chih; Lee, Jyh-Fu; Sheu, Hwo-Shuenn; Cheng, Bing-Ming; Liu, Ru-Shi

2016-08-03

Red phosphors (e.g., SrLiAl3N4:Eu(2+)) with high thermal stability and narrow-band properties are urgently explored to meet the next-generation high-power white light-emitting diodes (LEDs). However, to date, synthesis of such phosphors remains an arduous task. Herein, we report, for the first time, a facile method to synthesize SrLiAl3N4:Eu(2+) through Sr3N2, Li3N, Al, and EuN under atmospheric pressure. The as-synthesized narrow-band red-emitting phosphor exhibits excellent thermal stability, including small chromaticity shift and low thermal quenching. Intriguingly, the title phosphor shows an anomalous increase in theoretical lumen equivalent with the increase of temperature as a result of blue shift and band broadening of the emission band, which is crucial for high-power white LEDs. Utilizing the title phosphor, commercial YAG:Ce(3+), and InGaN-based blue LED chip, a proof-of-concept warm white LEDs with a color rendering index (CRI) of 91.1 and R9 = 68 is achieved. Therefore, our results highlight that this method, which is based on atmospheric pressure synthesis, may open a new means to explore narrow-band-emitting nitride phosphor. In addition, the underlying requirements to design Eu(2+)-doped narrow-band-emitting phosphors were also summarized.

Blue-shifted and red-shifted hydrogen bonds: Theoretical study of the CH3CHO· · ·HNO complexes

NASA Astrophysics Data System (ADS)

Yang, Yong; Zhang, Weijun; Gao, Xiaoming

The blue-shifted and red-shifted H-bonds have been studied in complexes CH3CHO?HNO. At the MP2/6-31G(d), MP2/6-31+G(d,p) MP2/6-311++G(d,p), B3LYP/6-31G(d), B3LYP/6-31+G(d,p) and B3LYP/6-311++G(d,p) levels, the geometric structures and vibrational frequencies of complexes CH3CHO?HNO are calculated by both standard and CP-corrected methods, respectively. Complex A exhibits simultaneously red-shifted C bond H?O and blue-shifted N bond H?O H-bonds. Complex B possesses simultaneously two blue-shifted H-bonds: C bond H?O and N bond H?O. From NBO analysis, it becomes evident that the red-shifted C bond H?O H-bond can be explained on the basis of the two opposite effects: hyperconjugation and rehybridization. The blue-shifted C bond H?O H-bond is a result of conjunct C bond H bond strengthening effects of the hyperconjugation and the rehybridization due to existence of the significant electron density redistribution effect. For the blue-shifted N bond H?O H-bonds, the hyperconjugation is inhibited due to existence of the electron density redistribution effect. The large blue shift of the N bond H stretching frequency is observed because the rehybridization dominates the hyperconjugation.

Red carbon dots-based phosphors for white light-emitting diodes with color rendering index of 92.

PubMed

Zhai, Yuechen; Wang, Yi; Li, Di; Zhou, Ding; Jing, Pengtao; Shen, Dezhen; Qu, Songnan

2018-05-29

Exploration of solid-state efficient red emissive carbon dots (CDs) phosphors is strongly desired for the development of high performance CDs-based white light-emitting diodes (WLEDs). In this work, enhanced red emissive CDs-based phosphors with photoluminescence quantum yields (PLQYs) of 25% were prepared by embedding red emissive CDs (PLQYs of 23%) into polyvinyl pyrrolidone (PVP). Because of the protection of PVP, the phosphors could preserve strong luminescence under long-term UV excitation or being mixed with conventional packaging materials. By applying the red emissive phosphors as the color conversion layer, WLEDs with high color rendering index of 92 and color coordinate of (0.33, 0.33) are fabricated. Copyright © 2018 Elsevier Inc. All rights reserved.

A highly selective colorimetric and ratiometric fluorescent chemodosimeter for detection of fluoride ions based on 1,8-naphthalimide derivatives.

PubMed

Kai, Yumei; Hu, Yonghong; Wang, Kai; Zhi, Wenbiao; Liang, Mengmeng; Yang, Wenge

2014-01-24

A high selective colorimetric and ratiometric fluorescent probe based on 4-hydroxy-1, 8-naphthalimide was designed and synthesized to detect fluoride ions (F(-)). The sensing behavior of this probe was studied by UV-visible and fluorescence spectroscopy. The probe displays an 110 nm red-shift of fluorescence emission and the color changes from colorless to yellow by virtue of the strong affinity of F(-) toward silicon which can act as a new visual sensor for F(-). Copyright © 2013 Elsevier B.V. All rights reserved.

The effect of nonequilibrium ionization on ultraviolet line shifts in the solar transition region

NASA Technical Reports Server (NTRS)

Spadaro, D.; Noci, G.; Zappala, R. A.; Antiochos, S. K.

1990-01-01

The line profiles and wavelength positions of all the important emission lines due to carbon were computed for a variety of steady state siphon flow loop models. For the lines from the lower ionization states (C II-C IV) a preponderance of blueshifts was found, contrary to the observations. The lines from the higher ionization states can show either a net red- or blueshift, depending on the position of the loop on the solar disk. Similar results are expected for oxygen. It is concluded that the observed redshifts cannot be explained by the models proposed here.

Absorption of laser plasma in competition with oscillation currents for a terahertz spectrum.

PubMed

Li, Xiaolu; Bai, Ya; Li, Na; Liu, Peng

2018-01-01

We generate terahertz radiation in a supersonic jet of nitrogen molecules pumped by intense two-color laser pulses. The tuning of terahertz spectra from blue shift to red shift is observed by increasing laser power and stagnation pressure, and the red shift range is enlarged with the increased stagnation pressure. Our simulation reveals that the plasma absorption of the oscillation currents and expanded plasma column owing to increased laser intensity and gas number density are crucial factors in the recurrence of the red shift of terahertz spectra. The findings disclose the microscopic mechanism of terahertz radiation and present a controlling knob for the manipulation of a broadband terahertz spectrum from laser plasma.

Room temperature spectrally resolved single-molecule spectroscopy reveals new spectral forms and photophysical versatility of aequorea green fluorescent protein variants.

PubMed

Blum, Christian; Meixner, Alfred J; Subramaniam, Vinod

2004-12-01

It is known from ensemble spectroscopy at cryogenic temperatures that variants of the Aequorea green fluorescent protein (GFP) occur in interconvertible spectroscopically distinct forms which are obscured in ensemble room temperature spectroscopy. By analyzing the fluorescence of the GFP variants EYFP and EGFP by spectrally resolved single-molecule spectroscopy we were able to observe spectroscopically different forms of the proteins and to dynamically monitor transitions between these forms at room temperature. In addition to the predominant EYFP B-form we have observed the blue-shifted I-form thus far only seen at cryogenic temperatures and have followed transitions between these forms. Further we have identified for EYFP and for EGFP three more, so far unknown, forms with red-shifted fluorescence. Transitions between the predominant forms and the red-shifted forms show a dark time which indicates the existence of a nonfluorescent intermediate. The spectral position of the newly-identified red-shifted forms and their formation via a nonfluorescent intermediate hint that these states may account for the possible photoactivation observed in bulk experiments. The comparison of the single-protein spectra of the red-shifted EYFP and EGFP forms with single-molecule fluorescence spectra of DsRed suggest that these new forms possibly originate from an extended chromophoric pi-system analogous to the DsRed chromophore.

Red Shifts with Obliquely Approaching Light Sources.

ERIC Educational Resources Information Center

Head, C. E.; Moore-Head, M. E.

1988-01-01

Refutes the Doppler effect as the explanation of large red shifts in the spectra of distant galaxies and explains the relativistic effects in which the light sources approach the observer obliquely. Provides several diagrams and graphs. (YP)

Spectral behaviour of eosin Y in different solvents and aqueous surfactant media.

PubMed

Chakraborty, Moumita; Panda, Amiya Kumar

2011-10-15

Photophysical behaviour of the anionic xanthene dye, eosin Y (EY) was investigated in solvents of different polarities as well as in the presence of aqueous cationic surfactants. From the correlation between E(T)(30) and Kosower Z values of EY in different solvents, subsequent parameters for EY were determined in the presence of surfactants. A red shift, both in the absorption and emission spectra of EY, was observed with decreasing solvent polarity. Dimerisation of EY was found to be dependent on solvent polarity. Cationic surfactants retarded the process of dimerisation, which were evident from the lower dimerisation constant (K(D)) values, compared to that of in pure water. Dye-surfactant interaction constants were determined at different temperatures (298-318 K) and subsequently the thermodynamic parameters, viz., ΔG°, ΔH° and ΔS° were evaluated using the interaction constant values. The fluorescence spectra of EY followed the same trend as in the absorption spectra, although with lesser extents. Stokes shifts were calculated and correlated with the polarity of the medium. Fluorescence of EY was initially quenched by the cationic surfactants in their pre-micellar region, which then followed a red shift with intensity enhancement. Fluorescence quenching was found to be of Stern-Volmer type where the excited state lifetime of EY remained unchanged in different surfactant media. However, the anisotropy value of EY was changed in the post micellar region of surfactants. Copyright © 2011 Elsevier B.V. All rights reserved.

A Quninolylthiazole Derivatives as an ICT-Based Fluorescent Probe of Hg(II) and its Application in Ratiometric Imaging in Live HeLa Cells.

PubMed

Bai, Jian-Ying; Xie, Yu-Zhong; Wang, Chang-Jiang; Fang, Shu-Qing; Cao, Lin-Nan; Wang, Ling-Li; Jin, Jing-Yi

2018-05-28

As a structural analogue of pyridylthiazole, 2-(2-benzothiazoyl)-phenylethynylquinoline (QBT) was designed as a fluorescent probe for Hg(II) based on an intramolecular charge transfer (ICT) mechanism. The compound was synthesized in three steps starting from 6-bromo-2-methylquinoline, with moderate yield. Corresponding studies on the optical properties of QBT indicate that changes in the fluorescence ratio of QBT in response to Hg(II) could be quantified based on dual-emission changes. More specifically, the emission spectrum of QBT before and after interactions with Hg(II) exhibited a remarkable red shift of about 120 nm, which is rarely reported in ICT-based fluorescent sensors. Finally, QBT was applied in the two-channel imaging of Hg(II) in live HeLa cells.

Femtosecond laser fluorescence and propagation in very dense potassium vapor.

PubMed

Makdisi, Y; Kokaj, J; Afrousheh, K; Nair, R; Mathew, J; Pichler, G

2013-12-16

Femtosecond (fs) laser propagation and fluorescence of dense potassium vapor was studied, and the spectral region around the first and the second doublets of the principal series lines of potassium atoms was investigated. In our search we did not observe the conical emission in the far field, although it was previously observed in the case of rubidium. We discuss the possible reason of this unexpected result. The fluorescence spectrum revealed Rb impurity resonance lines in emission due to the collisional redistribution from the K(4p) levels into the Rb(5p) levels. In the forward propagation of 400 nm femtosecond light we observed the molecular band red shifted from potassium second doublet. However, no molecular spectrum was observed when the mode-locked fs laser light was discretely tuned within the wings of the first resonance lines, at 770 nm.

A novel fluorescence "turn-on" sensor based on a photochromic diarylethene for the selective detection of Al(III)

NASA Astrophysics Data System (ADS)

Wang, Niansheng; Wang, Renjie; Tu, Yayi; Pu, Shouzhi; Liu, Gang

2018-05-01

A novel photochromic diarylethene with a triazole-containing 2-(2‧-phenoxymethyl)-benzothiazole group has been synthesized via "click" reaction. The diarylethene exhibited good photochromism and photoswitchable fluorescence. Its fluorescence emission intensity was enhanced 7-fold by acids, accompanied by the red-shift of emission peak from 526 nm to 566 nm and the concomitant color change from dark to bright flavogreen. The diarylethene selectively formed a 1:1 metal complex with Al3+, resulting in a "turn-on" fluorescence signal. The complexation - reaction between Al3+ and the diarylethene is reversible with the binding constant of 2.73 × 103 L mol-1. The limit of detection (LOD) of Al3+ was determined to be 5.94 × 10-8 mol L-1. Based on this unimolecular platform, a logic circuit was fabricated using the fluorescence emission intensity at 572 nm as the output and the combined stimuli of Al3+/EDTA and UV/Vis as the inputs.

Correlation between emission property and concentration of Sn2+ center in the SnO-ZnO-P2O5 glass.

PubMed

Masai, Hirokazu; Tanimoto, Toshiro; Fujiwara, Takumi; Matsumoto, Syuji; Tokuda, Yomei; Yoko, Toshinobu

2012-12-03

The authors report on the correlation between the photoluminescence (PL) property and the SnO amount in SnO-ZnO-P2O5 (SZP) glass. In the PL excitation (PLE) spectra of the SZP glass containing Sn2+ emission center, two S1 states, one of which is strongly affected by SnO amount, are assumed to exist. The PLE band closely correlates with the optical band edge originating from Sn2+ species, and they both largely red-shifts with increasing amount of SnO. The emission decay time of the SZP glass decreased with increasing amount of SnO and the internal quantum efficiencies of the SZP glasses containing 1~5 mol% of SnO are comparable to that of MgWO4. It is expected that the composition-dependent S1 state (the lower energy excitation band) governs the quantum efficiency of the SZP glasses.

A Comparative Cathodoluminescence Emission Study of Feldspathic Glasses in SNC Meteorites and Quenched Melts of These Glasses

NASA Astrophysics Data System (ADS)

Kubny, A.; Jagoutz, E.

2001-12-01

In this study the cathodoluminescence (electron-excited luminescence) emission spectra were measured in the range 200 to 900 nm of individual feldspathic glass grains in the SNC meteorites Shergotty 101, Shergotty 232, ALHA 84001, EETA 79001-47, EETA 79001-276, and Dar al Gani 476 and those of quenched melts of the feldspathic glass grains. The quenching experiments of the original feldspathic glasses were conducted at 1500° C and atmospheric pressure. The aim of this CL emission study was the characterization of feldspathic glasses of SNC meteorites by comparison of the diagnostic spectral features of the feldspathic glasses of SNC meteorites with those of their quenched melts. In the CL emission spectra of the studied feldspathic glasses generally broad bands in the blue (ca. 460 nm), green (ca. 560 nm), and red (ca. 700 nm) can appear. These emission bands are assigned to structural defects (Al-O--Al centers), and the structural incorporation of Mn2+ and Fe3+ , respectively. The blue emission band at about 460 nm attributed to Al-O--Al centers is observed in the spectra of the original feldspathic glasses whereas it is not present (or only in low relative intensity) in the spectra of the quenched melts. The green emission band at 550 to 575 nm assigned to electronic transitions of Mn2+ in M sites is observed in the spectra of the original feldspathic glasses. It is shifted to longer wavelengths of 590 to 605 nm in the spectra of the quenched melts. The occurrence of the red emission band at about 700 nm attributed to electronic transition of Fe3+ in the spectra of the quenched melts of the feldspathic glasses indicates the presence of structural units which allow the occupancy of Fe3+ on tetrahedral sites. The results obtained by CL emission spectroscopy confirm results of Raman spectroscopic studies that the stuctures of feldspathic glasses of the studied SNC meteorites are modified by melting and quenching at atmospheric pressure. Additionally, comparison with published work on CL emission of shocked oligoclases shows that the feldspathic glasses of the studied SNC meteorites are not diaplectic but melt glasses.

Prefibrillar Formation Conditions of β-Lactoglobulin by Titration and Chaotropes Urea and KSCN Under Thermal Load

NASA Astrophysics Data System (ADS)

Babcock, Jeremiah; Valdez, Rolando; Brancaleon, Lorenzo

2009-10-01

The harmful growth of toxic oligomers in the formation of protein amyloid fibrils have been connected to degenerative diseases like Alzheimer's and Huntington's diseases. Understanding the fundamental mechanisms behind protein unfolding and subsequent fibrillogenesis may provide a way to stop the process from occurring. The purpose of this study was to identify favorable fibril growth conditions for a globular model protein β-lactoglobulin using the chaotropes urea and KSCN, along with titration of a pH 7.04 phosphate buffer solution at 40 ^oC over five days. Time-resolved and steady-state fluorescence was used to examine the shift in emission of the tryptophan amino acids over the applied denaturation ranges. BLG, a dimer in native form, monomerized and partially unfolded at 5 M Urea, 2 M KSCN and at pH 2 in phosphate buffer in vitro. Exposure of the solutions to continuous heat over time caused a increase in the lifetimes and red shift in the emission spectra, indicating the possible beginning of nucleation. The study has provided a base for continuation of the study of oligomerization and subsequent fibrillation of BLG, which may provide a fundamental mechanism of formation transferable to other proteins in vivo.

Interband emission energy in a dilute nitride quaternary semiconductor quantum dot for longer wavelength applications

NASA Astrophysics Data System (ADS)

Mageshwari, P. Uma; Peter, A. John; Lee, Chang Woo; Duque, C. A.

2016-07-01

Excitonic properties are studied in a strained Ga1-xInxNyAs1-y/GaAs cylindrical quantum dot. The optimum condition for the desired band alignment for emitting wavelength 1.55 μm is investigated using band anticrossing model and the model solid theory. The band gap and the band discontinuities of a Ga1-xInxNyAs1-y/GaAs quantum dot on GaAs are computed with the geometrical confinement effect. The binding energy of the exciton, the oscillator strength and its radiative life time for the optimum condition are found taking into account the spatial confinement effect. The effects of geometrical confinement and the nitrogen incorporation on the interband emission energy are brought out. The result shows that the desired band alignment for emitting wavelength 1.55 μm is achieved for the inclusion of alloy contents, y=0.0554% and x=0.339% in Ga1-xInxNyAs1-y/GaAs quantum dot. And the incorporation of nitrogen and indium shows the red-shift and the geometrical confinement shows the blue-shift. And it can be applied for fibre optical communication networks.

Growth of fluorescence gold clusters using photo-chemically activated ligands

NASA Astrophysics Data System (ADS)

Mishra, Dinesh; Aldeek, Fadi; Michael, Serge; Palui, Goutam; Mattoussi, Hedi

2016-03-01

Ligands made of lipoic acid (LA) appended with a polyethylene glycol (PEG) chain have been used in the aqueous phase growth of luminescent gold clusters with distinct emission from yellow to near-IR, using two different routes. In the first route, the gold-ligand complex was chemically reduced using sodium borohydride in alkaline medium, which gave near- IR luminescent gold clusters with maximum emission around 745 nm. In the second method, LA-PEG ligand was photochemically modified to a mixture of thiols, oligomers and oxygenated species under UV-irradiation, which was then used as both reducing agent and stabilizing ligand. By adjusting the pH, temperature, and time of the reaction, we were able to obtain clusters with two distinct emission properties. Refluxing the gold-ligand complex in alkaline medium in the presence of excess ligand gave yellow emission within the first two hours and the emission shifted to red after overnight reaction. Mass spectrometry and chemical assay were used to understand the photo-chemical transformation of Lipoic Acid (LA). Mass spectroscopic studies showed the photo-irradiated product contains thiols, oligomers (dimers, trimers and tetramers) as well as oxygenated species. The amount of thiol formed under different conditions of irradiation was estimated using Ellman's assay.

Contrasting guest binding interaction of cucurbit[7-8]urils with neutral red dye: controlled exchange of multiple guests.

PubMed

Shaikh, Mhejabeen; Choudhury, Sharmistha Dutta; Mohanty, Jyotirmayee; Bhasikuttan, Achikanath C; Pal, Haridas

2010-07-14

Interactions among macrocyclic hosts and dyes/drugs have been explored extensively for their direct usage in controlled uptake and release of large number of potential drug molecules. In this paper we report the non-covalent interaction of cucurbit[8]uril macrocycle (CB8) with a biologically important dye, neutral red, by absorption and fluorescence spectroscopy. A comparative analysis with the complexation behaviour of the dye with CB7, the lower homologue of CB8, indicates contrasting guest binding behaviour with significant changes in the photophysical characteristics of the dye. While CB7 interaction leads to a 1 ratio 1 stoichiometry resulting in approximately 6 fold enhancement in the fluorescence emission of the dye, CB8 displays signatures for a 1 ratio 2 host-guest stoichiometry with drastic reduction in the fluorescence emission. Apart from the evaluation of approximately 2 unit shift in the protolytic equilibrium on complexation (pK(a) shift), the measurements with tryptophan established a selective guest exchange to favour a co-localized dimer inside the CB8 cavity. In a protein medium (BSA), the 1 ratio 2 complex was converted to a 1 ratio 1 ratio 1 CB8-NRH(+)-BSA complex. The finding that NRH(+) can be transferred from CB8 to BSA, even though the binding constant for NRH(+)-CB8 is much higher than NRH(+)-BSA, is projected for a controlled slow release of NRH(+) towards BSA. Since the release and activity of drugs can be controlled by regulating the protolytic equilibrium, the macromolecular encapsulation and release of NRH(+) demonstrated here provide information relevant to host-guest based drug delivery systems and its applications.

Efficient light harvesting within a C153@Zr-based MOF embedded in a polymeric film: spectral and dynamical characterization.

PubMed

Gutiérrez, M; López-González, M; Sánchez, F; Douhal, A

2017-07-21

Light harvesting is a natural phenomenon that scientists try to mimic in artificial systems. Having this in mind, attention has been focused on using new smart-materials for photonics. Herein, we report on the photobehaviour of a Zr-NDC MOF (NDC = dimethyl 2,6-naphthalenedicarboxylate) and its composite material, Coumarin153@Zr-NDC, embedded within a polymeric membrane of poly[bisphenol A carbonate-co-4,4'-(3,3,5-trimethylcyclohexylidene)diphenol carbonate] (PC). For the mixed matrix membrane (MMM) Zr-NDC/PC, we observed interparticle excimer-like formation, taking place in times shorter than 15 ps and giving rise to a red-shifted broad emission band. The interparticle interactions are supported by the SEM images, as they reflect the contact between the MOF crystals. The C153@Zr-NDC/PC material presents an energy transfer (ET) process from the excited MOF to the trapped C153 molecules in 820 ps, with a 35 nm red-shifted emission band corresponding to C153 in PC. The fluorescence quantum yield, as a result of this ET from the MOF, is high enough (25%) to explore the possibility of using this new composite material in a LED device. To elucidate the observed photobehavior, we compared it with those of C153/PC and (2,6-NDC + C153)/PC films. These results shed light on the spectroscopic and dynamical properties of these new composite materials formed by a highly fluorescent molecule, and easily synthesized MOFs and polymeric matrices, opening the way for more research based on these mixed inorganic and organic compounds for possible applications in the fields of luminescence sensing and emitting devices.

Red and near-infrared fluorophores inspired by chlorophylls: consideration of practical brightness in multicolor flow cytometry and biomedical sciences

NASA Astrophysics Data System (ADS)

Taniguchi, Masahiko; Hu, Gongfang; Liu, Rui; Du, Hai; Lindsey, Jonathan S.

2018-02-01

Demands in flow cytometry for increased multiplexing (for detection of multiple antigens) and brightness (for detection of rare entities) require new fluorophores (i.e., "colors") with spectrally distinct fluorescence outside the relatively congested visible spectral region. Flow cytometry fluorophores typically must function in aqueous solution upon bioconjugation and ideally should exhibit a host of photophysical features: (i) strong absorption, (ii) sizable Stokes shift, (iii) modest if not strong fluorescence, and (iv) narrow fluorescence band. Tandem dyes have long been pursued to achieve a large effective Stokes shift, increased brightness, and better control over the excitation and emission wavelengths. Here, the attractive photophysical features of chlorophylls and bacteriochlorophylls - Nature's chosen photoactive pigments for photosynthesis - are described with regards to use in flow cytometry. A chlorophyll (or bacteriochlorophyll) constitutes an intrinsic tandem dye given the red (or near-infrared) fluorescence upon excitation in the higher energy ultraviolet (UV) or visible absorption bands (due to rapid internal conversion to the lowest energy state). Synthetic (bacterio)chlorins are available with strong absorption (near-UV molar absorption coefficient ɛ(λexc) 105 M-1cm-1), modest fluorescence quantum yield (Φf = 0.05-0.30), and narrow fluorescence band (10-25 nm) tunable from 600-900 nm depending on synthetic design. The "relative practical brightness" is given by intrinsic brightness [ɛ(λexc) x Φf] times ηf, the fraction of the fluorescence band that is captured by an emission filter in a multicolor experiment. The spectroscopic features of (bacterio)chlorins are evaluated quantitatively to illustrate practical brightness for this novel class of fluorophores in a prospective 8-color panel.

Diaryl-substituted norbornadienes with red-shifted absorption for molecular solar thermal energy storage.

PubMed

Gray, Victor; Lennartson, Anders; Ratanalert, Phasin; Börjesson, Karl; Moth-Poulsen, Kasper

2014-05-25

Red-shifting the absorption of norbornadienes (NBDs), into the visible region, enables the photo-isomerization of NBDs to quadricyclanes (QCs) to be driven by sunlight. This is necessary in order to utilize the NBD-QC system for molecular solar thermal (MOST) energy storage. Reported here is a study on five diaryl-substituted norbornadienes. The introduced aryl-groups induce a significant red-shift of the UV/vis absorption spectrum of the norbornadienes, and device experiments using a solar-simulator set-up demonstrate the potential use of these compounds for MOST energy storage.

Condition for dust evacuation from the first galaxies

NASA Astrophysics Data System (ADS)

Fukushima, Hajime; Yajima, Hidenobu; Omukai, Kazuyuki

2018-06-01

Dust enables low-mass stars to form from low-metallicity gas by inducing fragmentation of clouds via cooling by thermal emission. Dust may, however, be evacuated from star-forming clouds due to the radiation force from massive stars. We study here the condition for dust evacuation by comparing the dust evacuation time with the time of cloud destruction due to either expansion of H II regions or supernovae. The cloud destruction time has a weak dependence on cloud radius, while the dust evacuation time is shorter for a cloud with a smaller radius. Dust evacuation, thus, occurs in compact star-forming clouds whose column density is NH ≃ 1024-1026 cm-2. The critical halo mass above which dust evacuation occurs is lower for higher formation red shift, e.g. ˜109 M⊙ at red shift z ˜ 3 and ˜107 M⊙ at z ˜ 9. In addition, the metallicity of the gas should be less than ˜10-2 Z⊙, otherwise attenuation by dust reduces the radiation force significantly. From the dust-evacuated gas, massive stars are likely to form, even with a metallicity above ˜10-5 Z⊙, the critical value for low-mass star formation due to dust cooling. This can explain the dearth of ultra-metal-poor stars with a metallicity lower than ˜10-4 Z⊙.

Rare-Earth Activated Nitride Phosphors: Synthesis, Luminescence and Applications

PubMed Central

Xie, Rong-Jun; Hirosaki, Naoto; Li, Yuanqiang; Takeda, Takashi

2010-01-01

Nitridosilicates are structurally built up on three-dimensional SiN4 tetrahedral networks, forming a very interesting class of materials with high thermomechanical properties, hardness, and wide band gap. Traditionally, nitridosilicates are often used as structural materials such as abrasive particles, cutting tools, turbine blade, etc. Recently, the luminescence of rare earth doped nitridosilicates has been extensively studied, and a novel family of luminescent materials has been developed. This paper reviews the synthesis, luminescence and applications of nitridosilicate phosphors, with emphasis on rare earth nitrides in the system of M-Si-Al-O-N (M = Li, Ca, Sr, Ba, La) and their applications in white LEDs. These phosphors exhibit interesting luminescent properties, such as red-shifted excitation and emission, small Stokes shift, small thermal quenching, and high conversion efficiency, enabling them to use as down-conversion luminescent materials in white LEDs with tunable color temperature and high color rendering index.

Absorption and emission spectroscopic characterisation of 8-amino-riboflavin

NASA Astrophysics Data System (ADS)

Tyagi, A.; Zirak, P.; Penzkofer, A.; Mathes, T.; Hegemann, P.; Mack, M.; Ghisla, S.

2009-10-01

The flavin dye 8-amino-8-demethyl- D-riboflavin (AF) in the solvents water, DMSO, methanol, and chloroform/DMSO was studied by absorption and fluorescence spectroscopy. The first absorption band is red-shifted compared to riboflavin, and blue-shifted compared to roseoflavin (8-dimethylamino-8-demethyl-D-riboflavin). The fluorescence quantum yield of AF in the studied solvents varies between 20% and 50%. The fluorescence lifetimes were found to be in the 2-5 ns range. AF is well soluble in DMSO, weakly soluble in water and methanol, and practically insoluble in chloroform. The limited solubility causes AF aggregation, which was seen in differences between measured absorption spectra and fluorescence excitation spectra. Light scattering in the dye absorption region is discussed and approximate absorption cross-section spectra are determined from the combined measurement of transmission and fluorescence excitation spectra. The photo-stability of AF was studied by prolonged light exposure. The photo-degradation routes of AF are discussed.

Study on the inclusion interaction of p-sulfonated calix[ n]arenes with Vitamin K 3 using methylene blue as a spectral probe

NASA Astrophysics Data System (ADS)

Lu, Qin; Gu, Jiashan; Yu, Huapeng; Liu, Chun; Wang, Lun; Zhou, Yunyou

2007-09-01

The characteristics of host-guest complexation between p-sulfonated calix[ n]arene ( SCnA, n = 4, 6) and Vitamin K 3 ( VK3) were investigated by fluorescence spectrometry and absorption spectrometry using methylene blue ( MB) as a probe. Interaction with MB and SCnA led to an obvious decrease in fluorescence intensity of MB, accompanying with shifts of emission peaks. Absorption peaks also showed interesting changes; however, when VK3 was added, fluorescence intensity and absorbance recovered and a slight and slow red shift was observed. The obtained results showed that the inclusion ability of p-sulphonated calix[ n]arenes towards VK3 was the order: p-sulphonated calix[6]arene ( SC6A) > p-sulphonated calix[4]arene ( SC4A). Relative mechanism was proposed to explain the inclusion process.

Study on the inclusion interaction of p-sulfonated calix[n]arenes with Vitamin K3 using methylene blue as a spectral probe.

PubMed

Lu, Qin; Gu, Jiashan; Yu, Huapeng; Liu, Chun; Wang, Lun; Zhou, Yunyou

2007-09-01

The characteristics of host-guest complexation between p-sulfonated calix[n]arene (SCnA, n = 4, 6) and Vitamin K(3) (VK(3)) were investigated by fluorescence spectrometry and absorption spectrometry using methylene blue (MB) as a probe. Interaction with MB and SCnA led to an obvious decrease in fluorescence intensity of MB, accompanying with shifts of emission peaks. Absorption peaks also showed interesting changes; however, when VK(3) was added, fluorescence intensity and absorbance recovered and a slight and slow red shift was observed. The obtained results showed that the inclusion ability of p-sulphonated calix[n]arenes towards VK(3) was the order: p-sulphonated calix[6]arene (SC6A) >p-sulphonated calix[4]arene (SC4A). Relative mechanism was proposed to explain the inclusion process.

Tunneling electron induced molecular electroluminescence from individual porphyrin J-aggregates

DOE Office of Scientific and Technical Information (OSTI.GOV)

Meng, Qiushi; Zhang, Chao; Zhang, Yang, E-mail: zhyangnano@ustc.edu.cn, E-mail: zcdong@ustc.edu.cn

2015-07-27

We investigate molecular electroluminescence from individual tubular porphyrin J-aggregates on Au(111) by tunneling electron excitations in an ultrahigh-vacuum scanning tunneling microscope (STM). High-resolution STM images suggest a spiral tubular structure for the porphyrin J-aggregate with highly ordered “brickwork”-like arrangements. Such aggregated nanotube is found to behave like a self-decoupled molecular architecture and shows red-shifted electroluminescence characteristics of J-aggregates originated from the delocalized excitons. The positions of the emission peaks are found to shift slightly depending on the excitation sites, which, together with the changes in the observed spectral profiles with vibronic progressions, suggest a limited exciton coherence number within severalmore » molecules. The J-aggregate electroluminescence is also found unipolar, occurring only at negative sample voltages, which is presumably related to the junction asymmetry in the context of molecular excitations via the carrier injection mechanism.« less

Low-Temperature Preparation of Ag-Doped ZnO Nanowire Arrays, DFT Study, and Application to Light-Emitting Diode.

PubMed

Pauporté, Thierry; Lupan, Oleg; Zhang, Jie; Tugsuz, Tugba; Ciofini, Ilaria; Labat, Frédéric; Viana, Bruno

2015-06-10

Doping ZnO nanowires (NWs) by group IB elements is an important challenge for integrating nanostructures into functional devices with better and tuned performances. The growth of Ag-doped ZnO NWs by electrodeposition at 90 °C using a chloride bath and molecular oxygen precursor is reported. Ag acts as an electrocatalyst for the deposition and influences the nucleation and growth of the structures. The silver atomic concentration in the wires is controlled by the additive concentration in the deposition bath and a content up to 3.7 atomic % is reported. XRD analysis shows that the integration of silver enlarges the lattice parameters of ZnO. The optical measurements also show that the direct optical bandgap of ZnO is reduced by silver doping. The bandgap shift and lattice expansion are explained by first principle calculations using the density functional theory (DFT) on the silver impurity integration as an interstitial (Ag(i)) and as a substitute of zinc atom (Ag(Zn)) in the crystal lattice. They notably indicate that Ag(Zn) doping forms an impurity band because of Ag 4d and O 2p orbital interactions, shifting the Fermi level toward the valence band. At least, Ag-doped ZnO vertically aligned nanowire arrays have been epitaxially grown on GaN(001) substrate. The heterostructure has been inserted in a light emitting device. UV-blue light emission has been achieved with a low emission threshold of 5 V and a tunable red-shifted emission spectrum related to the bandgap reduction induced by silver doping of the ZnO emitter material.

Electrostatics determine vibrational frequency shifts in hydrogen bonded complexes.

PubMed

Dey, Arghya; Mondal, Sohidul Islam; Sen, Saumik; Ghosh, Debashree; Patwari, G Naresh

2014-12-14

The red-shifts in the acetylenic C-H stretching vibration of C-H∙∙∙X (X = O, N) hydrogen-bonded complexes increase with an increase in the basicity of the Lewis base. Analysis of various components of stabilization energy suggests that the observed red-shifts are correlated with the electrostatic component of the stabilization energy, while the dispersion modulates the stabilization energy.

Semiconductor Microcavity Flow Spectroscopy of Intracellular Protein in Human Cells

NASA Astrophysics Data System (ADS)

Gourley, Paul; Cox, Jim; Hendricks, Judy; McDonald, Anthony; Copeland, Guild; Sasaki, Darryl; Skirboll, Steve; Curry, Mark

2001-03-01

The speed of light through a biofluid or biological cell is inversely related to the biomolecular concentration of proteins and other complex molecules that modify the refractive index at wavelengths accessible to semiconductor lasers. By placing a fluid or cell into a semiconductor microcavity laser, these decreases in light speed can be sensitively recorded in picoseconds as frequency red-shifts in the laser output spectrum. This biocavity laser equipped with microfluidics for transporting cells at high speed through the laser microcavity has shown potential for rapid analysis of biomolecular mass of normal and malignant human cells in their physiologic condition without time-consuming fixing, staining, or tagging. We have used biocavity laser spectroscopy to measure the optical properties of solutions of standard biomolecules (sugars, proteins, DNA, and ions) and human cells. The technique determines the frequency shift, relative to that of water, of spontaneous or stimulated emission from cavity filled with a biomolecular solution. The shift was also measured in human glioblastoma cells that had been sorted by conventional fluorescence-activated cell sorting according to protein content. The results show a direct correlation between protein measured by fluorescence and the frequency shift observed in the microcavity laser.

Greenhouse gas emissions of different land uses in the delta region of Red River, Vietnam

NASA Astrophysics Data System (ADS)

Zhou, Minghua; Ha, Thu; An, Ngo The; Brüggemann, Nicolas

2017-04-01

Agricultural activities are responsible for up to a third of total anthropogenic GHG emissions. The subtropical/tropical delta areas of the large rivers in Southeast Asia are long-term history agricultural regions in the world. However, due to lack of field measurements, the estimation of the contribution of agro-ecosystems in the subtropical/tropical delta areas to global greenhouse gas emissions remains largely uncertain. Here, we conducted field experiments since January 2016 to quantify greenhouse gases (CO2, CH4 and N2O) emissions from four agricultural land uses of annual rice-rice, rice-vegetable, continuous vegetable system and fish pond in Red River delta region of Vietnam by using the transparent static chamber-gas chromatography technique. Higher N2O emissions were observed in the rice-vegetable and continuous vegetable systems, while lower N2O emissions were observed in the rice-rice and find pond systems. Compared to rice-rice system the cumulative N2O fluxes were on average twenty-fold higher in the rice-vegetable and continuous vegetable systems but significantly lower (75%) in the fish pond. Overall the net CO2 sinks were observed in the rice-rice system while other three land uses of rice-vegetable, continuous vegetable and fish pond acted as the net CO2 sources. The rice-rice and fish pond showed net CH4 emissions while variations of CH4 emissions (i.e. shifting between sources and sinks) along variations of soil moisture and temperature were observed in rice-vegetable and continuous vegetable systems. Compared to rice-rice system, the cumulative CH4 fluxes were significantly decreased by 100% for continuous vegetable system, 94% for rice-vegetable system and 89% for fish pond. Overall, the data suggest that conversion of traditional rice-rice paddy system to rice-vegetable, continuous vegetable system and find pond, which are currently undergoing driven by the economical requests and environmental changes (e.g., salinity intrusion) in this delta region, could alter CH4, CO2 and N2O emissions.

Impact of firing temperature on multi-wavelength selective Stokes and anti-Stokes luminescent behavior by Gd2O2S:Er,Yb phosphor and its application in solar energy harvesting

NASA Astrophysics Data System (ADS)

Kataria, V.; Mehta, D. S.

2018-04-01

Erbium (Er3+)-ytterbium (Yb3+) doped gadolinium oxysulphide (Gd2O2S) phosphor has been developed via a facile method of solid-state flux fusion, and offers two-fold spectrum modification with highly intense Stokes and anti-Stokes shift. The effect of the firing cycle on the photoluminescent response and morphology of Gd2O2S:Er,Yb is scrutinized, wherein the firing temperature was varied (1000 °C-1250 °C), keeping firing time and all other parameters constant. Interestingly, the nanostructures fired below 1150 °C showed nanorods of diameter ~200 nm and length ~1-2 µm, whereas firing at 1150 °C and above rendered nanospheres with small diameter, ~350 nm. Highly bright upconversion (UC) emission was achieved even under an extremely low excitation power density of 800 µW cm-2 from a 980 nm laser, and was comfortably visible to the naked eye. The incident power dependent studies disclosed increase in UC-emission intensity with increasing excitation power and a quasi-linear dependence on excitation power density. Intense characteristic UC-emission of Er3+ excited states at 525 nm, 556 nm and 668 nm were observed, and the green emission band was found to be dominant over the red band in intensity. Concurrently, downconversion (DC) emission at 556 nm and 669 nm was also exhibited under ultraviolet excitation (285 nm and 380 nm), with the red band being more powerful than the green, unlike UC-emission. Firing temperature dependent studies divulged the dependence of luminescence intensity on the firing cycle of the luminophore and formation of the respective luminescent phase. The UC-emission intensity was found to be maximum for samples fired at 1150 °C, whereas samples fired at 1000 °C showed the highest DC-emission intensity. The excitation and emission profile of single Gd2O2S:Er,Yb phosphor lying in the desired spectral region and as a dual spectral converter marks its possible application for enhanced harvesting of sunlight.

C IV Doppler shifts observed in active region filaments

NASA Technical Reports Server (NTRS)

Klimchuk, J. A.

1986-01-01

The Doppler shift properties of 21 active region filaments were studied using C IV Dopplergram data. Most are associated with corridors of weak magnetic field that separate opposite polarity strong fields seen in photospheric magnetograms. A majority of the filaments are relatively blue shifted, although several lie very close to the dividing lines between blue and red shift. Only one filament in the samples is clearly red shifted. A new calibration procedure for Dopplergrams indicates that sizable zero point offsets are often required. The center-to-limb behavior of the resulting absolute Doppler shifts suggests that filament flows are usually quite small. It is possible that they vanish.

Molecular Imaging for Breast Cancer Using Magnetic Resonance-Guided Positron Emission Mammography and Excitation-Resolved Near-Infrared Fluorescence Imaging

NASA Astrophysics Data System (ADS)

Cho, Jaedu

The aim of this work is to develop novel breast-specific molecular imaging techniques for management of breast cancer. In this dissertation, we describe two novel molecular imaging approaches for breast cancer management. In Part I, we introduce our multimodal molecular imaging approach for breast cancer therapy monitoring using magnetic resonance imaging and positron emission mammography (MR/PEM). We have focused on the therapy monitoring technique for aggressive cancer molecular subtypes, which is challenging due to time constraint. Breast cancer therapy planning relies on a fast and accurate monitoring of functional and anatomical change. We demonstrate a proof-of-concept of sequential dual-modal magnetic resonance and positron emission mammography (MR/PEM) for the cancer therapy monitoring. We have developed dedicated breast coils with breast compression mechanism equipped with MR-compatible PEM detector heads. We have designed a fiducial marker that allows straightforward image registration of data obtained from MRI and PEM. We propose an optimal multimodal imaging procedure for MR/PEM. In Part II, we have focused on the development of a novel intraoperative near-infrared fluorescence imaging system (NIRF) for image-guided breast cancer surgery. Conventional spectrally-resolved NIRF systems are unable to resolve various NIR fluorescence dyes for the following reasons. First, the fluorescence spectra of viable NIR fluorescence dyes are heavily overlapping. Second, conventional emission-resolved NIRF suffers from a trade-off between the fluence rate and the spectral resolution. Third, the multiple scattering in tissue degrades not only the spatial information but also the spectral contents by the red-shift. We develop a wavelength-swept laser-based NIRF system that can resolve the excitation shift of various NIR fluorescence dyes without substantial loss of the fluence rate. A linear ratiometric model is employed to measure the relative shift of the excitation spectrum of a fluorescence dye.

Synthesis and Characterizations of Pb-modified CdSe Aqueous Quantum Dots and Their Applications in Quantum Dot-Sensitized Solar Cells

NASA Astrophysics Data System (ADS)

Lu, Cheng-Hsin

Quantum Dots (QDs) are semiconductor nanocrystals with typical size ranges around 1-20 nm. They exhibit distinctive size-dependent photoluminescence (PL) properties due to the quantum confinement effect. QDs have great potentials in display, lighting, lasing, bioimaging, fluorescent label, sensor, photodetector, and photovoltaic applications, and have been widely studied in the past decades. Cadmium selenide (CdSe) QDs have been synthesized using an environmentally friendly, aqueous method under low temperature. While traditional QDs synthesized by hot injection method using organic solvent generally exhibit edge-state emission with narrow peaks, aqueous quantum dots (AQDs) tend to have trap-state emissions with broad peaks. The objective of this thesis is to investigate how Pb modifications in CdSe AQDs synthesis can affect the optoelectronic properties of the QDs and how these modifications affect their corresponding photovoltaic performance in quantum dot-sensitized solar cell (QDSSC) applications. Lead (Pb) precursor has been introduced either during the synthesis or after the synthesis of CdSe AQDs forming either Pb-doped or Pb-coated CdSe QDs, respectively. Pb-doped CdSe QDs exhibit red-shift in both absorption and emission spectra while Pb-coated CdSe QDs exhibit blue-shift in both absorption and emission spectra along with the generation of more surface defects. Although blue-shifted absorption indicating a narrower absorption range and the surface defects providing undesired recombination pathways are detrimental to solar cell performance, however surprisingly, we found that QDSSCs made from Pb-coated CdSe QDs actually had better solar cell performance than that made from Pb-doped CdSe QDs. We attributed this finding to a protection/passivation layer formed in-situ when the coated Pb react with the iodide/triiodide electrolyte during solar cell operation resulting in QDSSCs with better charge injection and stability.

Rotation-Infall Motion around the Protostar IRAS 16293-2422 Traced by Water Maser Emission

NASA Astrophysics Data System (ADS)

Imai, Hiroshi; Iwata, Takahiro; Miyoshi, Makoto

1999-08-01

We made VLBI observations of the water maser emission associated with a protostar, IRAS 16293-2422, using the Kashima-Nobeyama Interferometer (KNIFE) and the Japanese domestic VLBI network (J-Net).\\footnote[2]. These distributions of water maser features showed the blue-shifted and red-shifted components separated in the north-south direction among three epochs spanning three years. The direction of the separation was perpendicular to the molecular outflow and parallel to the elongation of the molecular disk. These steady distributions were successfully modeled by a rotating-infalling disk with an outer radius of 100 AU around a central object with a mass of 0.3 MO . The local specific angular momentum of the disk was calculated to be 0.2-1.0times 10-3 km s-1 pc at a radius of 20-100 AU. This value is roughly equal to that of the disk of IRAS 00338+6312 in L1287 and those of the molecular disks around the protostars in the Taurus molecular cloud. The relatively large disk radius of about 100 AU traced by water maser emission suggests that impinging clumps onto the disk should be hotter than 200 K to excite the water maser emission. Mizusawa, Nobeyama, and Kagoshima stations are operated by staff members of National Astronomical Observatory of the Ministry of Education, Science, Sports and Culture. Kashima station is operated by staff members of Communications Research Laboratory of the Ministry of Posts and Telecomunications. The recent status of J-Net is seen in the WWW home page: http://www.nro.nao.ac.jp/\\ \\ miyaji/Jnet.

Kinematics of Extremely Metal-poor Galaxies: Evidence for Stellar Feedback

NASA Astrophysics Data System (ADS)

Olmo-García, A.; Sánchez Almeida, J.; Muñoz-Tuñón, C.; Filho, M. E.; Elmegreen, B. G.; Elmegreen, D. M.; Pérez-Montero, E.; Méndez-Abreu, J.

2017-01-01

The extremely metal-poor (XMP) galaxies analyzed in a previous paper have large star-forming regions with a metallicity lower than the rest of the galaxy. Such a chemical inhomogeneity reveals the external origin of the metal-poor gas fueling star formation, possibly indicating accretion from the cosmic web. This paper studies the kinematic properties of the ionized gas in these galaxies. Most XMPs have a rotation velocity around a few tens of km s-1. The star-forming regions appear to move coherently. The velocity is constant within each region, and the velocity dispersion sometimes increases within the star-forming clump toward the galaxy midpoint, suggesting inspiral motion toward the galaxy center. Other regions present a local maximum in velocity dispersion at their center, suggesting a moderate global expansion. The Hα line wings show a number of faint emission features with amplitudes around a few per cent of the main Hα component, and wavelength shifts between 100 and 400 km s-1. The components are often paired, so that red and blue emission features with similar amplitudes and shifts appear simultaneously. Assuming the faint emission to be produced by expanding shell-like structures, the inferred mass loading factor (mass loss rate divided by star formation rate) exceeds 10. Since the expansion velocity far exceeds the rotational and turbulent velocities, the gas may eventually escape from the galaxy disk. The observed motions involve energies consistent with the kinetic energy released by individual core-collapse supernovae. Alternative explanations for the faint emission have been considered and discarded.

KINEMATICS OF EXTREMELY METAL-POOR GALAXIES: EVIDENCE FOR STELLAR FEEDBACK

DOE Office of Scientific and Technical Information (OSTI.GOV)

Olmo-García, A.; Sánchez Almeida, J.; Muñoz-Tuñón, C.

2017-01-10

The extremely metal-poor (XMP) galaxies analyzed in a previous paper have large star-forming regions with a metallicity lower than the rest of the galaxy. Such a chemical inhomogeneity reveals the external origin of the metal-poor gas fueling star formation, possibly indicating accretion from the cosmic web. This paper studies the kinematic properties of the ionized gas in these galaxies. Most XMPs have a rotation velocity around a few tens of km s{sup −1}. The star-forming regions appear to move coherently. The velocity is constant within each region, and the velocity dispersion sometimes increases within the star-forming clump toward the galaxymore » midpoint, suggesting inspiral motion toward the galaxy center. Other regions present a local maximum in velocity dispersion at their center, suggesting a moderate global expansion. The H α line wings show a number of faint emission features with amplitudes around a few per cent of the main H α component, and wavelength shifts between 100 and 400 km s{sup −1}. The components are often paired, so that red and blue emission features with similar amplitudes and shifts appear simultaneously. Assuming the faint emission to be produced by expanding shell-like structures, the inferred mass loading factor (mass loss rate divided by star formation rate) exceeds 10. Since the expansion velocity far exceeds the rotational and turbulent velocities, the gas may eventually escape from the galaxy disk. The observed motions involve energies consistent with the kinetic energy released by individual core-collapse supernovae. Alternative explanations for the faint emission have been considered and discarded.« less

Infrared absorption of methanethiol clusters (CH3SH)n, n = 2-5, recorded with a time-of-flight mass spectrometer using IR depletion and VUV ionization

NASA Astrophysics Data System (ADS)

Fu, Lung; Han, Hui-Ling; Lee, Yuan-Pern

2012-12-01

We investigated IR spectra in the CH- and SH-stretching regions of size-selected methanethiol clusters, (CH3SH)n with n = 2-5, in a pulsed supersonic jet using infrared (IR)-vacuum ultraviolet (VUV) ionization. VUV emission at 132.50 nm served as the source of ionization in a time-of-flight mass spectrometer. Clusters were dissociated with light from a tunable IR laser before ionization. The variations in intensity of methanethiol cluster ions (CH3SH)n+ were monitored as the IR laser light was tuned across the range 2470-3100 cm-1. In the SH-stretching region, the spectrum of (CH3SH)2 shows a weak band near 2601 cm-1, red-shifted only 7 cm-1 from that of the monomer. In contrast, all spectra of (CH3SH)n, n = 3-5, show a broad band near 2567 cm-1 with much greater intensity. In the CH-stretching region, absorption bands of (CH3SH)2 are located near 2865, 2890, 2944, and 3010 cm-1, red-shifted by 3-5 cm-1 from those of CH3SH. These red shifts increase slightly for larger clusters and bands near 2856, 2884, 2938, and 3005 cm-1 were observed for (CH3SH)5. These spectral results indicate that the S-H...S hydrogen bond plays an important role in clusters with n = 3-5, but not in (CH3SH)2, in agreement with theoretical predictions. The absence of a band near 2608 cm-1 that corresponds to absorption of the non-hydrogen-bonded SH moiety and the large width of observed feature near 2567 cm-1 indicate that the dominant stable structures of (CH3SH)n, n = 3-5, have a cyclic hydrogen-bonded framework.

A new method to measure the virial factors in the reverberation mapping of active galactic nuclei

NASA Astrophysics Data System (ADS)

Liu, H. T.; Feng, H. C.; Bai, J. M.

2017-04-01

Based on the gravitational red shift, which is a prediction of Einstein's general relativity theory, of broad optical emission lines in active galactic nuclei (AGNs), a new method is proposed to estimate the virial factors f in measuring black hole masses MRM by the reverberation mapping of AGNs. The factors f can be measured based on two physical quantities, I.e. the gravitational red shifts zg and the full widths at half maxima vFWHM of broad lines. In the past, it has been difficult to determine the factors f for individual AGNs. We apply this new method to several reverberation-mapped type 1 Seyfert galaxies. There is a correlation between f and the radius of the broad-line region (BLR) rBLR, f=5.4 r_{BLR}^{0.3}, for the gravitationally red-shifted broad lines He II, He I, Hβ and Hα in the narrow-line type 1 Seyfert galaxy (NLS1) Mrk 110. This correlation results from the influence of the radiation pressure of the accretion disc on the BLR clouds. This influence seems to be more important than usually thought so in AGNs. Mrk 110 has f ≈ 8-16, distinctly larger than the mean ≈ 1 usually used to estimate MRM for vFWHM. NGC 4593 and NLS1 Mrk 486 have f ≈ 3 and f ≈ 9, respectively. Higher f values of several tens are derived for three other NLS1s. There is a correlation between f and accretion rate dot{M}_{f=1}, f=6.8dot{M}^{0.4}_{f=1} for five objects, where dot{M}_{f=1}=dot{M}_{bullet }/L_{Edd}c^{-2} as f = 1 is assumed when estimating MRM used in the Eddington luminosity LEdd, dot{M}_{bullet } is the mass accretion rate, and c is the speed of light. These larger f values will produce higher MRM values and lower Eddington ratios.

Adapting photosynthesis to the near-infrared: non-covalent binding of phycocyanobilin provides an extreme spectral red-shift to phycobilisome core-membrane linker from Synechococcus sp. PCC7335.

PubMed

Miao, Dan; Ding, Wen-Long; Zhao, Bao-Qing; Lu, Lu; Xu, Qian-Zhao; Scheer, Hugo; Zhao, Kai-Hong

2016-06-01

Phycobiliproteins that bind bilins are organized as light-harvesting complexes, phycobilisomes, in cyanobacteria and red algae. The harvested light energy is funneled to reaction centers via two energy traps, allophycocyanin B and the core-membrane linker, ApcE1 (conventional ApcE). The covalently bound phycocyanobilin (PCB) of ApcE1 absorbs near 660 nm and fluoresces near 675 nm. In cyanobacteria capable of near infrared photoacclimation, such as Synechococcus sp. PCC7335, there exist even further spectrally red shifted components absorbing >700 nm and fluorescing >710 nm. We expressed the chromophore domain of the extra core-membrane linker from Synechococcus sp. PCC7335, ApcE2, in E. coli together with enzymes generating the chromophore, PCB. The resulting chromoproteins, PCB-ApcE2(1-273) and the more truncated PCB-ApcE2(24-245), absorb at 700 nm and fluoresce at 714 nm. The red shift of ~40 nm compared with canonical ApcE1 results from non-covalent binding of the chromophore by which its full conjugation length including the Δ3,3(1) double bond is preserved. The extreme spectral red-shift could not be ascribed to exciton coupling: dimeric PCB-ApcE2(1-273) and monomeric-ApcE2(24-245) absorbed and fluoresced similarly. Chromophorylation of ApcE2 with phycoerythrobilin- or phytochromobilin resulted in similar red shifts (absorption at 615 and 711 nm, fluorescence at 628 or 726 nm, respectively), compared to the covalently bound chromophores. The self-assembled non-covalent chromophorylation demonstrates a novel access to red and near-infrared emitting fluorophores. Brightly fluorescent biomarking was exemplified in E. coli by single-plasmid transformation. Copyright © 2016 Elsevier B.V. All rights reserved.

Optical and electrical properties of copper-incorporated ZnS films applicable as solar cell absorbers

NASA Astrophysics Data System (ADS)

Mehrabian, M.; Esteki, Z.; Shokrvash, H.; Kavei, G.

2016-10-01

Un-doped and Cu-doped ZnS (ZnS:Cu) thin films were synthesized by Successive Ion Layer Absorption and Reaction (SILAR) method. The UV-visible absorption studies have been used to calculate the band gap values of the fabricated ZnS:Cu thin films. It was observed that by increasing the concentration of Cu2+ ions, the Fermi level moves toward the edge of the valence band of ZnS. Photoluminescence spectra of un-doped and Cu-doped ZnS thin films was recorded under 355 nm. The emission spectrum of samples has a blue emission band at 436 nm. The peak positions of the luminescence showed a red shift as the Cu2+ ion concentration was increased, which indicates that the acceptor level (of Cu2+) is getting close to the valence band of ZnS.

Synthesis, photophysical, and electrochemical properties of wide band gap tetraphenylsilane-carbazole derivatives: Effect of the substitution position and naphthalene side chain

NASA Astrophysics Data System (ADS)

Ho, Kar Wei; Ariffin, A.

2016-12-01

Four tetraphenylsilane-carbazole derivatives with wide bandgaps (3.38-3.55 eV) were synthesized. The effects of the substitution position and of the presence of naphthalene groups on the photophysical, electrochemical and thermal properties were investigated. The derivatives exhibited maximum absorption peaks ranging from 293 to 304 nm and maximum emission peaks ranging from 347 to 386 nm. Changing the carbazole substitution position on the tetraphenylsilane did not significantly change the photophysical and electrochemical properties. However, p-substituted compounds exhibited higher glass transition temperatures than m-substituted compounds. Naphthalene groups with bulky structures had extended the conjugation lengths that red-shifted both the absorption and emission spectra. The LUMO level was decreased, which reduced the optical bandgap and triplet energy level. However, the naphthalene groups significantly improved the thermal stability by increasing the glass transition temperature of the compounds.

A highly selective long-wavelength fluorescent probe for hydrazine and its application in living cell imaging

NASA Astrophysics Data System (ADS)

Hao, Yuanqiang; Zhang, Yintang; Ruan, Kehong; Meng, Fanteng; Li, Ting; Guan, Jinsheng; Du, Lulu; Qu, Peng; Xu, Maotian

2017-09-01

A highly selective long-wavelength turn-on fluorescent probe has been developed for the detection of N2H4. The probe was prepared by conjugation the tricyanofuran-based D-π-A system with a recognizing moiety of acetyl group. In the presence of N2H4, the probe can be effectively hydrazinolysized and produce a turn-on fluorescent emission at 610 nm as well as a large red-shift in the absorption spectrum corresponding to a color change from yellow to blue. The sensing mechanism was confirmed by HPLC, MS, UV-vis, emission spectroscopic and theoretical calculation studies. The probe displayed high selectivity and sensitivity for N2H4 with a LOD (limit of detection) of 0.16 μM. Moreover, the probe was successfully utilized for the detection of hydrazine in living cells.

SERS of Individual Nanoparticles on a Mirror: Size Does Matter, but so Does Shape

PubMed Central

2016-01-01

Coupling noble metal nanoparticles by a 1 nm gap to an underlying gold mirror confines light to extremely small volumes, useful for sensing on the nanoscale. Individually measuring 10 000 of such gold nanoparticles of increasing size dramatically shows the different scaling of their optical scattering (far-field) and surface-enhanced Raman emission (SERS, near-field). Linear red-shifts of the coupled plasmon modes are seen with increasing size, matching theory. The total SERS from the few hundred molecules under each nanoparticle dramatically increases with increasing size. This scaling shows that maximum SERS emission is always produced from the largest nanoparticles, irrespective of tuning to any plasmonic resonances. Changes of particle facet with nanoparticle size result in vastly weaker scaling of the near-field SERS, without much modifying the far-field, and allows simple approaches for optimizing practical sensing. PMID:27223478

SERS of Individual Nanoparticles on a Mirror: Size Does Matter, but so Does Shape.

PubMed

Benz, Felix; Chikkaraddy, Rohit; Salmon, Andrew; Ohadi, Hamid; de Nijs, Bart; Mertens, Jan; Carnegie, Cloudy; Bowman, Richard W; Baumberg, Jeremy J

2016-06-16

Coupling noble metal nanoparticles by a 1 nm gap to an underlying gold mirror confines light to extremely small volumes, useful for sensing on the nanoscale. Individually measuring 10 000 of such gold nanoparticles of increasing size dramatically shows the different scaling of their optical scattering (far-field) and surface-enhanced Raman emission (SERS, near-field). Linear red-shifts of the coupled plasmon modes are seen with increasing size, matching theory. The total SERS from the few hundred molecules under each nanoparticle dramatically increases with increasing size. This scaling shows that maximum SERS emission is always produced from the largest nanoparticles, irrespective of tuning to any plasmonic resonances. Changes of particle facet with nanoparticle size result in vastly weaker scaling of the near-field SERS, without much modifying the far-field, and allows simple approaches for optimizing practical sensing.

Dynamics of the bleaching of tail states in CdS1- x Se x mixed crystals

NASA Astrophysics Data System (ADS)

Breitkopf, T.; Kalt, H.; Klingshirn, C.; Reznitsky, A.

1996-06-01

The kinetics of excitons localized by statistic potential fluctuations have been studied in CdS 1-xSex ternary alloys under quasi-stationary excitation conditions and have been time resolved after picosecond-pulse excitation. In luminescence experiments we observe the filling of the band tail with rising excitation intensity. The reduction of carrier density with time by recombination leads to a red shift of the luminescence band after picosecond-pulse excitation. Bleaching of absorption of the localized states is found in pump-probe experiments. Its dynamics depend on the localization depth of the excitons and on the pump-pulse energy. Using higher excitation intensities, we observe stimulated emission in luminescence, correlated with significant changes in the behavior of the absorption bleaching. The possible origin of the stimulated emission situated in the spectral region of localized states is discussed.

Role of antenna modes and field enhancement in second harmonic generation from dipole nanoantennas.

PubMed

de Ceglia, Domenico; Vincenti, Maria Antonietta; De Angelis, Costantino; Locatelli, Andrea; Haus, Joseph W; Scalora, Michael

2015-01-26

We study optical second harmonic generation from metallic dipole antennas with narrow gaps. Enhancement of the fundamental-frequency field in the gap region plays a marginal role on conversion efficiency. In the symmetric configuration, i.e., with the gap located at the center of the antenna axis, reducing gap size induces a significant red-shift of the maximum conversion efficiency peak. Either enhancement or inhibition of second-harmonic emission may be observed as gap size is decreased, depending on the antenna mode excited at the harmonic frequency. The second-harmonic signal is extremely sensitive to the asymmetry introduced by gap's displacements with respect to the antenna center. In this situation, second-harmonic light can couple to all the available antenna modes. We perform a multipolar analysis that allows engineering the far-field SH emission and find that the interaction with quasi-odd-symmetry modes generates radiation patterns with a strong dipolar component.

Syntheses, crystal structures and luminescent properties of two salts with 2-((1H-imidazol-1-yl)methyl)-1H-benzimidazole

NASA Astrophysics Data System (ADS)

Wang, Yong-Tao; Lü, Lin-Rui; Tang, Gui-Mei

2018-03-01

Two new benzimidazole salts, namely, [H2IBI]2+ 2X (X = NO3- (1), ClO4- (2) [IBI = 2-((1H-imidazol-1-yl)methyl)-1H-benzimidazole], were grown through reacting IBI and two different inorganic acids by slow evaporation method, respectively. Compounds 1 and 2 have been characterized by single-crystal X-ray diffraction, IR, UV-Vis, and thermogravimetric analyses (TGA). In both compounds, a set of hydrogen bonds (C/Nsbnd H⋯O) can be clearly observed, through which a three-dimensional framework will be generated. The luminescent spectra show the emission peaks in compounds 1 and 2 are found at 375 and 371 nm, respectively. By comparison with the free IBI, the emission maxima of compounds 1 and 2 are obviously red-shifted about 67 and 63 nm, respectively.

Electrosynthesis and characterization of oligophenylene deriving from 4-(methoxyphenyl)acetonitrile

NASA Astrophysics Data System (ADS)

Amor, Sarra Ben; Said, Ayoub Haj; Chemek, Mourad; Ayachi, Sahbi; Massuyeau, Florian; Wéry, Jany; Alimi, Kamel; Roudesli, Sadok

2013-01-01

An oligophenylene deriving from the 4-(methoxyphenyl)acetonitrile (MPA), was electrosynthesized by direct anodic oxidation at a constant potential in acetonitrile on a platinium electrode. This oligomer (OMPA) showed a good solubility in common organic solvents. The results of osmometry and gel permeation chromatography analyzes indicated that the average chain length for OMPA was about 5 units. Its chemical structure was elucidated by 1H and 13C NMR, FTIR and UV spectroscopy. A thermal study carried out by thermogravimetric analysis and Differential Scanning Calorimetry showed that the oligomer was stable up to 268 °C. In addition, the photoluminescent properties of OMPA were investigated. In solution, an emission was recorded in the indigo-blue region, however, in solid state this emission was shifted to the orange-red zone. Finally a mechanism for the electro-oligomerization was evoked in the light of the electronic structures of the MPA and its radical cation obtained by DFT calculation.

Ultrafast relaxation dynamics of amine-substituted bipyridyl ruthenium(II) complexes

NASA Astrophysics Data System (ADS)

Song, Hongwei; Wang, Xian; Yang, WenWen; He, Guiying; Kuang, Zhuoran; Li, Yang; Xia, Andong; Zhong, Yu-Wu; Kong, Fan'ao

2017-09-01

The excited state properties of a series of ruthenium(II) amine-substituted bipyridyl complexes, [Ru(bpy)n(NNbpy)3-n]2+, were investigated by steady-state and transient absorption spectroscopy, as well as quantum chemical calculations. The steady-state absorption spectra of these complexes in CH3CN show a distinct red-shift of the 1MLCT absorption with increasing numbers of amine substituent, whereas the emission spectra indicate an energy gap order of [Ru(bpy)3]2+ > [Ru(bpy)2(NNbpy)]2+ > [Ru(NNbpy)3]2+ > [Ru(bpy)(NNbpy)2]2+. Nanosecond, femtosecond transient absorption and electrochemical measurements suggest that NNbpy ligand has a strong influence on the electronic and emission properties of these complexes, due to electron-rich amine substituent. We illustrate how the numbers of amine substituent modulate the spectroscopic properties of transition metal complexes, which is related to the design of new electro-active systems with novel photoelectrochemical properties.

On the Temporal Evolution of Red Sprites, Runaway Theory Versus Data

NASA Technical Reports Server (NTRS)

Yukhimuk, V.; Roussel-Dupre, R. A.; Symbalisty, E. M. D.

1999-01-01

The results of numerical simulations of red sprite discharges, namely the temporal evolutions of optical emissions, are presented and compared with observations. The simulations are done using the recently recalculated runaway avalanche rates. The temporal evolution of these simulations is in good agreement with ground-based photometer and CCD TV camera observations of red sprites. Our model naturally explains the "hairline" of red sprites as a boundary between the region where the intensity of optical emissions associated with runaway breakdown has a maximum and the region where the intensity of optical emissions caused by conventional breakdown and ambient electron heating has a maximum. We also present for the first time simulations of red sprites with a daytime conductivity profile.

Change in structural morphology on addition of ZnO and its effect on fluorescence of Yb³⁺/Er³⁺ doped Y₂O₃.

PubMed

Yadav, R V; Verma, R K; Kaur, G; Rai, S B

2013-02-15

Yb(3+)/Er(3+) codoped Y(2)O(3) phosphor and its composite with ZnO have been synthesized by combustion method. Morphology of the materials has been investigated using X-ray diffraction pattern (XRD) and scanning electron microscopy (SEM) techniques. XRD confirms the constituents as Y(2)O(3) and ZnO, with average crystallite size of 112 nm. On addition of ZnO, a small shifting in XRD pattern of Y(2)O(3) is observed. SEM pattern suggests that the average particle size lies in micro-range (0.5 μm). A dumble like structure is observed for hybrid material on annealing at 1473 K. A strong green (525, 546 nm) with weak blue (411 nm) and red (657 nm) emissions through upconversion has been observed from the phosphor on excitation with 976 nm diode laser. The observed emissions involve (2)H(9/2)→(4)I(15/2), (2)H(11/2)→(4)I(15/2), (4)S(3/2)→(4)I(15/2) and (4)F(9/2)→(4)I(15/2) electronic transitions, respectively. The upconversion process has been confirmed by power dependence measurements and its slope value was found to be 1.85, 1.72 for green and red emissions, respectively. On addition of ZnO, the intensity of these emissions is enhanced several times. The reason behind the enhancement is discussed with the help of the emitting level lifetime. An interesting dual mode property (upconversion and downconversion) to the same material has been observed on excitation with 532 nm laser source. Copyright © 2012 Elsevier B.V. All rights reserved.

Dithieno[3,2-c:2',3'-e]-2,7-diketophosphepin: a unique building block for multifunctional π-conjugated materials.

PubMed

He, Xiaoming; Borau-Garcia, Javier; Woo, Alva Y Y; Trudel, Simon; Baumgartner, Thomas

2013-01-23

A series of conjugated materials based on the new dithieno[3,2-c:2',3'-e]-2,7-diketophosphepin (DTDKP) building block have been studied for the first time. Theoretical calculations predict DTDKP to be a better electron acceptor than the well-known dithienophosphole and the nitrogen analogue, bithiopheneimide. Cyclic voltammetry studies revealed two reduction processes that support their promising electron-acceptor properties, and modification of the P center with O or gold(I) further reduced the LUMO energy to ca. -3.6 eV. Expansion of the DTDKP core with various aromatic moieties has been realized using the Huisgen alkynyl click reaction, resulting in altered optical and electrochemical properties with compounds showing a high-energy absorption band at ca. 270-290 nm and a low-energy band at ca. 390-460 nm. The acceptor character of the DTDKP core was demonstrated by a red shift following the electron-donating strength of the appended aromatic moiety. Intriguing white-light emission from just a single species with the CIE coordinates of (0.33, 0.34) was observed for some of the extended species as the result of an unexpected dual-emission behavior. The high-energy emission in the blue-to-green region and the low-energy emission in the orange-to-red region are attributed to a π* → π transition of the DTDKP core and charge transfer from the triazole moiety to DTDKP, respectively. Apart from tuning of the molecular properties, this novel building block has also been applied in a self-assembled organogel, which exhibited pronounced luminescence. Scanning electron microscopy confirmed that the gel self-assembled by forming a network of entangled 1D fibrous structures on the micrometer scale.

Study of chemical shift in Kα, Kβ1,3 and Kβ// X-ray emission lines of 37Rb compounds with WDXRF

NASA Astrophysics Data System (ADS)

Kainth, Harpreet Singh; Singh, Ranjit; Singh, Tejbir; Mehta, D.; Shahi, J. S.; Kumar, Sanjeev

2018-05-01

The positive and negative chemical shifts in Kα, Kβ1,3 and Kβ// X-ray emission lines of rubidium compounds were measured with high resolution WDXRF spectrometer. The measured energy shifts in Kα emission lines ranges from -2.95 eV to -3.64 eV, Kβ1,3 emission lines ranges from 1.16 eV to 1.32 eV and Kβ// emission lines ranges from 1.31 eV to 4.36 eV respectively. In the present work, it has been found that chemical shift in Kβ// X-ray emission lines were found to be larger than Kα and Kβ1,3 X-ray emission lines. To find the cause of chemical shift, various factors like effective charge, line intensity ratio, bond length and electro-negativity were calculated and correlated with the chemical shift.

Detection of metal stress in boreal forest species using the 0.67-micron chlorophyll absorption band

NASA Technical Reports Server (NTRS)

Singhroy, Vernon H.; Kruse, Fred A.

1991-01-01

Several recent studies have shown that a shift of the red-edge inflection near 0.70 micron in vegetation reflectance spectra is an indicator of metal stress, partially attributable to changes in chlorophyll concentration. This 'red-edge shift', however, is difficult to detect and has been reported both toward longer (red) and shorter (blue) wavelengths. Our work demonstrates that direct measurement of the depth and width of the chlorophyll absorption band at 0.67 micron using digital feature extraction and absorption band characterization procedures developed for the analysis of mineral spectra is a more consistent indicator of metal stress. Additionally, the magnitude of these parameters is generally greater than that of the red edge shift and thus should be more amenable to detection and mapping using field and aircraft spectrometers.

Synthesis and properties of Asante Calcium Red--a novel family of long excitation wavelength calcium indicators.

PubMed

Hyrc, Krzysztof L; Minta, Akwasi; Escamilla, P Rogelio; Chan, Patrick P L; Meshik, Xenia A; Goldberg, Mark P

2013-10-01

Although many synthetic calcium indicators are available, a search for compounds with improved characteristics continues. Here, we describe the synthesis and properties of Asante Calcium Red-1 (ACR-1) and its low affinity derivative (ACR-1-LA) created by linking BAPTA to seminaphthofluorescein. The indicators combine a visible light (450-540 nm) excitation with deep-red fluorescence (640 nm). Upon Ca2+ binding, the indicators raise their fluorescence with longer excitation wavelengths producing higher responses. Although the changes occur without any spectral shifts, it is possible to ratio Ca(2+)-dependent (640 nm) and quasi-independent (530 nm) emission when using visible (< 490 nm) or multiphoton (∼780 nm) excitation. Therefore, both probes can be used as single wavelength or, less dynamic, ratiometric indicators. Long indicator emission might allow easy [Ca2+]i measurement in GFP expressing cells. The indicators bind Ca2+ with either high (Kd = 0.49 ± 0.07 μM; ACR-1) or low affinity (Kd = 6.65 ± 0.13 μM; ACR-1-LA). Chelating Zn2+ (Kd = 0.38 ± 0.02 nM) or Mg2+ (Kd∼5mM) slightly raises and binding Co2+ quenches dye fluorescence. New indicators are somewhat pH-sensitive (pKa = 6.31 ± 0.07), but fairly resistant to bleaching. The probes are rather dim, which combined with low AM ester loading efficiency, might complicate in situ imaging. Despite potential drawbacks, ACR-1 and ACR-1-LA are promising new calcium indicators. Copyright © 2013 Elsevier Ltd. All rights reserved.

Synthesis and Properties of Asante Calcium Red –a Novel Family of Long Excitation Wavelength Calcium Indicators

PubMed Central

Hyrc, Krzysztof L.; Minta, Akwasi; Escamilla, P. Rogelio; Chan, Patrick P.L.; Meshik, Xenia A.; Goldberg, Mark P.

2013-01-01

Although many synthetic calcium indicators are available, a search for compounds with improved characteristics continues. Here, we describe the synthesis and properties of Asante Calcium Red-1 (ACR-1) and its low affinity derivative (ACR-1-LA) created by linking BAPTA to seminaphthofluorescein. The indicators combine a visible light (450–540 nm) excitation with deep-red fluorescence (640 nm). Upon Ca2+ binding, the indicators raise their fluorescence with longer excitation wavelengths producing higher responses. Although the changes occur without any spectral shifts, it is possible to ratio Ca2+-dependent (640 nm) and quasi-independent (530 nm) emission when using visible (<490 nm) or multiphoton (~780 nm) excitation. Therefore, both probes can be used as single wavelength or, less dynamic, ratiometric indicators. Long indicator emission might allow easy [Ca2+]i measurement in GFP expressing cells. The indicators bind Ca2+ with either high (Kd=0.49±0.07 μM; ACR-1) or low affinity (Kd=6.65±0.13 μM; ACR-1-LA). Chelating Zn2+ (Kd =0.38±0.02 nM) or Mg2+ (Kd ~5 mM) slightly raises and binding Co2+ quenches dye fluorescence. New indicators are somewhat pH-sensitive (pKa=6.31±0.07), but fairly resistant to bleaching. The probes are rather dim, which combined with low AM ester loading efficiency, might complicate in situ imaging. Despite potential drawbacks, ACR-1 and ACR-1-LA are promising new calcium indicators. PMID:24017967

Probing me Reverse Shock in an Oxygen-Rich Supernova Remnant

NASA Technical Reports Server (NTRS)

Gaetz, Terrance; Sonneborn, George (Technical Monitor)

2004-01-01

The aim of this project is to examine the O VI emission at three positions around the X- ray bright ring of the remnant in order to investigate the relation between the O VI emission, the X-ray O VII and O VIII emission, and the optical [OIII} emission, and how these vary around the rim of the remnant. All three pointings and the background pointing have now been observed; the archive notification for the most recent dataset was Oct 30, 2003. After reprocessing and screening, the net exposure time for the SE exposure is only 54 percent of the approved time (15 kilosec). for the SE exposure, the available statistics are not good enough for analysis. A request for reobservation to make up for the lost time in the SE pointing has been approved. Broad O VI 1032 and O VI 1038 emission is detected with velocity width of at least 800 km/s, and possibly exceeding 1000 km/s. The Flanagan et al. analysis of the Chandra grating data show bulk velocities in the X-ray gas of order +/- 1000 km/s. In the region of the FUSE E0lO2-SE pointing, the Chandra data indicate both blue-shifted and red-shifted emission. Analysis of the velocity structure of the O VI emission will provide additional constraints on the kinematics of the gas: is it emission from a tilted expanding barrel, or a more symmetric expansion? The O VI fluxes are also needed to assess whether the O VI is radiation from recombining O VII or instead fiom cooler gas ionizing toward O VII. The emission is faint, however, which complicates the analysis. Because the lines are so broad, absorption by intervening H2, CII, and foreground OVI must be considered. A number of stars in the SMC have been observed which provide information on foreground OVI absorption. The initial analyses have concentrated on the Li1F channel since the guidance is based on that channel. The Li2F channel is being examined exposure by exposure to see if any of the data can be used to improve the signal to noise in the Li1F data.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pletneva, Nadya V.; Pletnev, Vladimir Z.; Shemiakina, Irina I.

The wild type red fluorescent protein eqFP578 (from sea anemone Entacmaea quadricolor, {lambda}{sub ex} = 552 nm, {lambda}{sub em} = 578 nm) and its bright far-red fluorescent variant Katushka ({lambda}{sub ex} = 588 nm, {lambda}{sub em} = 635 nm) are characterized by the pronounced pH dependence of their fluorescence. The crystal structures of eqFP578f (eqFP578 with two point mutations improving the protein folding) and Katushka have been determined at the resolution ranging from 1.15 to 1.85 {angstrom} at two pH values, corresponding to low and high level of fluorescence. The observed extinguishing of fluorescence upon reducing pH in eqFP578f andmore » Katushka has been shown to be accompanied by the opposite trans-cis and cis-trans chromophore isomerization, respectively. Asn143, Ser158, His197 and Ser143, Leu174, and Arg197 have been shown to stabilize the respective trans and cis fluorescent states of the chromophores in eqFP578f and Katushka at higher pH. The cis state has been suggested as being primarily responsible for the observed far-red shift of the emission maximum of Katushka relative to that of eqFP578f.« less

Heat- and light-induced transformations of Yb trapping sites in an Ar matrix

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tao, L.-G.; Lambo, R., E-mail: lambo@mail.ustc.edu.cn; Zhou, X.-G.

2015-11-07

The low-lying electronic states of Yb isolated in a solid Ar matrix grown at 4.2 K are characterized through absorption and emission spectroscopy. Yb atoms are found to occupy three distinct thermally stable trapping sites labeled “red,” “blue,” and “violet” according to the relative positions of the absorption features they produce. Classical simulations of the site structure and relative stability broadly reproduced the experimentally observed matrix-induced frequency shifts and thus identified the red, blue, and violet sites as due to respective single substitutional (SS), tetravacancy (TV), and hexavacancy (HV) occupation. Prolonged excitation of the {sup 1}S → {sup 1}P transitionmore » was found to transfer the Yb population from HV sites into TV and SS sites. The process showed reversibility in that annealing to 24 K predominantly transferred the TV population back into HV sites. Population kinetics were used to deduce the effective rate parameters for the site transformation processes. Experimental observations indicate that the blue and violet sites lie close in energy, whereas the red one is much less stable. Classical simulations identify the blue site as the most stable one.« less

KINETICS OF LEAF TEMPERATURE FLUCTUATION AFFECT ISOPRENE EMISSION FROM RED OAK (QUERCUS RUBRA) LEAVES

EPA Science Inventory

Because the rate of isoprene (2-methyl-1,3-butadiene) emission from plants is highly temperature-dependent, we investigated the natural fluctuations on leaf temperature and the effects of rapid temperature change on isoprene emission of red oak (Quercus rubra L.) leaves at the to...

Evaluation of an Ultrafast Molecular Rotor, Auramine O, as a Fluorescent Amyloid Marker.

PubMed

Mudliar, Niyati H; Sadhu, Biswajit; Pettiwala, Aafrin M; Singh, Prabhat K

2016-10-13

Recently, Auramine O (AuO) has been projected as a fluorescent fibril sensor, and it has been claimed that AuO has an advantage over the most extensively utilized fibril marker, Thioflavin-T (ThT), owing to the presence of an additional large red-shifted emission band for AuO, which was observed exclusively for AuO in the presence of fibrillar media and not in protein or buffer media. As fibrils are very rich in β-sheet structure, a fibril sensor should be more specific toward the β-sheet structure so as to produce a large contrast between the fibril form and native protein form, for efficient detection and in vitro mechanistic studies of fibrillation. However, in this report, we show that AuO interacts significantly with the native form of bovine serum albumin (BSA), which is an all-α-helical protein and lacks the β-sheet structure, which are the hallmarks of a fibrillar structure. This strong interaction of AuO with the native form of BSA leads to a large emission enhancement of AuO for the native protein itself, and leads to a low contrast between the BSA protein and its fibrils. More importantly, the large red-shifted emission band of AuO, reported in the presence of human insulin fibrils, and which was projected as its major advantage over ThT, is not observed in the presence of BSA fibrils as well as fibrils from other proteins, such as lysozyme, human serum albumin, and β-lactoglobulin. Thus, our results provide information on the universal applicability of the distinctive and claimed-to-be-advantageous photophysical features reported for AuO in human insulin fibrils towards fibrils from other proteins. Time-resolved fluorescence measurements also support the proposition of a strong interaction of AuO with native BSA. Additionally, tryptophan emission of the protein has been explored to further elucidate the binding mechanism of AuO with native BSA. Evaluation of thermodynamic parameters revealed that the binding of AuO with native BSA involved positive enthalpy and entropy changes, suggesting dominant contributions from hydrophobic and electrostatic interactions toward the association of AuO with native BSA. Molecular docking calculations have been performed to identify the principal binding location of AuO in native BSA.

Tuning light emission of PbS nanocrystals from infrared to visible range by cation exchange

PubMed Central

Binetti, Enrico; Striccoli, Marinella; Sibillano, Teresa; Giannini, Cinzia; Brescia, Rosaria; Falqui, Andrea; Comparelli, Roberto; Corricelli, Michela; Tommasi, Raffaele; Agostiano, Angela; Curri, M Lucia

2015-01-01

Colloidal semiconductor nanocrystals, with intense and sharp-line emission between red and near-infrared spectral regions, are of great interest for optoelectronic and bio-imaging applications. The growth of an inorganic passivation layer on nanocrystal surfaces is a common strategy to improve their chemical and optical stability and their photoluminescence quantum yield. In particular, cation exchange is a suitable approach for shell growth at the expense of the nanocrystal core size. Here, the cation exchange process is used to promote the formation of a CdS passivation layer on the surface of very small PbS nanocrystals (2.3 nm in diameter), blue shifting their optical spectra and yielding luminescent and stable nanostructures emitting in the range of 700–850 nm. Structural, morphological and compositional investigation confirms the nanocrystal size contraction after the cation-exchange process, while the PbS rock-salt crystalline phase is retained. Absorption and photoluminescence spectroscopy demonstrate the growth of a passivation layer with a decrease of the PbS core size, as inferred by the blue-shift of the excitonic peaks. The surface passivation strongly increases the photoluminescence intensity and the excited state lifetime. In addition, the nanocrystals reveal increased stability against oxidation over time. Thanks to their absorption and emission spectral range and the slow recombination dynamics, such highly luminescent nano-objects can find interesting applications in sensitized photovoltaic cells and light-emitting devices. PMID:27877842

Microhydration and the Enhanced Acidity of Free Radicals.

PubMed

Walton, John C

2018-02-14

Recent theoretical research employing a continuum solvent model predicted that radical centers would enhance the acidity (RED-shift) of certain proton-donor molecules. Microhydration studies employing a DFT method are reported here with the aim of establishing the effect of the solvent micro-structure on the acidity of radicals with and without RED-shifts. Microhydration cluster structures were obtained for carboxyl, carboxy-ethynyl, carboxy-methyl, and hydroperoxyl radicals. The numbers of water molecules needed to induce spontaneous ionization were determined. The hydration clusters formed primarily round the CO₂ units of the carboxylate-containing radicals. Only 4 or 5 water molecules were needed to induce ionization of carboxyl and carboxy-ethynyl radicals, thus corroborating their large RED-shifts.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kadria-Vili, Yara; Bachilo, Sergei M.; Blackburn, Jeffrey L.

Photoluminescence spectra of single-walled carbon nanotubes (SWCNTs) have been recorded and analyzed for selected individual nanotubes and structurally sorted bulk samples to clarify the nature of secondary emission features. Room temperature spectra show, in addition to the main peak arising from the E 11 bright exciton, three features at lower frequency, which are identified here (in descending order of energy difference from E 11 emission) as G 1, X 1, and Y 1. The weakest (G 1) is interpreted as a vibrational satellite of E 11 involving excitation of the ~1600 cm -1 G mode. The X 1 feature, althoughmore » more intense than G 1, has a peak amplitude only ~3% of E 11. X 1 emission was found to be polarized parallel to E 11 and to be separated from that peak by 1068 cm -1 in SWCNTs with natural isotopic abundance. The separation remained unchanged for several ( n,m) species, different nanotube environments, and various levels of induced axial strain. In 13C SWCNTs, the spectral separation decreased to 1023 cm -1. The measured isotopic shift points to a phonon-assisted transition that excites the D vibration. This supports prior interpretations of the X 1 band as emission from the dark K-momentum exciton, whose energy we find to be ~230 cm -1 above E 11. The remaining sideband, Y 1, is red-shifted ~300 cm -1 from E 11 and varies in relative intensity among and within individual SWCNTs. We assign it as defect-induced emission, either from an extrinsic state or from a brightened triplet state. In contrast to single-nanotube spectra, bulk samples show asymmetric zero-phonon E 11 peaks, with widths inversely related to SWCNT diameter. As a result, an empirical expression for this dependence is presented to aid the simulation of overlapped emission spectra during quantitative fluorimetric analysis of bulk SWCNT samples.« less

Photoluminescence side band spectroscopy of individual single-walled carbon nanotubes

DOE PAGES

Kadria-Vili, Yara; Bachilo, Sergei M.; Blackburn, Jeffrey L.; ...

2016-09-27

Photoluminescence spectra of single-walled carbon nanotubes (SWCNTs) have been recorded and analyzed for selected individual nanotubes and structurally sorted bulk samples to clarify the nature of secondary emission features. Room temperature spectra show, in addition to the main peak arising from the E 11 bright exciton, three features at lower frequency, which are identified here (in descending order of energy difference from E 11 emission) as G 1, X 1, and Y 1. The weakest (G 1) is interpreted as a vibrational satellite of E 11 involving excitation of the ~1600 cm -1 G mode. The X 1 feature, althoughmore » more intense than G 1, has a peak amplitude only ~3% of E 11. X 1 emission was found to be polarized parallel to E 11 and to be separated from that peak by 1068 cm -1 in SWCNTs with natural isotopic abundance. The separation remained unchanged for several ( n,m) species, different nanotube environments, and various levels of induced axial strain. In 13C SWCNTs, the spectral separation decreased to 1023 cm -1. The measured isotopic shift points to a phonon-assisted transition that excites the D vibration. This supports prior interpretations of the X 1 band as emission from the dark K-momentum exciton, whose energy we find to be ~230 cm -1 above E 11. The remaining sideband, Y 1, is red-shifted ~300 cm -1 from E 11 and varies in relative intensity among and within individual SWCNTs. We assign it as defect-induced emission, either from an extrinsic state or from a brightened triplet state. In contrast to single-nanotube spectra, bulk samples show asymmetric zero-phonon E 11 peaks, with widths inversely related to SWCNT diameter. As a result, an empirical expression for this dependence is presented to aid the simulation of overlapped emission spectra during quantitative fluorimetric analysis of bulk SWCNT samples.« less

Investigation of intrinsic and extrinsic defects effective role on producing intense red emission in ZnO:Eu nanostructures

DOE Office of Scientific and Technical Information (OSTI.GOV)

Najafi, Mehrdad, E-mail: najafi@shahroodut.ac.ir; Haratizadeh, Hamid

2015-05-15

Highlights: • Effective role of defects on producing red emission at indirect excitation. • V{sub Zn} and V{sub O} defects have important role on energy transfer. • Mg related defects and Zn{sub i} defects were responsible for blue emission. • Extrinsic and intrinsic defects mediated energy transfer to sensitize Eu{sup 3+} ions. • Decrease of red emission because of diminishing in oxygen vacancy. - Abstract: Europium doped ZnO nanorads and nanosheets were synthesized by hydrothermal method. Effects of Mg doping, morphology and annealing in oxygen ambient on structural and optical properties of ZnO nanostructures were investigated using X-ray diffraction (XRD),more » particle size analysis (PSA), thermo gravimetric analysis (TGA), differential thermal analysis (DTA), differential thermo gravimetry (DTG), scanning electron microscopy (SEM) and photoluminescence spectroscopy (PL). This study recommends that both of intrinsic and extrinsic defects facilitate energy transfer (ET) from the ZnO host to Eu{sup 3+} ions and consequently have efficient role on producing intense red emission at indirect excitation. The results also showed that annealing process improved the crystal structure of ZnO nanosheets due to decrease of surface defects; however decreased ET and red emission because of diminishing in oxygen vacancy. In addition in ZnO nanorods sample with more surface area in comparison with ZnO nanosheets sample deep level emissions are enhanced.« less

Second-Chance Forward Isomerization Dynamics of the Red/Green Cyanobacteriochrome NpR6012g4 from Nostoc punctiforme

PubMed Central

Kim, Peter W.; Freer, Lucy H.; Rockwell, Nathan C.; Martin, Shelley S.; Lagarias, J. Clark; Larsen, Delmar S.

2011-01-01

The primary ultrafast Z-to-E isomerization photodynamics of the phytochrome-related cyanobacteriochrome (CBCR) NpR6012g4 from N. punctiforme were studied by transient absorption pump-dump-probe spectroscopy. A 2-ps dump pulse resonant with the stimulated emission band depleted 21 % of the excited-state population, while the initial photoproduct Lumi-R was depleted by only 11 %. We observe a red-shifted ground-state intermediate (GSI) that we assign to a metastable state that failed to fully isomerize. Multi-component global analysis implicates the generation of additional Lumi-R from GSI via crossing over the ground-state thermal barrier for full isomerization, explaining the discrepancy of excited-state and Lumi-R depletion by the dump pulse. This second-chance ground-state dynamics provides a plausible explanation for the unusually high quantum yield of 40 % for the primary isomerization step in the forward reaction of NpR6012g4. PMID:22107125

Second-chance forward isomerization dynamics of the red/green cyanobacteriochrome NpR6012g4 from Nostoc punctiforme.

PubMed

Kim, Peter W; Freer, Lucy H; Rockwell, Nathan C; Martin, Shelley S; Lagarias, J Clark; Larsen, Delmar S

2012-01-11

The primary ultrafast Z-to-E isomerization photodynamics of the phytochrome-related cyanobacteriochrome NpR6012g4 from Nostoc punctiforme was studied by transient absorption pump-dump-probe spectroscopy. A 2 ps dump pulse resonant with the stimulated emission band depleted 21% of the excited-state population, while the initial photoproduct Lumi-R was depleted by only 11%. We observed a red-shifted ground-state intermediate (GSI) that we assign to a metastable state that failed to isomerize fully. Multicomponent global analysis implicates the generation of additional Lumi-R from the GSI via crossing over the ground-state thermal barrier for full isomerization, explaining the discrepancy between excited-state and Lumi-R depletion by the dump pulse. This second-chance ground-state dynamics provides a plausible explanation for the unusually high quantum yield of 40% for the primary isomerization step in the forward reaction of NpR6012g4. © 2011 American Chemical Society

Deep-Red Fluorescent Gold Nanoclusters for Nucleoli Staining: Real-Time Monitoring of the Nucleolar Dynamics in Reverse Transformation of Malignant Cells.

PubMed

Wang, Xiaojuan; Wang, Yanan; He, Hua; Ma, Xiqi; Chen, Qi; Zhang, Shuai; Ge, Baosheng; Wang, Shengjie; Nau, Werner M; Huang, Fang

2017-05-31

Nucleoli are important subnuclear structures inside cells. We report novel fluorescent gold nanoclusters (K-AuNCs) that are able to stain the nucleoli selectively and make it possible to explore the nucleolar morphology with fluorescence imaging technique. This novel probe is prepared through an easy synthesis method by employing a tripeptide (Lys-Cys-Lys) as the surface ligand. The properties, including deep-red fluorescence emission (680 nm), large Stocks shift, broad excitation band, low cytotoxicity, and good photostability, endow this probe with potential for bioanalytical applications. Because of their small size and their positively charged surface, K-AuNCs are able to accumulate efficiently at the nucleolar regions and provide precise morphological information. K-AuNCs are also used to monitor the nucleolar dynamics along the reverse-transformation process of malignant cells, induced by the agonist of protein A, 8-chloro-cyclic adenosine monophosphate. This gives a novel approach for investigating the working mechanism of antitumor drugs.

A coumarin-derived Cu2 +-fluorescent chemosensor and its direct application in aqueous media

NASA Astrophysics Data System (ADS)

Mergu, Naveen; Kim, Myeongjin; Son, Young-A.

2018-01-01

A novel coumarin-based receptor bearing a benzohydrazide (FCBH) was developed as a fluorescent chemosensor with high selectivity toward Cu2 +. The sensor was successfully applied to the monitoring of Cu2 + in aqueous solution. After the addition of Cu2 + to FCBH, the color of the solution changed from greenish-yellow to red, and the absorption band at 457 nm red-shifted to 517 nm. The fluorescent green color of FCBH disappeared and the fluorescence emission was completely quenched in the presence of Cu2 +. Upon the addition of Cu2 +, deprotonation of FCBH occurred, and a 1:1 metal-ligand complex formed. DFT theoretical investigation was carried out to understand the behavior of the sensing probe toward Cu2 +. Additionally, the quenched fluorescence of the FCBH-Cu2 + complex was restored upon the addition of CN- ions. The possible sensing mechanism of FCBH toward Cu2 + was derived from experimental and theoretical examinations.

Jet-Cooled Chlorofluorobenzyl Radicals: Spectroscopy and Mechanism

NASA Astrophysics Data System (ADS)

Yoon, Young; Lee, Sang

2016-06-01

Whereas the benzyl radical, a prototypic aromatic free radical, has been the subject of numerous spectroscopic studies, halo-substituted benzyl radicals have received less attention, due to the difficulties associated with production of radicals from precursors. In particular, chloro-substituted benzyl radicals have been much less studied because of the weak visible emission intensity and weak C-Cl bond dissociation energy. The jet-cooled chlorofluorobenzyl radicals were generated in a technique of corona excited supersonic jet expansion using a pinhole-type glass nozzle for the vibronic assignments and measurements of electronic energies of the D_1 → D_0 transition. The 2,4-,2.5-, and 2.6- chlorofluorobenzyl radicals were generated by corona discharge of corresponding precursors, chlorofluorotoluenes seeded in a large amount of helium carrier gas. The vibronic emission spectra were recorded with a long-path monochromator in the visible region. The emission spectra show the vibronic bands originating from two types of benzyl-type radicals, chlorofluorobenzyl and fluorobenzyl benzyl radicals, in which fluorobenzyl radicals were obtained by displacement of Cl by H produced by dissociation of methyl C-H bond. From the analysis of the spectra observed, we could determine the electronic energies in D_1 → D_0 transition and vibrational mode frequencies at the D_0 state of chlorofluorobenzyl radicals, which show the origin band of the electronic transition to be shifted to red region, comparing with the parental benzyl radical. From the quantitative analysis of the red-shift, it has been found that the additivity rule can be applied to dihalo-substituted benzyl radicals. In this presentation, the dissociation process of precursors in corona discharge is discussed in terms of bond dissociation energy as well as the spectroscopic analysis of the radicals. C. S. Huh, Y. W. Yoon, and S. K. Lee, J. Chem. Phys. 136, 174306 (2012). Y. W. Huh, S. Y. Chae, and S. K. Lee, Chem. Phys. Lett. 608, 6 (2014). Y. W. Yoon, S. Y. Chae, M. Lim, and S. K. Lee, Chem. Phys. Lett. 637, 148 (2015).

A pyrene-benzthiazolium conjugate portraying aggregation induced emission, a ratiometric detection and live cell visualization of HSO3(.).

PubMed

Diwan, Uzra; Kumar, Virendra; Mishra, Rakesh K; Rana, Nishant Kumar; Koch, Biplob; Singh, Manish Kumar; Upadhyay, K K

2016-07-27

The present study deals with the photophysical property of a pyrene-benzthiazolium conjugate R1, as a strong intramolecular charge transfer (ICT) probe exhibiting long wavelength emission in the red region. Unlike traditional planar polyaromatic hydrocarbons whose aggregation generally quenches the light emission, the pyrene based R1 was found to display aggregation-induced emission (AIE) property along with simultaneous increase in its quantum yield upon increasing the water content of the medium. The R1 exhibits high specificity towards HSO3(-)/SO3(2-) by interrupting its own ICT producing there upon a large ratiometric blue shift of ∼220 nm in its emission spectrum. The lowest detection limit for the above measurement was found to be 8.90 × 10(-8) M. The fluorescent detection of HSO3(-) was also demonstrated excellently by test paper strip and silica coated TLC plate incorporating R1. The live cell imaging of HSO3(─) through R1 in HeLa cells was studied using fluorescence microscopic studies. The particle size and morphological features of R1 and R1-HSO3(-) aggregates in aqueous solution were characterized by DLS along with SEM analysis. Copyright © 2016 Elsevier B.V. All rights reserved.

Photophysical parameters and laser performance of 3-(4‧-dimethylaminophenyl)-1-(2-furanyl)prop-2-en-1-one (DMAFP): A new laser dye

NASA Astrophysics Data System (ADS)

El-Daly, S. A.; Gaber, M.; El-Sayed, Y. S.

2009-09-01

The spectral properties such as singlet absorption, molar absorptivity, emission spectra, fluorescence quantum yield and excited state lifetime of 3-(4'-dimethylaminophenyl)-1-(2-furanyl)prop-2-en-1-one (DMAFP) have been determined in different solvents. DMAFP dye exhibits a large red shift in both electronic absorption and emission spectra as the solvent polarity increases, indicating a large change in the dipole moment of molecules upon excitation. A crystalline solid of DMAFP gives an excimer like emission at 566 nm due to the excitation of molecular aggregates. This is expected from the idealized crystal structure of the dye that belongs to the B-type class of Steven's classification. The ground and excited state protonation constants of DMAFP are calculated and amounted to 1.71 and 8.3, respectively. DMAFP acts as a good laser dye upon pumping with nitrogen laser ( λex=337.1 nm) in chloroform, methylene chloride and dioxane and gives laser emission in the range 460-590 nm. The laser parameters such as the tuning range, gain coefficient ( α), emission cross section ( σ e) and half-life energy ( E1/2) are calculated. The photoreactivity and net photochemical quantum yield of DMAFP in chloromethane solvents are also studied.

Adding worms during composting of organic waste with red mud and fly ash reduces CO2 emissions and increases plant available nutrient contents.

PubMed

Barthod, J; Rumpel, C; Calabi-Floody, M; Mora, M-L; Bolan, N S; Dignac, M-F

2018-09-15

Alkaline industrial wastes such as red mud and fly ash are produced in large quantities. They may be recycled as bulking agent during composting and vermicomposting, converting organic waste into soil amendments or plant growth media. The aim of this study was to assess the microbial parameters, greenhouse gas emissions and nutrient availability during composting and vermicomposting of household waste with red mud and fly ash 15% (dry weight). CO 2 , CH 4 and N 2 O emissions were monitored during 6 months in controlled laboratory conditions and microbial biomass and phospholipid acids, N and P availability were analysed in the end-products. Higher CO 2 emissions were observed during vermicomposting compared to composting. These emissions were decreased by red mud addition, while fly ash had no effect. Nitrate (NO 3 -N) content of the end-products were more affected by worms than by alkaline materials, while higher ammonium (NH 4 -N) contents were recorded for composts than vermicomposts. Red mud vermicompost showed higher soluble P proportion than red mud compost, suggesting that worm presence can counterbalance P adsorption to the inorganic matrix. Final composts produced with red mud showed no harmful heavy metal concentrations. Adding worms during composting thus improved the product nutrient availability and did not increase metal toxicity. From a practical point of view, this study suggests that for carbon stabilisation and end-product quality, the addition of red mud during composting should be accompanied by worm addition to counterbalance negative effects on nutrient availability. Copyright © 2018. Published by Elsevier Ltd.

Gravitational red shift tests and a spectroscopy in Japan

NASA Astrophysics Data System (ADS)

Yokoo, Hiromitsu

Japanese astronomers and physicians tried to test the Einstein theory by gravitational red shift tests at 1920's. Spectroscopists in Japan contributed to Stark broadening of spectrum lines. Rikiti Kinoshita (1877 - 1935) probably started experiments according to Voigt's prediction earlier than Stark. Tokyo Astronomical Observatory constructed and used another Einstein Tower in Mitaka.

Near-infrared studies of glucose and sucrose in aqueous solutions: water displacement effect and red shift in water absorption from water-solute interaction.

PubMed

Jung, Youngeui; Hwang, Jungseek

2013-02-01

We used near infrared spectroscopy to obtain concentration dependent glucose absorption spectra in aqueous solutions in the near-infrared range (3800-7500 cm(-1)). Here we introduce a new method to obtain reliable glucose absorption bands from aqueous glucose solutions without measuring the water displacement coefficients of glucose separately. Additionally, we were able to extract the water displacement coefficients of glucose, and this may offer a new general method using spectroscopy techniques applicable to other water-soluble materials. We also observed red shifts in the absorption bands of water in the hydration shell around solute molecules, which comes from the contribution of the interacting water molecules around the glucose molecules in solutions. The intensity of the red shift gets larger as the concentration increases, which indicates that as the concentration increases more water molecules are involved in the interaction. However, the red shift in frequency does not seem to depend significantly on the concentration. We also performed the same measurements and analysis with sucrose instead of glucose as solute and compared.

Role of the oxyallyl substructure in the near infrared (NIR) absorption in symmetrical dye derivatives: A computational study.

PubMed

Prabhakar, Ch; Chaitanya, G Krishna; Sitha, Sanyasi; Bhanuprakash, K; Rao, V Jayathirtha

2005-03-24

It is well-known from experimental studies that the oxyallyl-substructure-based squarylium and croconium dyes absorb in the NIR region of the spectrum. Recently, another dye has been reported (J. Am. Chem. Soc. 2003, 125, 348) which contains the same basic chromophore, but the absorption is red-shifted by at least 300 nm compared to the former dyes and is observed near 1100 nm. To analyze the reasons behind the large red shift, in this work we have carried out symmetry-adapted cluster-configuration interaction (SAC-CI) studies on some of these NIR dyes which contain the oxyallyl substructure. From this study, contrary to the earlier reports, it is seen that the donor groups do not seem to play a major role in the red-shift of the absorption. On the other hand, on the basis of the results of the high-level calculations carried out here and using qualitative molecular orbital theory, it is observed that the orbital interactions play a key role in the red shift. Finally, design principles for the oxyallyl-substructure-based NIR dyes are suggested.

Structural and photophysical properties of (2E)-3-[4-(dimethylamino) phenyl]-1-(naphthalen-1-yl) prop-2-en-1-one (DPNP) in different media.

PubMed

Pannipara, Mehboobali; Asiri, Abdullah M; Alamry, Khalid A; Salem, Ibrahim A; El-Daly, Samy A

2015-01-01

The spectral and photophysical properties of a new chalcone derivative (2E)-3-[4-(dimethylamino) phenyl]-1-(naphthalen-1-yl) prop-2-en-1-one (DPNP) containing donor-acceptor group has been synthesized and characterized on the basis of the spectral (IR, (1)HNMR & (13)C NMR) and X- ray crystallographic data. The effect of solvents on photophysical parameters such as singlet absorption, molar absorptivity, oscillator strength, dipole moment, fluorescence spectra, and fluorescence quantum yield of DPNP have been investigated comprehensively. Significant red shift was observed in the emission spectrum of DPNP compared to the absorption spectrum upon increasing the solvent polarity, indicating a higher dipole moment in the excited state than in the ground state. The difference between the excited and ground state dipole moments (Δμ) were obtained from Lippert-Mataga and Reichardts correlations by means of solvatochromic shift method. The effects of medium acidity on the electronic absorption and emission spectra of DPNP were studied. The interaction of DPNP with colloidal silver nanoparticles (AgNPs) was also studied in ethanol and ethylene glycol using steady state fluorescence quenching measurements. The fluorescence quenching data reveal that dynamic quenching and energy transfer play a major role in the fluorescence quenching of DPNP by Ag NPs.

Fermi-edge superfluorescence from a quantum-degenerate electron-hole gas

NASA Astrophysics Data System (ADS)

Kim, Ji-Hee; , G. Timothy Noe, II; McGill, Stephen A.; Wang, Yongrui; Wójcik, Aleksander K.; Belyanin, Alexey A.; Kono, Junichiro

2013-11-01

Nonequilibrium can be a source of order. This rather counterintuitive statement has been proven to be true through a variety of fluctuation-driven, self-organization behaviors exhibited by out-of-equilibrium, many-body systems in nature (physical, chemical, and biological), resulting in the spontaneous appearance of macroscopic coherence. Here, we report on the observation of spontaneous bursts of coherent radiation from a quantum-degenerate gas of nonequilibrium electron-hole pairs in semiconductor quantum wells. Unlike typical spontaneous emission from semiconductors, which occurs at the band edge, the observed emission occurs at the quasi-Fermi edge of the carrier distribution. As the carriers are consumed by recombination, the quasi-Fermi energy goes down toward the band edge, and we observe a continuously red-shifting streak. We interpret this emission as cooperative spontaneous recombination of electron-hole pairs, or superfluorescence (SF), which is enhanced by Coulomb interactions near the Fermi edge. This novel many-body enhancement allows the magnitude of the spontaneously developed macroscopic polarization to exceed the maximum value for ordinary SF, making electron-hole SF even more ``super'' than atomic SF.

Investigation on the photophysical properties of tungsten trioxide and tungstate based nanocomposites

NASA Astrophysics Data System (ADS)

Palanisamy, G.; Pazhanivel, T.

2018-04-01

Tungsten trioxide (WO3), Metal tungstates (SrWO4, Cr2WO6), WO3/SrWO4 and WO3/Cr2WO6 nanocomposites were successfully prepared by microwave irradiation method at relatively low temperature (500 °C). The synthesized samples were subjected to different investigation techniques, to know the materials physical and chemical properties. The structural and phase change formation of nanoparticles were investigated through XRD analysis. It shows that, the nanoparticles have highly crystalline nature. The shape and composition of the prepared nanoparticles were investigated through SEM and EDAX analysis. The optical properties of the synthesized samples were verified by Ultraviolet-diffuse reflectance spectroscopy and photoluminescence spectrometer. The emission intensity maximum of WO3 nanoparticle was red shifted when compared to composites. It may be due to the effect of delocalized electrons in the parent material. Simultaneously, the emission intensity was decreased because of trap states occurred on the surface of the composite nanoparticles. The photoluminescence spectra of the synthesized samples exhibit different emission (violet and blue) behavior. Hence, it may be useful for light emitting diode (LED) applications.

[Properties of synthesized CdS nanoparticles by reverse micelle method].

PubMed

Li, Heng-Da; Wang, Qing-Wei; Zhai, Hong-Ju; Li, Wen-Lian

2008-07-01

Micelle system with reverse phase (water/CTAB/n-hexyl alcohol/n-heptane) is a weenie liquid-globelet of surface active agent molecule which can be stably and uniformly dispersed in continuous oil medium. The micelle system with reverse phase can work as a "micro-reactor" to synthesize CdS nano-particle with excellent performance. In the present article considering the effects of W value (W= [water]/[surface agent]) of the micelle system with reverse phase, we observed that the ratio of [Cd2+] and [S2-] ions to the original concentrations of the Cd2+ and S2- ions can affect the luminescent properties of CdS nano-particle. Using regurgitant treatment process the surface of CdS nano-particle can be modified, and as a result the defect emission was reduced and even disappeared, but exciton emissions markedly increased. On the other hand, a red-shift of the exciton emission peak with the increase in the particle size was observed, indicating considerable quantum confinement effect. A maximum quantum efficiency of 11% for the synthesized CdS nano-material was achieved.

A novel fluorescence "turn-on" sensor based on a photochromic diarylethene for the selective detection of Al(III).

PubMed

Wang, Niansheng; Wang, Renjie; Tu, Yayi; Pu, Shouzhi; Liu, Gang

2018-05-05

A novel photochromic diarylethene with a triazole-containing 2-(2'-phenoxymethyl)-benzothiazole group has been synthesized via "click" reaction. The diarylethene exhibited good photochromism and photoswitchable fluorescence. Its fluorescence emission intensity was enhanced 7-fold by acids, accompanied by the red-shift of emission peak from 526nm to 566nm and the concomitant color change from dark to bright flavogreen. The diarylethene selectively formed a 1:1 metal complex with Al 3+ , resulting in a "turn-on" fluorescence signal. The complexation - reaction between Al 3+ and the diarylethene is reversible with the binding constant of 2.73×10 3 Lmol -1 . The limit of detection (LOD) of Al 3+ was determined to be 5.94×10 -8 molL -1 . Based on this unimolecular platform, a logic circuit was fabricated using the fluorescence emission intensity at 572nm as the output and the combined stimuli of Al 3+ /EDTA and UV/Vis as the inputs. Copyright © 2018 Elsevier B.V. All rights reserved.

Redox-responsive nanoparticles with Aggregation-Induced Emission (AIE) characteristic for fluorescence imaging.

PubMed

Cheng, Weiren; Wang, Guan; Pan, Xiaoyong; Zhang, Yong; Tang, Ben Zhong; Liu, Ye

2014-08-01

The redox environment between intracellular compartments and extracellular matrix is significantly different, and the cellular redox homeostasis determines many physiological functions. Here, redox-responsive nanoparticles with aggregation-induced emission (AIE) characteristic for fluorescence imaging are developed by encapsulation of fluorophore with redox "turn-on" AIE characteristic, TPE-MI, into the micelles of poly(ethylene glycol) (PEG)- and cholesterol (CE)-conjugated disulfide containing poly(amido amine)s. The redox-responsive fluorescence profiles of the nanoparticles are investigated after reaction with glutathione (GSH). The encapsulation of TPE-MI in micelles leads to a higher efficiency and red shift in emission, and the fluorescence intensity of the nanoparticles increases with the concentration of GSH. Confocal microscopy imaging shows that the nanoparticles can provide obvious contrast between the intracellular compartments and the extracellular matrix in MCF-7 and HepG2 cells. So the nanoparticles with PEG shells and low cytotoxicity are promising to provide fluorescence bioimaging with a high contrast and for differentiation of cellular redox environment. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Photoinduced intramolecular charge transfer and photophysical characteristics of (2Z)-3-[4-(dimethylamino) phenyl]-2-(2-methylphenyl) prop-2-ene-nitrile (DPM) in different media

NASA Astrophysics Data System (ADS)

Asiri, Abdullah M.; El-Daly, Samy A.; Alamry, Khalid A.; Arshad, Muhammad Nadeem; Pannipara, Mehboobali

2015-10-01

A new fluorophore, (2Z)-3-[4-(dimethylamino) phenyl]-2-(2-methylphenyl) prop-2-ene-nitrile (DPM), was synthesized by knoevenagel condensation of 4-(dimethylamino) benzaldehyde and 2-methylbenzyl cyanide in ethanol using NaOH as base. The electronic absorption and emission characteristic of DPM was studied in different solvents. The X-ray crystallographic structure of DPM was also investigated. A crystalline solid of DPM gives a strong green emission at about 533 nm; these phenomena are important for the application of DPM dye in organic photo emitting diode. DPM exhibits a red shift in its emission spectrum as solvent polarity increases, indicating a large change in the dipole moment of dye molecule upon excitation due to intramolecular charge transfer in excited DPM*. The fluorescence quantum yield depends strongly on the properties of the solvents, which was attributed to positive and negative solvatokinetic effects. The DPM dye displays solubilization in cationic (CTAB) micelle and could be used as a probe to determine the critical micelle concentration (CMC) of CTAB.

[Luminescence properties of white LED blue light conversion materials].

PubMed

Hao, Hai-tao; Zhou, He-feng; Liang, Jian; Liu, Xu-guang; Xu, Bing-she

2007-02-01

Using rare earth oxides as raw materials, yttrium aluminum garnets activated by cerium and gadolinium ions were prepared by high energy ball milling and solid-state reaction at 1300 degrees C. The crystal structures of the products were studied by XRD, and the luminescence characteristics of Ce ion and the influence of Gd ion were studied by emission and excitation spectra. The results indicated that the products were yttrium aluminum garnet crystals of cubic system, and they were excited by blue light chips effectively. The emission peak of phosphors could change among 530-560 nm by adjusting the mole density of doping ions. The red shift of emission spectra could be interpreted with the configuration coordination figure. White LEDs were fabricated by phosphor conversion. When electric current is 20 mA, and the working voltage is 3.5 V, the white light LED chromaticity coordinates are x=0.310 and y=0.323, the lumen efficiency is 26.131 m x W(-1), the color rendering index is 81.8, and the color temperature is 6605 K.

High efficient white organic light-emitting diodes with single emissive layer using phosphorescent red, green, and blue dopants

NASA Astrophysics Data System (ADS)

Kim, You-Hyun; Wai Cheah, Kok; Young Kim, Woo

2013-07-01

Phosphorescent white organic light-emitting diodes (PHWOLEDs) with single emissive layer were fabricated by co-doping phosphorescent blue, green, and red emitters with different concentrations. WOLEDs using Ir(piq)3 and Ir(ppy)3 as red and green dopants along with 8% of Firpic as blue dopant with host materials of 4CzPBP in the emissive layer were compared under various doping ratio between Ir(piq)3 and Ir(ppy)3. Triplet-triplet Dexter energy transfer in single emissive PHWOLEDs including three primary colors was saturated from higher triplet energy levels to lower triplet energy levels directly.

Red electroluminescence and photoluminescence properties of new porphyrin compounds

NASA Astrophysics Data System (ADS)

Zhang, X. H.; Xie, Z. Y.; Wu, F. P.; Zhou, L. L.; Wong, O. Y.; Lee, C. S.; Kwong, H. L.; Lee, S. T.; Wu, S. K.

2003-12-01

Three new porphyrin compounds with saturated red emission were synthesized and their photoluminescence and electroluminescence were studied. The emission of the new dopants peaked at about 635-655 nm and the half-width of the emission peaks was very narrow (below 30 nm). Of the three porphyrin compounds, the one (TBDPP) with the smallest conjugation system had the highest fluorescent quantum yield of 21% in solution. Organic light-emitting diodes using TBDPP as a dopant showed saturated red emission (CIE coordinates of x=0.69, y=0.29) with a luminance of 150 cd/m 2 at a driving voltage of 22 V.

The interacting winds of Eta Carinae: Observed forbidden line changes and the Forbidden Blue(-Shifted) Crab

NASA Astrophysics Data System (ADS)

Gull, Theodore R.; Madura, Thomas; Corcoran, Michael F.; Teodoro, Mairan; Richardson, Noel; Hamaguchi, Kenji; Groh, Jose H.; Hillier, Desmond John; Damineli, Augusto; Weigelt, Gerd

2015-01-01

The massive binary, Eta Carinae (EC), produces such massive winds that strong forbidden line emission of singly- and doubly-ionized iron traces wind-wind interactions from the current cycle plus fossil interactions from one, two and three 5.54-year cycles ago.With an eccentricity of >0.9, the >90 solar mass primary (EC-A) and >30 solar mass secondary (EC-B) approach to within 1.5 AU during periastron and recede to nearly 30 AU across apastron. The wind-wind structures move outward driven by the 420 km/s primary wind interacting with the ~3000 km/s secondary wind yielding partially-accelerated compressed primary wind shells that are excited by mid-UV from EC-A and in limited lines of sight, FUV from EC-B.These structures are spectroscopically and spatially resolved by HST's Space Telescope Imaging Spectrograph. At critical binary phases, we have mapped the central 2'x2' region in the light of [Fe III] and [Fe II] with spatial resolution of 0.12' and velocity resolution of 40 km/s.1) The bulk of forbidden emission originates from the large cavity northwest of EC and is due to ionization of massive ejecta from the 1840s and 1890s eruptions. The brightest clumps are the Weigelt Blobs C and D, but there are additionally multiple, fainter emission clumps. Weigelt B appears to have faded.2) Three concentric, red-shifted [FeII] arcs expand at ~470 km/s excited by mid-UV of EC-A.3) The structure of primarily blue-shifted [Fe III] emission resembles a Maryland Blue Crab. The claws appear at the early stages of the high-excitation recovery from the periastron passage, expand at radial velocities exceeding the primary wind terminal velocity, 420 km/s and fade as the binary system approaches periastron with the primary wind enveloping the FUV radiation from EC-B.4) All [Fe III] emission faded by late June 2014 and disappeared by August 2, 2014, the beginning of periastron passage.Comparisons to HST/STIS observations between 1998 to 2004.3 indicate long-term fading of [Fe II]. Likewise, Na D emission has faded. 3D hydro/radiative models suggest a small decrease (< factor of 2) in primary mass loss rate to be the cause.

Fluorescence studies on the interaction of choline-binding domain B of the major bovine seminal plasma protein, PDC-109 with phospholipid membranes.

PubMed

Damai, Rajani S; Anbazhagan, V; Rao, K Babu; Swamy, Musti J

2009-12-01

The microenvironment and accessibility of the tryptophan residues in domain B of PDC-109 (PDC-109/B) in the native state and upon ligand binding have been investigated by fluorescence quenching, time-resolved fluorescence and red-edge excitation shift (REES) studies. The increase in the intrinsic fluorescence emission intensity of PDC-109/B upon binding to lysophosphatidylcholine (Lyso-PC) micelles and dimyristoylphosphatidylcholine (DMPC) membranes was considerably less as compared to that observed with the whole PDC-109 protein. The degree of quenching achieved by different quenchers with PDC-109/B bound to Lyso-PC and DMPC membranes was significantly higher as compared to the full PDC-109 protein, indicating that membrane binding afforded considerably lesser protection to the tryptophan residues of domain B as compared to those in the full PDC-109 protein. Finally, changes in red-edge excitation shift (REES) seen with PDC-109/B upon binding to DMPC membranes and Lyso-PC micelles were smaller that the corresponding changes in the REES values observed for the full PDC-109. These results, taken together suggest that intact PDC-109 penetrates deeper into the hydrophobic parts of the membrane as compared to domain B alone, which could be the reason for the inability of PDC-109/B to induce cholesterol efflux, despite its ability to recognize choline phospholipids at the membrane surface.

Concise and Efficient Fluorescent Probe via an Intromolecular Charge Transfer for the Chemical Warfare Agent Mimic Diethylchlorophosphate Vapor Detection.

PubMed

Yao, Junjun; Fu, Yanyan; Xu, Wei; Fan, Tianchi; Gao, Yixun; He, Qingguo; Zhu, Defeng; Cao, Huimin; Cheng, Jiangong

2016-02-16

Sarin, used as chemical warfare agents (CWAs) for terrorist attacks, can induce a number of virulent effects. Therefore, countermeasures which could realize robust and convenient detection of sarin are in exigent need. A concise charge-transfer colorimetric and fluorescent probe (4-(6-(tert-butyl)pyridine-2-yl)-N,N-diphenylaniline, TBPY-TPA) that could be capable of real-time and on-site monitoring of DCP vapor was reported in this contribution. Upon contact with DCP, the emission band red-shifted from 410 to 522 nm upon exposure to DCP vapor. And the quenching rate of TBPY-TPA reached up to 98% within 25 s. Chemical substances such as acetic acid (HAc), dimethyl methylphosphonate (DMMP), pinacolyl methylphosphonate (PAMP), and triethyl phosphate (TEP) do not interfere with the detection. A detection limit for DCP down to 2.6 ppb level is remarkably achieved which is below the Immediately Dangerous to Life or Health concentration. NMR data suggested that a transformation of the pyridine group into pyridinium salt via a cascade reaction is responsible for the sensing process which induced the dramatic fluorescent red shift. All of these data suggest TBPY-TPA is a promising fluorescent sensor for a rapid, simple, and low-cost method for DCP detection, which could be easy to prepare as a portable chemosensor kit for its practical application in real-time and on-site monitoring.

Cerenkov Radiation Energy Transfer (CRET) Imaging: A Novel Method for Optical Imaging of PET Isotopes in Biological Systems

PubMed Central

Dothager, Robin S.; Goiffon, Reece J.; Jackson, Erin; Harpstrite, Scott; Piwnica-Worms, David

2010-01-01

Background Positron emission tomography (PET) allows sensitive, non-invasive analysis of the distribution of radiopharmaceutical tracers labeled with positron (β+)-emitting radionuclides in small animals and humans. Upon β+ decay, the initial velocity of high-energy β+ particles can momentarily exceed the speed of light in tissue, producing Cerenkov radiation that is detectable by optical imaging, but is highly absorbed in living organisms. Principal Findings To improve optical imaging of Cerenkov radiation in biological systems, we demonstrate that Cerenkov radiation from decay of the PET isotopes 64Cu and 18F can be spectrally coupled by energy transfer to high Stokes-shift quantum nanoparticles (Qtracker705) to produce highly red-shifted photonic emissions. Efficient energy transfer was not detected with 99mTc, a predominantly γ-emitting isotope. Similar to bioluminescence resonance energy transfer (BRET) and fluorescence resonance energy transfer (FRET), herein we define the Cerenkov radiation energy transfer (CRET) ratio as the normalized quotient of light detected within a spectral window centered on the fluorophore emission divided by light detected within a spectral window of the Cerenkov radiation emission to quantify imaging signals. Optical images of solutions containing Qtracker705 nanoparticles and [18F]FDG showed CRET ratios in vitro as high as 8.8±1.1, while images of mice with subcutaneous pseudotumors impregnated with Qtracker705 following intravenous injection of [18F]FDG showed CRET ratios in vivo as high as 3.5±0.3. Conclusions Quantitative CRET imaging may afford a variety of novel optical imaging applications and activation strategies for PET radiopharmaceuticals and other isotopes in biomaterials, tissues and live animals. PMID:20949021

Cerenkov radiation energy transfer (CRET) imaging: a novel method for optical imaging of PET isotopes in biological systems.

PubMed

Dothager, Robin S; Goiffon, Reece J; Jackson, Erin; Harpstrite, Scott; Piwnica-Worms, David

2010-10-11

Positron emission tomography (PET) allows sensitive, non-invasive analysis of the distribution of radiopharmaceutical tracers labeled with positron (β(+))-emitting radionuclides in small animals and humans. Upon β(+) decay, the initial velocity of high-energy β(+) particles can momentarily exceed the speed of light in tissue, producing Cerenkov radiation that is detectable by optical imaging, but is highly absorbed in living organisms. To improve optical imaging of Cerenkov radiation in biological systems, we demonstrate that Cerenkov radiation from decay of the PET isotopes (64)Cu and (18)F can be spectrally coupled by energy transfer to high Stokes-shift quantum nanoparticles (Qtracker705) to produce highly red-shifted photonic emissions. Efficient energy transfer was not detected with (99m)Tc, a predominantly γ-emitting isotope. Similar to bioluminescence resonance energy transfer (BRET) and fluorescence resonance energy transfer (FRET), herein we define the Cerenkov radiation energy transfer (CRET) ratio as the normalized quotient of light detected within a spectral window centered on the fluorophore emission divided by light detected within a spectral window of the Cerenkov radiation emission to quantify imaging signals. Optical images of solutions containing Qtracker705 nanoparticles and [(18)F]FDG showed CRET ratios in vitro as high as 8.8±1.1, while images of mice with subcutaneous pseudotumors impregnated with Qtracker705 following intravenous injection of [(18)F]FDG showed CRET ratios in vivo as high as 3.5±0.3. Quantitative CRET imaging may afford a variety of novel optical imaging applications and activation strategies for PET radiopharmaceuticals and other isotopes in biomaterials, tissues and live animals.

Mechanofluorochromic Carbon Nanodots: Controllable Pressure-Triggered Blue- and Red-Shifted Photoluminescence.

PubMed

Liu, Cui; Xiao, Guanjun; Yang, Mengli; Zou, Bo; Zhang, Zhi-Ling; Pang, Dai-Wen

2018-02-12

Mechanofluorochromic materials, which change their photoluminescence (PL) colors in responding to mechanical stimuli, can be used as mechanosensors, security papers, and photoelectronic devices. However, traditional mechanofluorochromic materials can only be adjusted to a monotone direction upon the external stimuli. Controllable pressure-triggered blue- and red-shifted PL is reported for C-dots. The origin of mechanofluorochromism (MFC) in C-dots is interpreted based on structure-property relationships. The carbonyl group and the π-conjugated system play key roles in the PL change of C-dots under high pressure. As the pressure increases, the enhanced π-π stacking of the π-conjugated system causes the red-shift of PL, while the conversion of carbonyl groups eventually induces a blue-shift. Together with their low toxicity, good hydrophilicity, and small size, the tunable MFC property would boost various potential applications of C-dots. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Multiparametric Flow Cytometry Using Near-Infrared Fluorescent Proteins Engineered from Bacterial Phytochromes

PubMed Central

Telford, William G.; Shcherbakova, Daria M.; Buschke, David; Hawley, Teresa S.; Verkhusha, Vladislav V.

2015-01-01

Engineering of fluorescent proteins (FPs) has followed a trend of achieving longer fluorescence wavelengths, with the ultimate goal of producing proteins with both excitation and emission in the near-infrared (NIR) region of the spectrum. Flow cytometers are now almost universally equipped with red lasers, and can now be equipped with NIR lasers as well. Most red-shifted FPs of the GFP-like family are maximally excited by orange lasers (590 to 610 nm) not commonly found on cytometers. This has changed with the development of the iRFP series of NIR FPs from the protein family of bacterial phytochromes. The shortest wavelength variants of this series, iRFP670 and iRFP682 showed maximal excitation with visible red lasers. The longer wavelength variants iRFP702, iRFP713 and iRFP720 could be optimally excited by NIR lasers ranging from 685 to 730 nm. Pairs of iRFPs could be detected simultaneously by using red and NIR lasers. Moreover, a novel spectral cytometry technique, which relies on spectral deconvolution rather than optical filters, allowed spectra of all five iRFPs to be analyzed simultaneously with no spectral overlap. Together, the combination of iRFPs with the advanced flow cytometry will allow to first image tissues expressing iRFPs deep in live animals and then quantify individual cell intensities and sort out the distinct primary cell subpopulations ex vivo. PMID:25811854

Bioluminescence resonance energy transfer (BRET) imaging of protein–protein interactions within deep tissues of living subjects

PubMed Central

Dragulescu-Andrasi, Anca; Chan, Carmel T.; Massoud, Tarik F.; Gambhir, Sanjiv S.

2011-01-01

Identifying protein–protein interactions (PPIs) is essential for understanding various disease mechanisms and developing new therapeutic approaches. Current methods for assaying cellular intermolecular interactions are mainly used for cells in culture and have limited use for the noninvasive assessment of small animal disease models. Here, we describe red light-emitting reporter systems based on bioluminescence resonance energy transfer (BRET) that allow for assaying PPIs both in cell culture and deep tissues of small animals. These BRET systems consist of the recently developed Renilla reniformis luciferase (RLuc) variants RLuc8 and RLuc8.6, used as BRET donors, combined with two red fluorescent proteins, TagRFP and TurboFP635, as BRET acceptors. In addition to the native coelenterazine luciferase substrate, we used the synthetic derivative coelenterazine-v, which further red-shifts the emission maxima of Renilla luciferases by 35 nm. We show the use of these BRET systems for ratiometric imaging of both cells in culture and deep-tissue small animal tumor models and validate their applicability for studying PPIs in mice in the context of rapamycin-induced FK506 binding protein 12 (FKBP12)-FKBP12 rapamycin binding domain (FRB) association. These red light-emitting BRET systems have great potential for investigating PPIs in the context of drug screening and target validation applications. PMID:21730157

Multiparametric flow cytometry using near-infrared fluorescent proteins engineered from bacterial phytochromes.

PubMed

Telford, William G; Shcherbakova, Daria M; Buschke, David; Hawley, Teresa S; Verkhusha, Vladislav V

2015-01-01

Engineering of fluorescent proteins (FPs) has followed a trend of achieving longer fluorescence wavelengths, with the ultimate goal of producing proteins with both excitation and emission in the near-infrared (NIR) region of the spectrum. Flow cytometers are now almost universally equipped with red lasers, and can now be equipped with NIR lasers as well. Most red-shifted FPs of the GFP-like family are maximally excited by orange lasers (590 to 610 nm) not commonly found on cytometers. This has changed with the development of the iRFP series of NIR FPs from the protein family of bacterial phytochromes. The shortest wavelength variants of this series, iRFP670 and iRFP682 showed maximal excitation with visible red lasers. The longer wavelength variants iRFP702, iRFP713 and iRFP720 could be optimally excited by NIR lasers ranging from 685 to 730 nm. Pairs of iRFPs could be detected simultaneously by using red and NIR lasers. Moreover, a novel spectral cytometry technique, which relies on spectral deconvolution rather than optical filters, allowed spectra of all five iRFPs to be analyzed simultaneously with no spectral overlap. Together, the combination of iRFPs with the advanced flow cytometry will allow to first image tissues expressing iRFPs deep in live animals and then quantify individual cell intensities and sort out the distinct primary cell subpopulations ex vivo.

Blue- and Red-Shifting Hydrogen Bonding: A Gas Phase FTIR and Ab Initio Study of RR'CO···DCCl3 and RR'S···DCCl3 Complexes.

PubMed

Behera, B; Das, Puspendu K

2018-05-10

Blue-shifting H-bonded (C-D···O) complexes between CDCl 3 and CH 3 HCO, (CH 3 ) 2 CO, and C 2 H 5 (CH 3 )CO, and red-shifting H-bonded (C-D···S) complexes between CDCl 3 with (CH 3 ) 2 S and (C 2 H 5 ) 2 S have been identified by Fourier transform infrared spectroscopy in the gas phase at room temperature. With increasing partial pressure of the components, a new band appears in the C-D stretching region of the vibrational spectra. The intensity of this band decreases with an increase in temperature at constant pressure, which provides the basis for identification of the H-bonded bands in the spectrum. The C-D stretching frequency of CDCl 3 is blue-shifted by +7.1, +4, and +3.2 cm -1 upon complexation with CH 3 HCO, (CH 3 ) 2 CO, and C 2 H 5 (CH 3 )CO, respectively, and red-shifted by -14 and -19.2 cm -1 upon complexation with (CH 3 ) 2 S and (C 2 H 5 ) 2 S, respectively. By using quantum chemical calculations at the MP2/6-311++G** level, we predict the geometry, electronic structural parameters, binding energy, and spectral shift of H-bonded complexes between CDCl 3 and two series of compounds named RCOR' (H 2 CO, CH 3 HCO, (CH 3 ) 2 CO, and C 2 H 5 (CH 3 )CO) and RSR' (H 2 S, CH 3 HS, (CH 3 ) 2 S, and (C 2 H 5 ) 2 S) series. The calculated and observed spectral shifts follow the same trends. With an increase in basicity of the H-bond acceptor, the C-D bond length increases, force constant decreases, and the frequency shifts to the red from the blue. The potential energy scans of the above complexes are done, which show that electrostatic attraction between electropositive D and electron-rich O/S causes bond elongation and red shift, and the electronic and nuclear repulsions lead to bond contraction and blue shifts. The dominance of the two opposing forces at the equilibrium geometry of the complex determines the nature of the shift, which changes both in magnitude and in direction with the basicity of the hydrogen-bond acceptor.

Three computational mise-en-scènes of red- and blue-shifted hydrogen bonding motifs: Concept of negative intramolecular coupling-What else?

NASA Astrophysics Data System (ADS)

Kryachko, Eugene S.

This work is a kind of attempt to rethink some problems which are related to the blue-shifted "hydrogen bonds" and which have been left in the past decade as not yet fully resolved. The impetus for such rethink is originated from the three computational mise-en-scènes on red- and blue-shifted hydrogen bonding motifs, which are aimed to be thoroughly studied in this work, thus resolving the above problems.

Low temperature preparation of Ag-doped ZnO nanowire arrays for sensor and light-emitting diode applications

NASA Astrophysics Data System (ADS)

Lupan, O.; Viana, B.; Cretu, V.; Postica, V.; Adelung, R.; Pauporté, T.

2016-02-01

Transition metal doped-oxide semiconductor nanostructures are important to achieve enhanced and new properties for advanced applications. We describe the low temperature preparation of ZnO:Ag nanowire/nanorod (NW/NR) arrays by electrodeposition at 90 °C. The NWs have been characterized by SEM, EDX, transmittance and photoluminescence (PL) measurements. The integration of Ag in the crystal is shown. Single nanowire/nanorod of ZnO:Ag was integrated in a nanosensor structure leading to new and enhanced properties. The ultraviolet (UV) response of the nanosensor was investigated at room temperature. Experimental results indicate that ZnO:Ag (0.75 μM) nanosensor possesses faster response/recovery time and better response to UV light than those reported in literature. The sensor structure has been also shown to give a fast response for the hydrogen detection with improved performances compared to pristine ZnO NWs. ZnO:Ag nanowire/nanorod arrays electrochemically grown on p-type GaN single crystal layer is also shown to act as light emitter in LED structures. The emission wavelength is red-shifted compared to pristine ZnO NW array. At low Ag concentration a single UV-blue emission is found whereas at higher concentration of dopant the emission is broadened and extends up to the red wavelength range. Our study indicates that high quality ZnO:Ag NW/NR prepared at low temperature by electrodeposition can serve as building nanomaterials for new sensors and light emitting diodes (LEDs) structures with low-power consumption.

The MIGHTI Wind Retrieval Algorithm: Description and Verification

NASA Astrophysics Data System (ADS)

Harding, Brian J.; Makela, Jonathan J.; Englert, Christoph R.; Marr, Kenneth D.; Harlander, John M.; England, Scott L.; Immel, Thomas J.

2017-10-01

We present an algorithm to retrieve thermospheric wind profiles from measurements by the Michelson Interferometer for Global High-resolution Thermospheric Imaging (MIGHTI) instrument on NASA's Ionospheric Connection Explorer (ICON) mission. MIGHTI measures interferometric limb images of the green and red atomic oxygen emissions at 557.7 nm and 630.0 nm, spanning 90-300 km. The Doppler shift of these emissions represents a remote measurement of the wind at the tangent point of the line of sight. Here we describe the algorithm which uses these images to retrieve altitude profiles of the line-of-sight wind. By combining the measurements from two MIGHTI sensors with perpendicular lines of sight, both components of the vector horizontal wind are retrieved. A comprehensive truth model simulation that is based on TIME-GCM winds and various airglow models is used to determine the accuracy and precision of the MIGHTI data product. Accuracy is limited primarily by spherical asymmetry of the atmosphere over the spatial scale of the limb observation, a fundamental limitation of space-based wind measurements. For 80% of the retrieved wind samples, the accuracy is found to be better than 5.8 m/s (green) and 3.5 m/s (red). As expected, significant errors are found near the day/night boundary and occasionally near the equatorial ionization anomaly, due to significant variations of wind and emission rate along the line of sight. The precision calculation includes pointing uncertainty and shot, read, and dark noise. For average solar minimum conditions, the expected precision meets requirements, ranging from 1.2 to 4.7 m/s.

[Effects of water stress on red-edge parameters and yield in wheat cropping].

PubMed

He, Ke-Xun; Zaho, Shu-He; Lai, Jian-Bin; Luo, Yun-Xiao; Qin, Zhi-Hao

2013-08-01

The objective of the present paper is to study the influence of water stress on wheat spectrum red edge parameters by using field wheat spectrum data obtained from water stress experiment. Firstly, the authors analyzed the influence of water stress on wheat spectrum reflectance. Then the authors got the wheat red edge position and red edge peak through calculating wheat spectrum first-order differential and analyzed the influence of water stress on wheat red edge parameters. Finally the authors discussed the relationship between red peak and wheat yield. The results showed that the wheat red edge position shows "red shift" at the beginning of the wheat growth period and "blue shift" at the later period of the wheat growth period under the water stress experiment. Also, the red edge peak of the wheat showed that red edge peak increased with the water stress sharpening at the beginning of the wheat growth period, and then the red edge peak reduced with the water stress sharpening. The wheat red edge peak presented positive correlation with the wheat yield before the elongation period, and exhibited negative correlation after that period.

Ratiometric imaging of gastrodermal lipid bodies in coral-dinoflagellate endosymbiosis

NASA Astrophysics Data System (ADS)

Luo, Y.-J.; Wang, L.-H.; Chen, W.-N. U.; Peng, S.-E.; Tzen, J. T.-C.; Hsiao, Y.-Y.; Huang, H.-J.; Fang, L.-S.; Chen, C.-S.

2009-03-01

Cnidaria-dinoflagellate endosymbiosis is the phenomenon of autotrophic symbionts living inside the gastrodermal cells of their animal hosts. The molecular mechanism that regulates this association remains unclear. Using quantitative microscopy, we now provide evidence that the dynamic lipid changes in gastrodermal “lipid bodies” (LBs) reflect the symbiotic status of the host cell and its symbiont in the hermatypic coral Euphyllia glabrescens. By dual-emission ratiometric imaging with a solvatochromic fluorescent probe, Nile red (9-diethylamino-5H-benzo[α]phenoxazine-5-one), we showed that the in situ distribution of polar versus neutral lipids in LBs in living gastrodermal cells and symbionts can be analyzed. The ratio of Nile red fluorescence at red (R) versus green (G) wavelength region (i.e., R/G ratio) correlated with the relative molar ratio of polar (P) versus neutral (NP) lipids (i.e., P/NP ratio). The R/G ratio in host LBs increased after bleaching, indicating a decrease in neutral lipid accumulation in gastrodermal cells. On the other hand, neutral lipid accumulation inside the symbiont LBs resulted in gradual decreases of the R/G ratio as a result of bleaching. In comparison with the bleaching event, there was no relative lipid concentration change in host LBs under continual light or dark treatments as shown by insignificant R/G ratio shift. Patterns of R/G ratio shift in symbiont LBs were also different between corals undergoing bleaching and continual light/dark treatment. In the latter, there was little lipid accumulation in symbionts, with no resulting R/G ratio decrease. These results, demonstrating that the symbiotic status positively correlated with morphological and compositional changes of lipid bodies, not only highlight the pivotal role of LBs, but also implicate an involvement of lipid trafficking in regulating the endosymbiosis.

First direct comparison of high and low ionization line kinematics in active galactic nuclei

NASA Technical Reports Server (NTRS)

Sulentic, J. W.; Marziani, P.; Dultzin-Hacyan, D.; Calvani, M.; Moles, M.

1995-01-01

We present first results of a comparison of emission line shift properties for the high (HILs) and low (LILs) ionization lines in 43 low-reshift quasars. We identify a core sample of C IV lambda 1549 and hydrogen beta profiles with a wide distribution of red- and blueshifts (less than or equal to +/- 1000 km/sec). We also identify two tails in this distribution: one with large hydrogen beta redshifts (greater than or equal to 2000 km/sec) and another with large C IV blueshifts (greater than or equal to 1500 km/sec). The tails are mutually exclusive. All objects with extreme hydrogen beta redshift are radio loud, and all objects with extreme C IV blueshift are radio quiet. The core samples of smaller shifts can be most simply divided into: (1) hydrogen beta - a redshifted radio-loud population (related to the tail) and a radio-quiet population with mean shift near zero, and (2) C IV - a blueshifted radio-quiet population (related to the tail) and a radio-loud population with mean shift near zero. The results suggest fundamentally different kinematics for the HILs and LILs. They also suggest very different kinematics for radio-loud and radio-quiet active galactic nuclei. They also favor a predominance of radial motion in a large fraction of the sample.

Growth of Au nanoparticle films and the effect of nanoparticle shape on plasmon peak wavelength

NASA Astrophysics Data System (ADS)

Horikoshi, S.; Matsumoto, N.; Omata, Y.; Kato, T.

2014-05-01

Metal nanoparticles (NPs) exhibit localized surface plasmon resonance (LSPR) and thus have potential for use in a wide range of applications. A facile technique for the preparation of NP films using an electron-cyclotron-resonance plasma sputtering method without a dewetting process is described. Field emission scanning electron microscopy (FE-SEM) observations revealed that the Au NPs grew independently as island-like particles during the first stage of sputtering and then coalesced with one another as sputtering time increased to ultimately form a continuous film. A plasmon absorption peak was observed via optical measurement of absorption efficiency. The LSPR peak shifted toward longer wavelengths (red shift) with an increase in sputtering time. The cause of this plasmon peak shift was theoretically investigated using the finite-difference time-domain calculation method. A realistic statistical distribution of the particle shapes based on FE-SEM observations was applied for the analysis, which has not been previously reported. It was determined that the change in the shape of the NPs from spheroidal to oval or slender due to coalescence with neighbouring NPs caused the LSPR peak shift. These results may enable the design of LSPR devices by controlling the characteristics of the nanoparticles, such as their size, shape, number density, and coverage.

Long-term spectroscopic monitoring of the Luminous Blue Variable AG Carinae

NASA Astrophysics Data System (ADS)

Stahl, O.; Jankovics, I.; Kovács, J.; Wolf, B.; Schmutz, W.; Kaufer, A.; Rivinius, Th.; Szeifert, Th.

2001-08-01

We have extensively monitored the Luminous Blue Variable AG Car (HD 94910) spectroscopically. Our data cover the years 1989 to 1999. In this period, the star underwent almost a full S Dor cycle from visual minimum to maximum and back. Over several seasons, up to four months of almost daily spectra are available. Our data cover most of the visual spectral range with a high spectral resolution (lambda /Delta lambda ~ 20 000). This allows us to investigate the variability in many lines on time scales from days to years. The strongest variability occurs on a time scale of years. Qualitatively, the variations can be understood as changes of the effective temperature and radius, which are in phase with the optical light curve. Quantitatively, there are several interesting deviations from this behaviour, however. The Balmer lines show P Cygni profiles and have their maximum strength (both in equivalent width and line flux) after the peak of the optical light curve, at the descending branch of the light curve. The line-width during maximum phase is smaller than during minimum, but it has a local maximum close to the peak of the visual light curve. We derive mass-loss rates over the cycle from the Hα line and find the highest mass loss rates (log dot {M}/({M}_sun yr-1) ~ -3.8, about a factor of five higher than in the minimum, where we find log dot {M}/({M}_sun yr-1) ~ -4.5) after the visual maximum. Line-splitting is very commonly observed, especially on the rise to maximum and on the descending branch from maximum. The components are very long-lived (years) and are probably unrelated to similar-looking line-splitting events in normal supergiants. Small apparent accelerations of the components are observed. The change in radial velocity could be due to successive narrowing of the components, with the absorption disappearing at small expansion velocities first. In general, the line-splitting is more likely the result of missing absorption at intermediate velocities than of excess absorption at the velocities of the components. The HeI lines and other lines which form deep in the atmosphere show the most peculiar variations. The HeI lines show a central absorption with variable blue- and red-shifted emission components. Due to the variations of the emission components, the HeI lines can change their line profile from a normal P Cyg profile to an inverse P Cyg-profile or double-peak emission. In addition, very broad (+/-1500 km s-1) emission wings are seen at the strongest HeI lines of AG Car. At some phases, a blue-shifted absorption is also present. The central absorption of the HeI lines is blue-shifted before and red-shifted after maximum. Possibly, we directly see the expansion and contraction of the photosphere. If this explanation is correct, the velocity of the continuum-forming layer is not dominated by expansion but is only slightly oscillating around the systemic velocity. Based on observations collected at the European Southern Observatory at La Silla, Chile.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Saxena, Shailendra K., E-mail: phd1211512@iiti.ac.in; Sahu, Gayatri; Sagdeo, Pankaj R.

Quantum confinement effect has been studied in cheese like silicon nano-structures (Ch-SiNS) fabricated by metal induced chemical etching using different etching times. Scanning electron microscopy is used for the morphological study of these Ch-SiNS. A visible photoluminescence (PL) emission is observed from the samples under UV excitation at room temperature due to quantum confinement effect. The average size of Silicon Nanostructures (SiNS) present in the samples has been estimated by bond polarizability model using Raman Spectroscopy from the red-shift observed from SiNSs as compared to its bulk counterpart. The sizes of SiNS present in the samples decreases as etching timemore » increase from 45 to 75 mintunes.« less

A DFT-D study on the electronic and photophysical properties of ruthenium (II) complex with a chelating sulfoxide group

NASA Astrophysics Data System (ADS)

Li, Huifang; Zhang, Lisheng; Lin, Hui; Fan, Xiaolin

2014-06-01

Electronic and photophysical properties of [Ru(bpy)2(OSO)]+ (bpy = 2,2‧-bipyridine; OSO = methylsulfinylbenzoate) were examined theoretically to better understand the differences between S- and O-linked ruthenium sulfoxide complexes. It is found that the strength of Ru-O1 linkage is significantly larger than that of Ru-S linkage, which makes the charge transfer amount from surrounding ligands to central Ru decreased. The energy gap is closed due to the highest occupied molecular orbital energy increases to a larger extent than the lowest unoccupied molecular orbital energy. Thereby, red shifted absorption and emission maxima in such photochromic ruthenium sulfoxide complexes can be explained.

Dimeric fluorescent energy transfer dyes comprising asymmetric cyanine azole-indolenine chromophores

DOEpatents

Glazer, Alexander N.; Benson, Scott C.

1998-01-01

Novel fluorescent heterodimeric DNA-staining energy transfer dyes are provided combining asymmetric cyanine azole-indolenine dyes, which provide for strong DNA affinity, large Stokes shifts and emission in the red region of the spectrum. The dyes find particular application in gel electrophoresis and for labels which may be bound to a variety of compositions in a variety of contexts. Kits and individual compounds are provided, where the kits find use for simultaneous detection of a variety of moieties, particularly using a single narrow wavelength irradiation source. The individual compounds are characterized by high donor quenching and high affinity to dsDNA as a result of optimizing the length of the linking group separating the two chromophores.

On the modified active region design of interband cascade lasers

DOE Office of Scientific and Technical Information (OSTI.GOV)

Motyka, M.; Ryczko, K.; Dyksik, M.

2015-02-28

Type II InAs/GaInSb quantum wells (QWs) grown on GaSb or InAs substrates and designed to be integrated in the active region of interband cascade lasers (ICLs) emitting in the mid infrared have been investigated. Optical spectroscopy, combined with band structure calculations, has been used to probe their electronic properties. A design with multiple InAs QWs has been compared with the more common double W-shaped QW and it has been demonstrated that it allows red shifting the emission wavelength and enhancing the transition oscillator strength. This can be beneficial for the improvements of the ICLs performances, especially when considering their long-wavelengthmore » operation.« less

Chemical Synthesis of ZnS:Cu Nanosheets

NASA Astrophysics Data System (ADS)

Bodo, Bhaskarjyoti; Kalita, P. K.

2010-10-01

ZnS thin films are synthesized through chemical bath deposition (CBD) technique from aqueous solution of ZnSO4 and thiourea mixing in equal volume and equimolar ratio. A 1% CuSO4 solution is mixed with the ZnSO4 solution for doping before the final chemical reaction. SEM image shows the formation of mainly nanosheets, teeth and comb like structures. Absorption studies show red shift of enhanced band gap on Cu doping. Photoluminescence of ZnS:Cu reveals the enhancement of blue luminescence at 468 nm and low intensity green emission at 493 nm which is attributed to more Cu2+ lying in the interstices. XRD shows that the prepared ZnS nanophosphors possess cubic zinc blende structures.

Structural, optical and Carrier dynamics of self-assembled InGaN nanocolumns on Si(111)

NASA Astrophysics Data System (ADS)

Kumar, Praveen; Devi, Pooja; Soto Rodriguez, P. E. D.; Jain, Rishabh; Jaggi, Neena; Sinha, R. K.; Kumar, Mahesh

2018-05-01

We investigated the morphological, structural, optical, electrical and carrier relaxation dynamic changes on the self-assembled grown InGaN nanocolumns (NCs) directly on p-Si(111) substrate at two different substrate temperature, namely 580 °C (A) and 500 °C (B). The emission wavelength of comparably low temperature (LT) grown NCs was red-shifted from 3.2eV to 2.4eV. First observations on the charge carrier dynamics of these directly grown NCs show comparable broad excited state absorption (ESA) for LT gown NCs, which manifest bi-exponential decay due to the radiative defects generated during the coalescence of these NCs.

Room temperature enhanced red emission from novel Eu(3+) doped ZnO nanocrystals uniformly dispersed in nanofibers.

PubMed

Zhang, Yongzhe; Liu, Yanxia; Li, Xiaodong; Wang, Qi Jie; Xie, Erqing

2011-10-14

Achieving red emission from ZnO-based materials has long been a goal for researchers in order to realize, for instance, full-color display panels and solid-state light-emitting devices. However, the current technique using Eu(3+) doped ZnO for red emission generation has a significant drawback in that the energy transfer from ZnO to Eu(3+) is inefficient, resulting in a low intensity red emission. In this paper, we report an efficient energy transfer scheme for enhanced red emission from Eu(3+) doped ZnO nanocrystals by fabricating polymer nanofibers embedded with Eu(3+) doped ZnO nanocrystals to facilitate the energy transfer. In the fabrication, ZnO nanocrystals are uniformly dispersed in polymer nanofibers prepared by the high electrical field electrospinning technique. Enhanced red emission without defect radiation from the ZnO matrix is observed. Three physical mechanisms for this observation are provided and explained, namely a small ZnO crystal size, uniformity distribution of ZnO nanocrystals in polymers (PVA in this case), and strong bonding between ZnO and polymer through the -OH group bonding. These explanations are supported by high resolution transmission emission microscopy measurements, resonant Raman scattering characterizations, photoluminescence spectra and photoluminescence excitation spectra measurements. In addition, two models exploring the 'accumulation layer' and 'depletion layer' are developed to explain the reasons for the more efficient energy transfer in our ZnO nanocrystal system compared to that in the previous reports. This study provides an important approach to achieve enhanced energy transfer from nanocrystals to ions which could be widely adopted in rare earth ion doped materials. These discoveries also provide more insights into other energy transfer problems in, for example, dye-sensitized solar cells and quantum dot solar cells.

Assessment of AVIRIS data from vegetated sites in the Owens Valley, California

NASA Technical Reports Server (NTRS)

Rock, B. N.; Elvidge, Christopher D.; Defeo, N. J.

1988-01-01

Airborne Visible/Infrared Imaging Spectrometer (AVIRIS) data were acquired from the Bishop, CA area, located at the northern end of the Owens Valley, on July 30, 1987. Radiometrically-corrected AVIRIS data were flat-field corrected, and spectral curves produced and analyzed for pixels taken from both native and cultivated vegetation sites, using the JPS SPAM software program and PC-based spreadsheet programs. Analyses focussed on the chlorophyll well and red edge portions of the spectral curves. Results include the following: AVIRIS spectral data are acquired at sufficient spectral resolution to allow detection of blue shifts of both the chlorophyll well and red edge in moisture-stressed vegetation when compared with non-stressed vegetation; a normalization of selected parameters (chlorophyll well and near infrared shoulder) may be used to emphasize the shift in red edge position; and the presence of the red edge in AVIRIS spectral curves may be useful in detecting small amounts (20 to 30 pct cover) of semi-arid and arid vegetation ground cover. A discussion of possible causes of AVIRIS red edge shifts in respsonse to stress is presented.

The First Mutant of the Aequorea victoria Green Fluorescent Protein That Forms a Red Chromophore†

PubMed Central

Mishin, Alexander S.; Subach, Fedor V.; Yampolsky, Ilia V.; King, William; Lukyanov, Konstantin A.; Verkhusha, Vladislav V.

2010-01-01

Green fluorescent protein (GFP) from a jellyfish, Aequorea victoria, and its mutants are widely used in biomedical studies as fluorescent markers. In spite of the enormous efforts of academia and industry toward generating its red fluorescent mutants, no GFP variants with emission maximum at more than 529 nm have been developed during the 15 years since its cloning. Here, we used a new strategy of molecular evolution aimed at generating a red-emitting mutant of GFP. As a result, we have succeeded in producing the first GFP mutant that substantially matures to the red-emitting state with excitation and emission maxima at 555 and 585 nm, respectively. A novel, nonoxidative mechanism for formation of the red chromophore in this mutant that includes a dehydration of the Ser65 side chain has been proposed. Model experiments showed that the novel dual-color GFP mutant with green and red emission is suitable for multicolor flow cytometry as an additional color since it is clearly separable from both green and red fluorescent tags. PMID:18366185

Influence of etching current density on microstructural, optical and electrical properties of porous silicon (PS):n-Si heterostructure

NASA Astrophysics Data System (ADS)

Das, M.; Nath, P.; Sarkar, D.

2016-02-01

In this article effect of etching current density (J) on the microstructural, optical and electrical properties of photoelectrochemically prepared heterostructure is reported. Prepared samples are characterized by FESEM, XRD, UV-Visible, Raman and photoluminescence (PL) spectra and current-voltage (I-V) characteristics. FESEM shows presence of mixture of randomly distributed meso- and micro-pores. Porous layer thickness determined by cross section view of SEM is proportional to J. XRD shows crystalline nature but gradually extent of crystallinity decreases with increasing J. Raman spectra show large red-shift and asymmetric broadening with respect to crystalline silicon (c-Si). UV-visible reflectance and PL show blue shift in peaks with increasing J. The I-V characteristics are analyzed by the conventional thermionic emission (TE) model and Cheung's model to estimate the barrier height (φb), ideality factor (n) and series resistance (Rs) for comparison between the two models. The latter model is found to fit better.

A specific chemodosimeter for fluoride ion based on a pyrene derivative with trimethylsilylethynyl groups.

PubMed

Lu, Hua; Wang, Qiuhong; Li, Zhifang; Lai, Guoqiao; Jiang, Jianxiong; Shen, Zhen

2011-06-21

Pyrene derivative 1 containing four trimethylsilylethynyl substituents was synthesized and investigated as a chromogenic and fluorescent chemodosimeter sensor for fluoride ions. 1 showed a high sensitivity and specific selectivity over a rapid response time toward fluoride anions compared to other anions, such as Cl(-), Br(-), ClO(4)(-), H(2)PO(4)(-) and HPO(4)(2-). TD-DFT calculations showed that the delocalization of the σ-electrons of the silicon destabilized the HOMO energy level of 1, thus red shifting both its absorption and emission spectrum. The addition of F(-) removed the trimethylsilyl substituents and resulted in a blue shift of both the absorption and fluorescent spectra of 1, which could be monitored by the color change with the naked-eye. Moreover, an easy to prepare test paper, which was obtained by immersing a filter paper into a THF solution of 1, could be utilized to detect and estimate the concentration of fluoride anions in water.

Rational design of a monomeric and photostable far-red fluorescent protein for fluorescence imaging in vivo.

PubMed

Yu, Dan; Dong, Zhiqiang; Gustafson, William Clay; Ruiz-González, Rubén; Signor, Luca; Marzocca, Fanny; Borel, Franck; Klassen, Matthew P; Makhijani, Kalpana; Royant, Antoine; Jan, Yuh-Nung; Weiss, William A; Guo, Su; Shu, Xiaokun

2016-02-01

Fluorescent proteins (FPs) are powerful tools for cell and molecular biology. Here based on structural analysis, a blue-shifted mutant of a recently engineered monomeric infrared fluorescent protein (mIFP) has been rationally designed. This variant, named iBlueberry, bears a single mutation that shifts both excitation and emission spectra by approximately 40 nm. Furthermore, iBlueberry is four times more photostable than mIFP, rendering it more advantageous for imaging protein dynamics. By tagging iBlueberry to centrin, it has been demonstrated that the fusion protein labels the centrosome in the developing zebrafish embryo. Together with GFP-labeled nucleus and tdTomato-labeled plasma membrane, time-lapse imaging to visualize the dynamics of centrosomes in radial glia neural progenitors in the intact zebrafish brain has been demonstrated. It is further shown that iBlueberry can be used together with mIFP in two-color protein labeling in living cells and in two-color tumor labeling in mice. © 2015 The Protein Society.

Effects of non-enzymatic glycation in human serum albumin. Spectroscopic analysis

NASA Astrophysics Data System (ADS)

Szkudlarek, A.; Sułkowska, A.; Maciążek-Jurczyk, M.; Chudzik, M.; Równicka-Zubik, J.

2016-01-01

Human serum albumin (HSA), transporting protein, is exposed during its life to numerous factors that cause its functions become impaired. One of the basic factors - glycation of HSA - occurs in diabetes and may affect HSA-drug binding. Accumulation of advanced glycation end-products (AGEs) leads to diseases e.g. diabetic and non-diabetic cardiovascular diseases, Alzheimer disease, renal disfunction and in normal aging. The aim of the present work was to estimate how non-enzymatic glycation of human serum albumin altered its tertiary structure using fluorescence technique. We compared glycated human serum albumin by glucose (gHSAGLC) with HSA glycated by fructose (gHSAFRC). We focused on presenting the differences between gHSAFRC and nonglycated (HSA) albumin used acrylamide (Ac), potassium iodide (KI) and 2-(p-toluidino)naphthalene-6-sulfonic acid (TNS). Changes of the microenvironment around the tryptophan residue (Trp-214) of non-glycated and glycated proteins was investigated by the red-edge excitation shift method. Effect of glycation on ligand binding was examined by the binding of phenylbutazone (PHB) and ketoprofen (KP), which a primary high affinity binding site in serum albumin is subdomain IIA and IIIA, respectively. At an excitation and an emission wavelength of λex 335 nm and λem 420 nm, respectively the increase of fluorescence intensity and the blue-shift of maximum fluorescence was observed. It indicates that the glycation products decreases the polarity microenvironment around the fluorophores. Analysis of red-edge excitation shift method showed that the red-shift for gHSAFRC is higher than for HSA. Non-enzymatic glycation also caused, that the Trp residue of gHSAFRC becomes less accessible for the negatively charged quencher (I-), KSV value is smaller for gHSAFRC than for HSA. TNS fluorescent measurement demonstrated the decrease of hydrophobicity in the glycated albumin. KSV constants for gHSA-PHB systems are higher than for the unmodified serum albumin, while KSV values for gHSA-KP systems are only slightly lower than that obtained for HSA-KP. The affinity of PHB to the glycated HSA is stronger than to the non-glycated in the first class binding sites within subdomain IIA, in the vicinity of Trp-214. Ketoprofen bound to unmodified human serum albumin stronger than for glycated albumin and one class of binding sites is observed (Scatchard linear plots).

Inner filter effect and the onset of concentration dependent red shift of synchronous fluorescence spectra.

PubMed

Tarai, Madhumita; Mishra, Ashok Kumar

2016-10-12

The phenomenon of concentration dependent red shift, often observed in synchronous fluorescence spectra (SFS) of monofluorophoric as well as multifluorophoric systems at high chromophore concentrations, is known to have good analytical advantages. This was previously understood in terms of large inner filter effect (IFE) through the introduction of a derived absorption spectral profile that closely corresponds to the SFS profile. Using representative monofluorophoric and multifluorophoric systems, it is now explained how the SF spectral maximum changes with concentration of the fluorophore. For dilute solutions of monofluorophores the maximum is unchanged as expected. It is shown here that the onset of red shift of SFS maximum of both the mono as well as the multifluorophoric systems must occur at the derived absorption spectral parameter value of 0.32 that corresponds to the absorbance value of 0.87. This value is unique irrespective of the nature of the fluorophore under study. For monofluorophoric systems, the wavelength of derived absorption spectral maximum and the wavelength of synchronous fluorescence spectral maximum closely correspond with each other in the entire concentration range. In contrast, for multifluorophoric systems like diesel and aqueous humic acid, large deviations were noted that could be explained as to be due to the presence of non-fluorescing chromophores in the system. This work bridges the entire fluorophore concentration range over which the red shift of SFS maximum sets in; and in the process it establishes the importance of the derived absorption spectral parameter in understanding the phenomenon of concentration dependent red shift of SFS maximum. Copyright © 2016 Elsevier B.V. All rights reserved.

Molecular jet of IRAS 04166+2706

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Liang-Yao; Shang, Hsien; Su, Yu-Nung

2014-01-01

The molecular outflow from IRAS 04166+2706 was mapped with the Submillimeter Array at a 350 GHz continuum and CO J = 3-2 at an angular resolution of ∼1''. The field of view covers the central arcminute, which contains the inner four pairs of knots of the molecular jet. On the channel map, conical structures are clearly present in the low-velocity range (|V – V {sub 0}| < 10 km s{sup –1}), and the highly collimated knots appear in the extremely high velocity range (50 >|V – V {sub 0}| > 30 km s{sup –1}). The higher angular resolution of ∼1''more » reveals the first blue-shifted knot (B1) that was missing in previous Plateau de Bure Interferometer observation of Santiago-García et al. at an offset of ∼6'' to the northeast of the central source. This identification completes the symmetric sequence of knots in both the blue- and red-shifted lobes of the outflow. The innermost knots R1 and B1 have the highest velocities within the sequence. Although the general features appear to be similar to previous CO J = 2-1 images in Santiago-García et al., the emission in CO J = 3-2 almost always peaks further away from the central source than that of CO J = 2-1 in the red-shifted lobe of the channel maps. This gives rise to a gradient in the line-ratio map of CO J = 3-2/J = 2-1 from head to tail within a knot. A large velocity gradient analysis suggests that the differences may reflect a higher gas kinetic temperature at the head. We also explore possible constraints imposed by the nondetection of SiO J = 8-7.« less

Evidence for Cation-Controlled Excited-State Localization in a Ruthenium Polypyridyl Compound.

PubMed

Beauvilliers, Evan E; Meyer, Gerald J

2016-08-01

The visible absorption and photoluminescence (PL) properties of the four neutral ruthenium diimine compounds [Ru(bpy)2(dcb)] (B2B), [Ru(dtb)2(dcb)] (D2B), [Ru(bpy)2(dcbq)] (B2Q), and [Ru(dtb)2(dcbq)] (D2Q), where bpy is 2,2'-bipyridine, dcb is 4,4'-(CO2(-))2-bpy, dtb is 4,4'-(tert-butyl)2-bpy, and dcbq is 4,4'-(CO2(-))2-2,2'-biquinoline, are reported in the presence of Lewis acidic cations present in fluid solutions at room temperature. In methanol solutions, the measured spectra were insensitive to the presence of these cations, while in acetonitrile a significant red shift in the PL spectra (≤1400 cm(-1)) was observed consistent with stabilization of the metal-to-ligand charge transfer (MLCT) excited state through Lewis acid-base adduct formation. No significant spectral changes were observed in control experiments with the tetrabutylammonium cation. Titration data with Li(+), Na(+), Mg(2+), Ca(2+), Zn(2+), Al(3+), Y(3+), and La(3+) showed that the extent of stabilization saturated at high cation concentration with magnitudes that scaled roughly with the cation charge-to-size ratio. The visible absorption spectra of D2Q was particularly informative due to the presence of two well-resolved MLCT absorption bands: (1) Ru → bpy, λmax ≈ 450 nm; and (2) Ru → dcbq, λmax ≈ 540 nm. The higher-energy band blue-shifted and the lower-energy band red-shifted upon cation addition. The PL intensity and lifetime of the excited state of B2B first increased with cation addition without significant shifts in the measured spectra, behavior attributed to a cation-induced change in the localization of the emissive excited state from bpy to dcb. The importance of excited-state localization and stabilization for solar energy conversion is discussed.

Optical signal inverter of erbium-doped yttrium aluminum garnet with red shift of laser diodes.

PubMed

Maeda, Y

1994-08-10

An optical signal inverter was demonstrated in a simple structure that combined a laser diode with Er-doped YAG crystal. The optical signal inversion occurred at a response time of 7 ns and was caused by the decrease of transmission of Er:YAG against the red shift of the wavelength of the laser diode.

Amplifying the Red-Emission of Upconverting Nanoparticles for Biocompatible Clinically Used Prodrug-Induced Photodynamic Therapy

DOE PAGES

Punjabi, Amol; Wu, Xiang; Tokatli-Apollon, Amira; ...

2014-09-25

A class of biocompatible upconverting nanoparticles (UCNPs) with largely amplified red-emissions was developed. The optimal UCNP shows a high absolute upconversion quantum yield of 3.2% in red-emission, which is 15-fold stronger than the known optimal β-phase core/shell UCNPs. When conjugated to aminolevulinic acid, a clinically used photodynamic therapy (PDT) prodrug, significant PDT effect in tumor was demonstrated in a deep-tissue (>1.2 cm) setting in vivo at a biocompatible laser power density. Furthermore, we show that our UCNP–PDT system with NIR irradiation outperforms clinically used red light irradiation in a deep tumor setting in vivo. This study marks a major stepmore » forward in photodynamic therapy utilizing UCNPs to effectively access deep-set tumors.Lastly, it also provides an opportunity for the wide application of upconverting red radiation in photonics and biophotonics.« less

Amplifying the red-emission of upconverting nanoparticles for biocompatible clinically used prodrug-induced photodynamic therapy.

PubMed

Punjabi, Amol; Wu, Xiang; Tokatli-Apollon, Amira; El-Rifai, Mahmoud; Lee, Hyungseok; Zhang, Yuanwei; Wang, Chao; Liu, Zhuang; Chan, Emory M; Duan, Chunying; Han, Gang

2014-10-28

A class of biocompatible upconverting nanoparticles (UCNPs) with largely amplified red-emissions was developed. The optimal UCNP shows a high absolute upconversion quantum yield of 3.2% in red-emission, which is 15-fold stronger than the known optimal β-phase core/shell UCNPs. When conjugated to aminolevulinic acid, a clinically used photodynamic therapy (PDT) prodrug, significant PDT effect in tumor was demonstrated in a deep-tissue (>1.2 cm) setting in vivo at a biocompatible laser power density. Furthermore, we show that our UCNP-PDT system with NIR irradiation outperforms clinically used red light irradiation in a deep tumor setting in vivo. This study marks a major step forward in photodynamic therapy utilizing UCNPs to effectively access deep-set tumors. It also provides an opportunity for the wide application of upconverting red radiation in photonics and biophotonics.

Amplifying the Red-Emission of Upconverting Nanoparticles for Biocompatible Clinically Used Prodrug-Induced Photodynamic Therapy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Punjabi, Amol; Wu, Xiang; Tokatli-Apollon, Amira

A class of biocompatible upconverting nanoparticles (UCNPs) with largely amplified red-emissions was developed. The optimal UCNP shows a high absolute upconversion quantum yield of 3.2% in red-emission, which is 15-fold stronger than the known optimal β-phase core/shell UCNPs. When conjugated to aminolevulinic acid, a clinically used photodynamic therapy (PDT) prodrug, significant PDT effect in tumor was demonstrated in a deep-tissue (>1.2 cm) setting in vivo at a biocompatible laser power density. Furthermore, we show that our UCNP–PDT system with NIR irradiation outperforms clinically used red light irradiation in a deep tumor setting in vivo. This study marks a major stepmore » forward in photodynamic therapy utilizing UCNPs to effectively access deep-set tumors.Lastly, it also provides an opportunity for the wide application of upconverting red radiation in photonics and biophotonics.« less

Laser induced fluorescence spectroscopy of the Ca dimer deposited on helium and mixed helium/xenon clusters

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gaveau, Marc-André; Pothier, Christophe; Briant, Marc

2014-12-09

We study how the laser induced fluorescence spectroscopy of the calcium dimer deposited on pure helium clusters is modified by the addition of xenon atoms. In the wavelength range between 365 and 385 nm, the Ca dimer is excited from its ground state up to two excited electronic states leading to its photodissociation in Ca({sup 1}P)+Ca({sup 1}S): this process is monitored by recording the Ca({sup 1}P) fluorescence at 422.7nm. One of these electronic states of Ca{sub 2} is a diexcited one correlating to the Ca(4s4p{sup 3}P(+Ca(4s3d{sup 3}D), the other one is a repulsive state correlating to the Ca(4s4p1P)+Ca(4s21S) asymptote, accountingmore » for the dissociation of Ca{sub 2} and the observation of the subsequent Ca({sup 1}P) emission. On pure helium clusters, the fluorescence exhibits the calcium atomic resonance line Ca({sup 1}S←{sup 1}P) at 422.7 nm (23652 cm{sup −1}) assigned to ejected calcium, and a narrow red sided band corresponding to calcium that remains solvated on the helium cluster. When adding xenon atoms to the helium clusters, the intensity of these two features decreases and a new spectral band appears on the red side of calcium resonance line; the intensity and the red shift of this component increase along with the xenon quantity deposited on the helium cluster: it is assigned to the emission of Ca({sup 1}P) associated with the small xenon aggregate embedded inside the helium cluster.« less

Red Fluorescent Line Emission from Hydrogen Molecules in Diffuse Molecular Clouds

NASA Technical Reports Server (NTRS)

Neufeld, David A.; Spaans, Marco

1996-01-01

We have modeled the fluorescent pumping of electronic and vibrational emissions of molecular hydrogen (H2) within diffuse molecular clouds that are illuminated by ultraviolet continuum radiation. Fluorescent line intensities are predicted for transitions at ultraviolet, infrared, and red visible wavelengths as functions of the gas density, the visual extinction through the cloud, and the intensity of the incident UV continuum radiation. The observed intensity in each fluorescent transition is roughly proportional to the integrated rate of H2 photodissociation along the line of sight. Although the most luminous fluorescent emissions detectable from ground-based observatories lie at near-infrared wavelengths, we argue that the lower sky brightness at visible wavelengths makes the red fluorescent transitions a particularly sensitive probe. Fabry-Perot spectrographs of the type that have been designed to observe very faint diffuse Ha emissions are soon expected to yield sensitivities that will be adequate to detect H2 vibrational emissions from molecular clouds that are exposed to ultraviolet radiation no stronger than the mean radiation field within the Galaxy. Observations of red H2 fluorescent emission together with cospatial 21 cm H I observations could serve as a valuable probe of the gas density in diffuse molecular clouds.

Synthesis, Optical and Structural Properties of Copper Sulfide Nanocrystals from Single Molecule Precursors

PubMed Central

Ajibade, Peter A.; Botha, Nandipha L.

2017-01-01

We report the synthesis and structural studies of copper sulfide nanocrystals from copper (II) dithiocarbamate single molecule precursors. The precursors were thermolysed in hexadecylamine (HDA) to prepare HDA-capped CuS nanocrystals. The optical properties of the nanocrystals studied using UV–visible and photoluminescence spectroscopy showed absorption band edges at 287 nm that are blue shifted, and the photoluminescence spectra show emission curves that are red-shifted with respect to the absorption band edges. These shifts are as a result of the small crystallite sizes of the nanoparticles leading to quantum size effects. The structural studies were carried out using powder X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS), and atomic force microscopy. The XRD patterns indicates that the CuS nanocrystals are in hexagonal covellite crystalline phases with estimated particles sizes of 17.3–18.6 nm. The TEM images showed particles with almost spherical or rod shapes, with average crystallite sizes of 3–9.8 nm. SEM images showed morphology with ball-like microspheres on the surfaces, and EDS spectra confirmed the presence of CuS nanoparticles. PMID:28336865

zFP538, a yellow fluorescent protein from coral, belongs to the DsRed subfamily of GFP-like proteins but possesses the unexpected site of fragmentation.

PubMed

Zagranichny, Vasily E; Rudenko, Natalia V; Gorokhovatsky, Andrey Yu; Zakharov, Mikhail V; Shenkarev, Zakhar O; Balashova, Tamara A; Arseniev, Alexander S

2004-04-27

The yellow fluorescent protein (zFP538) from coral Zoanthus sp. belongs to a family of green fluorescent protein (GFP). Absorption and emission spectra of zFP538 show an intermediate bathochromic shift as compared with a number of recently cloned GFP-like red fluorescent and nonfluorescent chromoproteins of the DsRed subfamily. Here we report that the zFP538 chromophore is very close, if not identical, in chemical structure to that of DsRed. To gain insight into the mechanism of zFP538 fluorescence and chromophore structure and chemistry, we studied three chromophore-containing peptides isolated from enzymatic digests of zFP538. Like GFP and DsRed chromophores, these contain a p-hydroxybenzylideneimidazolinone moiety formed by Lys-66, Tyr-67, and Gly-68 of zFP538. One of the peptides studied, the hexapeptide FKYGDR derivative, is a proteolysis product of the zFP538 full-length polypeptide containing a GFP-type chromophore already formed and arrested at an earlier stage of maturation. The two other peptides are the derivatives of the pentapeptide KYGDR resulted from the protein in which the chromophore maturation process had been completed. One of these has an oxogroup at Lys-66 C(alpha) and is a hydrolysis product of another one, with the imino group at Lys-66 C(alpha). The N-unsubstituted imino moiety of the latter is generated by spontaneous polypeptide chain fragmentation at a very unexpected site, the former peptide bond between Phe-65 C' and Lys-66 N(alpha). Also observed in the entire protein under mild denaturing conditions, this fragmentation is likely the feature of native zFP538 chromophore that distinguishes it chemically from the DsRed chromophore.

Structures and interactions in N-methylacetamide-water mixtures studied by IR spectra and density functional theory

NASA Astrophysics Data System (ADS)

Zhang, Rong; Li, Haoran; Lei, Yi; Han, Shijun

2004-05-01

IR spectra have been performed to study the structures and interactions in N-methylacetamide and water mixtures. Because of the competitions of acceptor and donor of the strong hydrogen bonds, some interesting phenomena of red shifts and blue shifts are observed in νCO and νN-H. It is due to the blue-shifting C-H⋯O hydrogen bond, the νC-H blue shifts more obviously. Then some representative cluster structures are suggested and further investigated by density functional theory method. The changes in bond length and frequency shift of the structures give good reasons for the red shift and blue shift, which represents excellent agreement with the IR experiment. The investigations of IR spectra and DFT calculations reveal that the weak C-H⋯O interactions play different roles compared with the classical strong hydrogen bonds in the NMA-water mixtures.

Character displacement in the fighting colours of Hetaerina damselflies.

PubMed

Anderson, Christopher N; Grether, Gregory F

2010-12-07

Aggression between species is a seldom-considered but potentially widespread mechanism of character displacement in secondary sexual characters. Based on previous research showing that similarity in wing coloration directly influences interspecific territorial aggression in Hetaerina damselflies, we predicted that wing coloration would show a pattern of character displacement (divergence in sympatry). A geographical survey of four Hetaerina damselfly species in Mexico and Texas showed evidence for character displacement in both species pairs that regularly occurs sympatrically. Hetaerina titia, a species that typically has large black wing spots and small red wing spots, shifted to having even larger black spots and smaller red wing spots at sites where a congener with large red wing spots is numerically dominant (Hetaerina americana or Hetaerina occisa). Hetaerina americana showed the reverse pattern, shifting towards larger red wing spots where H. titia is numerically dominant. This pattern is consistent with the process of agonistic character displacement, but the ontogenetic basis of the shift remains to be demonstrated.

A Doppler-Cancellation Technique for Determining the Altitude Dependence of Gravitational Red Shift in an Earth Satellite

NASA Technical Reports Server (NTRS)

Badessa, R. S.; Kent, R. L.; Nowell, J. C.; Searle, C. L.

1960-01-01

A cancellation technique permits measurement of the frequency of a source moving relative to an observer without the obscuring effect of first-order Doppler shifts. The application of this method to a gravitational red shift experiment involving the use of an earth satellite containing a highly stable oscillator is described. The rapidity with which a measurement can be made permits the taking of data at various altitudes in a given elliptical orbit. Tropospheric and ionospheric effects upon the accuracy of results are estimated.

ATOTA-a very promising green fluorophore

NASA Astrophysics Data System (ADS)

Doan, Hung The

Despite the fact that fluorescence community nowadays has invested in developing near-infrared probes, green fluorescence dyes like fluorescein and substitutes are still among the most widely used fluorophores for labeling in cellular imaging and biomedical research. Trioxatriangulenium dye ATOTA + is a very promising green fluorophore with high extinction coefficient and outstanding fluorescence quantum yield. This study focuses on characterizing ATOTA+'s fundamental spectroscopic properties, including fluorescence and orientation of the transition moments. ATOTA's aggregation in aqueous solution and lipid bilayer membrane are also investigated. ATOTA+ has absorption maxima between 470 nm and 476 nm and emission maxima between 496 nm and 511 nm depending on the solvent. The molar extinction coefficient varies from 135,000 mol-1cm-1 in nonpolar dichloromethane to above 90,000 mol-1cm-1 in polar solvents such as methanol. The quantum yield of ATOTA+ is close to 1 in nonpolar DCM and decreases to 0.44 in polar DMF. ATOTA+'s fluorescence lifetimes vary between 3.25 ns in aprotic low polarity triacetin to 1.66 ns in polar DMF. Furthermore, both radiative and non-radiative rates are affected by solvent polarity. ATOTA+ has very low water solubility due to the presence of 6 diethyl substitutions, and forms H-aggregates with a blue-shifted absorption maxima around 450 nm and red-shifted emission maxima of 580 nm respectively with fluorescence lifetime above 20 ns. The excitation anisotropy approaches 0.35 at red edge of the absorption spectrum and shape of polarization spectrum suggests the presence of overlapping transition moments in a S0-S1 band which is confirmed by linear dichroism in stretched PVA film. In DMPC lipid vesicles, ATOTA + forms a tight ion pair with a counter anion and localizes in the hydrocarbon interior. Overall we conclude that ATOTA+ will be a highly useful and superior member of the green fluorophore family.

Preparation, characterization, physical properties, and photoconducting behaviour of anthracene derivative nanowires

NASA Astrophysics Data System (ADS)

Xiao, Jinchong; Yin, Zongyou; Yang, Bo; Liu, Yi; Ji, Li; Guo, Jun; Huang, Ling; Liu, Xuewei; Yan, Qingyu; Zhang, Hua; Zhang, Qichun

2011-11-01

Organic nanowires of 9,10-dibromoanthracene (DBA) and 9,10-dicyanoanthracene (DCNA) were obtained by adding the THF solution of DBA/DCNA into water containing P123 surfactants. The as-prepared nanowires were characterized by UV-vis, fluorescence spectra, Field Emission Scanning Electron Microscopy (FESEM), and Transmission Electron Microscopy (TEM). We found that DBA and DCNA nanowires emitted green light rather than blue light for molecules in THF solution. The red-shift UV and fluorescent spectra of DBA and DCNA nanowires implied that these nanowires were formed through J-aggregation. The photoconducting study of DBA/DCNA nanowire-based network on rGO/SiO2/Si shows different photocurrent behaviors upon irradiation, which displayed that electron transfer from DCNA nanowire to rGO was stronger than that of DBA nanowires to rGO.Organic nanowires of 9,10-dibromoanthracene (DBA) and 9,10-dicyanoanthracene (DCNA) were obtained by adding the THF solution of DBA/DCNA into water containing P123 surfactants. The as-prepared nanowires were characterized by UV-vis, fluorescence spectra, Field Emission Scanning Electron Microscopy (FESEM), and Transmission Electron Microscopy (TEM). We found that DBA and DCNA nanowires emitted green light rather than blue light for molecules in THF solution. The red-shift UV and fluorescent spectra of DBA and DCNA nanowires implied that these nanowires were formed through J-aggregation. The photoconducting study of DBA/DCNA nanowire-based network on rGO/SiO2/Si shows different photocurrent behaviors upon irradiation, which displayed that electron transfer from DCNA nanowire to rGO was stronger than that of DBA nanowires to rGO. Electronic supplementary information (ESI) available: XRD patterns and simulations, and FT-IR spectra. CCDC reference numbers 840471. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c1nr10655d

U.S. sulfur dioxide emission reductions: Shifting factors and a carbon dioxide penalty

DOE PAGES

Brown, Marilyn Ann; Li, Yufei; Massetti, Emanuele; ...

2017-01-18

For more than 20 years, the large-scale application of flue gas desulfurization technology has been a dominant cause of SO 2 emission reductions. From 1994–2004, electricity generation from coal increased, but the shift to low-sulfur coal eclipsed this. From 2004–2014, electricity generation from coal decreased, but a shift to higher-sulfur subbituminous and lignite coal overshadowed this. Here, the shift in coal quality has also created a CO 2 emissions penalty, representing 2% of the sector’s total emissions in 2014.

Assessment of emission scenarios for 2030 and impacts of black carbon emission reduction measures on air quality and radiative forcing in Southeast Asia

NASA Astrophysics Data System (ADS)

Agustian Permadi, Didin; Oanh, Nguyen Thi Kim; Vautard, Robert

2018-03-01

Our previously published paper (Permadi et al. 2018) focused on the preparation of emission input data and evaluation of WRF-CHIMERE performance in 2007. This paper details the impact assessment of the future (2030) black carbon (BC) emission reduction measures for Southeast Asia (SEA) countries on air quality, health and BC direct radiative forcing (DRF). The business as usual (BAU2030) projected emissions from the base year of 2007 (BY2007), assuming no intervention with the linear projection of the emissions based on the past activity data for Indonesia and Thailand and the sectoral GDP growth for other countries. The RED2030 featured measures to cut down emissions in major four source sectors in Indonesia and Thailand (road transport, residential cooking, industry, biomass open burning) while for other countries the Representative Concentration Pathway 8.5 (RCP8.5) emissions were assumed. WRF-CHIMERE simulated levels of aerosol species under BAU2030 and RED2030 for the modeling domain using the base year meteorology and 2030 boundary conditions from LMDZ-INCA. The extended aerosol optical depth module (AODEM) calculated the total columnar AOD and BC AOD for all scenarios with an assumption on the internal mixing state. Under RED2030, the health benefits were analyzed in terms of the number of avoided premature deaths associated with ambient PM2.5 reduction along with BC DRF reduction. Under BAU2030, the average number of the premature deaths per 100 000 people in the SEA domain would increase by 30 from BY2007 while under RED2030 the premature deaths would be cut down (avoided) by 63 from RED2030. In 2007, the maximum annual average BC DRF in the SEA countries was 0.98 W m-2, which would increase to 2.0 W m-2 under BAU2030 and 1.4 W m-2 under RED2030. Substantial impacts on human health and BC DRF reduction in SEA could result from the emission measures incorporated in RED2030. Future works should consider other impacts, such as for agricultural crop production, and the cost-benefit analysis of the measures' implementation to provide relevant information for policy making.

Multi-wavelength studies of wind driving cataclysmic variables

NASA Astrophysics Data System (ADS)

Witherick, Dugan Kenneth

This thesis presents several case studies of disc winds from high-state cataclysmic variable stars, based on multi-wavelength time-series spectroscopy. The research presented here primarily focuses on three low-inclination, nova-like systems: RW Sextansis, V592 Cassiopeiae and BZ Camelopardalis. The aim was to derive and compare key spectral line diagnostics of the outflows, spanning a wide range of ionisation and excitation using (new) FUSE, HST, IUE and optical data. Analysis of the far-UV time-series of RW Sex reveals the wind to be highly variable but generally confined to between ~ -1000 and ~ 0 km/s for all ionisation states; no evidence of the wind at red-shifted velocities is found. This wind is modulated on the orbital period of the system and it is argued that the observed variability is due to changes in the blue-shifted absorption rather than a variable velocity emission. The Balmer profiles observed in the optical time-series of V592 Cas were found to be characterised by three components: a broad, shallow absorption trough, a narrow central emission and a blue-shifted absorption from the disc wind. The wind is also found to be modulated on the systems orbital period, although this modulation is slightly out of phase with the Balmer emission radial velocities. The wind of BZ Cam was found to behave very differently to that of RW Sex and V592 Cas. At times, it was seen (in the Balmer lines and some of the He I lines) to be extremely strong and variable but at other times is was seemingly not present; there was no evidence to suggest that it is modulated on the orbital or any other period. This study is an immense source of data on CV disc winds and importantly tries to parameterise three nova-like CVs to understand the similarities and differences between them and their winds.

[Fluorescence spectroscopic characteristics of fulvic acid from the long-term located fertilization in black soil].

PubMed

Li, Yan-Ping; Wei, Dan; Zhou, Bao-Ku; Zhao, Yue; Zhang, Xi-Lin; Wei, Zi-Min; Li, Shu-Ling

2011-10-01

In order to investigate the effect of long-term located fertilization on soil fulvic acid (FA), in this study, four soil samples were taken from black soil with long-term located fertilization (about 30 year) in Harbin, Heilongjiang province. The fertilization treatments included control (CK), N, P and K fertilization (NPK), horse manure (OM), combination of organic manure and chemical fertilizations (MNPK). Soil FA was extracted from the samples and purified. The excitation, emission, synchronous, and three-dimensional-excitation emission matrix fluorescence spectroscopy (3DEEM) characteristics of the FA were determined. The excitation, emission and synchronous scan spectra all indicated that the main peaks of FA in the NPK treatment exhibited a significantly blue shift compared with CK, while those of MNPK, OM treatment caused a red shift to some extent. 3DEEM spectra of FA in all treatments exhibited four peaks (peak a, peak b, peak c, and peak d), compared with FA in CK, the wavelengths shift tendency of peak a, peak b, and peak c of FA 3DEEM in NPK, MNPK and OM treatments were similar to that of traditional spectra in FA. In order to provide quantitative information of FA humification degree in different treatments, we investigated the fluorescence index f450/500 (FI), area integration (A370-600 nm, A1 370-412 nm, A4 538-600 nm). Compared with CK, the f450/500, ratio of A1/A in NPK and A4/A in MNPK treatment increased by 4.62%, 6.12%, 7.22%, respectively. However, the f450/500, the ratio of A1/A in MNPK and A4/A in NPK treatment decreased by 3.86%, 15.31%, and 7.22% respectively. This indicated that NPK application gave a lower degree of FA humification, and combination of organic manure and chemical fertilizations would lead to a greater degree of FA aromatization in black soil with long-term located fertilization than CK.

Highly Efficient Spectrally Stable Red Perovskite Light-Emitting Diodes.

PubMed

Tian, Yu; Zhou, Chenkun; Worku, Michael; Wang, Xi; Ling, Yichuan; Gao, Hanwei; Zhou, Yan; Miao, Yu; Guan, Jingjiao; Ma, Biwu

2018-05-01

Perovskite light-emitting diodes (LEDs) have recently attracted great research interest for their narrow emissions and solution processability. Remarkable progress has been achieved in green perovskite LEDs in recent years, but not blue or red ones. Here, highly efficient and spectrally stable red perovskite LEDs with quasi-2D perovskite/poly(ethylene oxide) (PEO) composite thin films as the light-emitting layer are reported. By controlling the molar ratios of organic salt (benzylammonium iodide) to inorganic salts (cesium iodide and lead iodide), luminescent quasi-2D perovskite thin films are obtained with tunable emission colors from red to deep red. The perovskite/polymer composite approach enables quasi-2D perovskite/PEO composite thin films to possess much higher photoluminescence quantum efficiencies and smoothness than their neat quasi-2D perovskite counterparts. Electrically driven LEDs with emissions peaked at 638, 664, 680, and 690 nm have been fabricated to exhibit high brightness and external quantum efficiencies (EQEs). For instance, the perovskite LED with an emission peaked at 680 nm exhibits a brightness of 1392 cd m -2 and an EQE of 6.23%. Moreover, exceptional electroluminescence spectral stability under continuous device operation has been achieved for these red perovskite LEDs. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis and optical properties of metal (M) atom-doped polycarbosilane (PCS) with extended conjugation (M = Al, Dy, Er and Eu)

NASA Astrophysics Data System (ADS)

Yao, Rongqian; Zhao, Haoran; Feng, Zude; Chen, Lifu; Zhang, Ying

2013-10-01

Optical properties of metal atom-doped polycarbosilane (PCS) which originated from σ-conjugation effect were studied. Al, Dy, Er and Eu were introduced into PCS by one-pot method to yield polyaluminocarbosilane (PACS), polydysprosiumcarbosilane (PDCS), polyerbiumcarbosilane (PErCS) and polyeuropiumcarbosilane (PECS), respectively. Effects of oxidation curing and ultraviolet (UV) radiation on the photoluminescence (PL) properties of the samples were investigated. PL spectra show strong blue light-emissions and the intensity of PCS is enhanced by adding metal atoms. PACS with extended σ-conjugation exhibits an obvious PL red-shift, high intensity, high quantum yield and excellent oxidation resistance as compared with those of others. As treated under UV lamp for 3 h in air, PACS retains good UV resistance performance, owing to the AlOx (x = 4, 5, or 6) groups which effectively extend the σ-conjugation. The obtained results are expected to have important applications in active sources for electroluminescence (EL) devices, especially suitable for blue emission.

The faint intergalactic-medium red-shifted emission balloon: future UV observations with EMCCDs

NASA Astrophysics Data System (ADS)

Kyne, Gillian; Hamden, Erika T.; Lingner, Nicole; Morrissey, Patrick; Nikzad, Shouleh; Martin, D. Christopher

2016-08-01

We present the latest developments in our joint NASA/CNES suborbital project. This project is a balloon-borne UV multi-object spectrograph, which has been designed to detect faint emission from the circumgalactic medium (CGM) around low redshift galaxies. One major change from FIREBall-1 has been the use of a delta-doped Electron Multiplying CCD (EMCCD). EMCCDs can be used in photon-counting (PC) mode to achieve extremely low readout noise (¡ 1e-). Our testing initially focused on reducing clock-induced-charge (CIC) through wave shaping and well depth optimisation with the CCD Controller for Counting Photons (CCCP) from Nüvü. This optimisation also includes methods for reducing dark current, via cooling and substrate voltage adjustment. We present result of laboratory noise measurements including dark current. Furthermore, we will briefly present some initial results from our first set of on-sky observations using a delta-doped EMCCD on the 200 inch telescope at Palomar using the Palomar Cosmic Web Imager (PCWI).

[Performance dependence of organic light-emitting devices on the thickness of Alq3 emitting layer].

PubMed

Lian, Jia-rong; Liao, Qiao-sheng; Yang, Rui-bo; Zheng, Wei; Zeng, Peng-ju

2010-10-01

The dependence of opto-electronical characteristics in organic light-emitting devices on the thickness of Alq3 emitter layer was studied, where MoO3, NPB, and Alq3 were used as hole injector, hole transporter, and emitter/electron transporter, respectively. By increasing the thickness of Alq3 layer from 20 to 100 nm, the device current decreased gradually, and the EL spectra of devices performed a little red shift with an obvious broadening in long wavelength range but a little decrease in intensity of short wavelength range. The authors simulated the EL spectra using the photoluminescence (PL) spectra of Alq3 as Alq3 intrinsic emission, which coincided with the experimental EL spectra well. The simulated results suggested that the effect of interference takes the major role in broadening the long wavelength range of EL spectra, and the distribution of emission zone largely affects the profile of EL spectra in short wavelength range.

Ratiometric sensing of fluoride and acetate anions based on a BODIPY-azaindole platform and its application to living cell imaging.

PubMed

Mahapatra, Ajit Kumar; Maji, Rajkishor; Maiti, Kalipada; Adhikari, Susanta Sekhar; Das Mukhopadhyay, Chitrangada; Mandal, Debasish

2014-01-07

A new BODIPY-azaindole based fluorescent sensor 1 was designed and synthesized as a new colorimetric and ratiometric fluorescent chemosensor for fluoride. The binding and sensing abilities of sensor 1 towards various anions were studied by absorption, emission and (1)H NMR titration spectroscopies. The spectral responses of 1 to fluoride in acetonitrile-water were studied: an approximately 69 nm red shift in absorption and ratiometric fluorescent response was observed. The striking light yellow to deep brown color change in ambient light and green to blue emission color change are thought to be due to the deprotonation of the indole moiety of the azaindole fluorophore. From the changes in the absorption, fluorescence, and (1)H NMR titration spectra, proton-transfer mechanisms were deduced. Density function theory and time-dependent density function theory calculations were conducted to rationalize the optical response of the sensor. Results were supported by confocal fluorescence imaging and MTT assay of live cells.

Photoluminescence and lasing properties of MAPbBr3 single crystals grown from solution

NASA Astrophysics Data System (ADS)

Aryal, Sandip; Lafalce, Evan; Zhang, Chuang; Zhai, Yaxin; Vardeny, Z. Valy

Recent studies of solution-grown single crystals of inorganic-organic hybrid lead-trihalide perovskites have suggested that surface traps may play a significant role in their photophysics. We study electron-hole recombination in single crystal MAPbBr3 through such trap states using cw photoluminescence (PL) and ps transient photoinduced absorption (PA) spectroscopies. By varying the depth of the collecting optics we examined the contributions from surface and bulk radiative recombination. We found a surface dominated PL band at the band-edge that is similar to that observed from polycrystalline thin films, as well as a weaker red-shifted emission band that originates from the bulk crystal. The two PL bands are distinguished in their temperature, excitation intensity and polarization dependencies, as well as their ps dynamics. Additionally, amplified spontaneous emission and crystal-related cavity lasing modes were observed in the same spectral range as the PL band assigned to the surface recombination. This work was funded by AFOSR through MURI Grant RA 9550-14-1-0037.

Laser and thermal properties of Nd:YGd2Sc2Al2GaO12 garnet ceramic Laser and thermal properties of Nd:YSGG garnet ceramic

NASA Astrophysics Data System (ADS)

Brenier, A.; Alombert-Goget, G.; Guyot, Y.; Boulon, G.

2012-10-01

The absorption and fluorescence properties of the Nd-doped YGd2Sc2Al2GaO12 mixed garnet ceramics have been measured at different temperatures. Under laser diode pumping an efficient laser emission has been demonstrated with 45% slope efficiency. The emission is constituted by two lines at 1058.6 and 1061.3 nm, subjected to a red shift and a variable relative intensity versus pump power. The role of the temperature has been investigated playing with the cavity parameters. The thermal conductivity of the 1% Nd-doped material has been determined (3.2 W/m/K) measuring the radial temperature distribution of the exit face of the sample including the axial heat flow in the analysis. The M2 beam quality factor and the dioptric power of the thermal lens have been investigated versus the pump power. The thermo-optic coefficient χ was determined as 44.4×10-6 K-1.

Pollinator responses to floral colour change, nectar, and scent promote reproductive fitness in Quisqualis indica (Combretaceae).

PubMed

Yan, Juan; Wang, Gang; Sui, Yi; Wang, Menglin; Zhang, Ling

2016-04-13

Floral colour change is visual signals for pollinators to avoid old flowers and increase pollination efficiency. Quisqualis indica flowers change colour from white to pink to red may be associated with a shift from moth to butterfly pollination. To test this hypothesis, we investigated Q. indica populations in Southwest China. Flowers secreted nectar continuously from the evening of anthesis until the following morning, then decreased gradually with floral colour change. The scent compounds in the three floral colour stages were similar; however, the scent composition was different, and the scent emission rate decreased from the white to red stage. Dichogamy in Q. indica prevents self-pollination and interference of male and female functions. Controlled pollinations demonstrated that this species is self-incompatible and needs pollinators for seed production. Different pollinators were attracted in each floral colour stage; mainly moths at night and bees and butterflies during the day. Observations of open-pollinated inflorescences showed that white flowers had a higher fruit set than pink or red flowers, indicating the high contribution of moths to reproductive success. We concluded that the nectar and scent secretion are related to floral colour change in Q. indica, in order to attract different pollinators and promote reproductive fitness.

Insight into the performance of multi-color InGaN/GaN nanorod light emitting diodes.

PubMed

Robin, Y; Bae, S Y; Shubina, T V; Pristovsek, M; Evropeitsev, E A; Kirilenko, D A; Davydov, V Yu; Smirnov, A N; Toropov, A A; Jmerik, V N; Kushimoto, M; Nitta, S; Ivanov, S V; Amano, H

2018-05-09

We report on the thorough investigation of light emitting diodes (LEDs) made of core-shell nanorods (NRs) with InGaN/GaN quantum wells (QWs) in the outer shell, which are grown on patterned substrates by metal-organic vapor phase epitaxy. The multi-bands emission of the LEDs covers nearly the whole visible region, including UV, blue, green, and orange ranges. The intensity of each emission is strongly dependent on the current density, however the LEDs demonstrate a rather low color saturation. Based on transmission electron microscopy data and comparing them with electroluminescence and photoluminescence spectra measured at different excitation powers and temperatures, we could identify the spatial origination of each of the emission bands. We show that their wavelengths and intensities are governed by different thicknesses of the QWs grown on different crystal facets of the NRs as well as corresponding polarization-induced electric fields. Also the InGaN incorporation strongly varies along the NRs, increasing at their tips and corners, which provides the red shift of emission. With increasing the current, the different QW regions are activated successively from the NR tips to the side-walls, resulting in different LED colors. Our findings can be used as a guideline to design effectively emitting multi-color NR-LEDs.

183 GHz water line variation: An energetic outburst in orion KL

NASA Technical Reports Server (NTRS)

Kuiper, T. B. H.; Kuiper, E. N. R.; Swanson, P. N.; Dickinson, D. F.; Klein, M. J.; Zimmermann, P.

1984-01-01

Observations of the 3(13)-2(20) transition of water vapor in the direction of Ori MC1 in 1980 February show a 50% flux increase and an apparent additional red shift of approximately 2 km/s relative to the line observed in 1977 December. From a detailed examination of the amplitude and frequency calibration, it appears unlikely that the effect is due to systematic error. The increase is attributed to the appearance of a new component at a velocity of 12 km/s with respect to the local standard of rest. The new component also has broad wings. Increased emission from a region in the high-velocity core of Ori MC1 can be due either to additional far-IR radiation to pump the 1983 GHz transition or to a change in the physical conditions in the gas. Statistical equilibrium calculations using the large-velocity-gradient formalism were carried out to develop a model for the emission. The calculations support a model in which the gas in the region of enhanced emission is hotter than the dust. The temporal coincidence between the 183 GHZ increase and the 22 GH1 water maser outburst suggests a common, impulsive cause, which has heated the gas in a part of the HV source, enhancing the emission in both transitions.

Study on photophysical and aggregation induced emission recognition of 1,8-naphthalimide probe for casein by spectroscopic method

NASA Astrophysics Data System (ADS)

Sun, Yang; Liu, Zhen; Liang, Xuhua; Fan, Jun; Han, Quan

2013-05-01

A novel water-soluble 1,8-naphthalimide derivative 1, bearing two acetic carboxylic groups, exhibited fluorescent turn-on recognition for casein based on the aggregation induced emission (AIE) character. The photophysical properties of 1 consisting of donor and acceptor units were investigated in different solutions. The fluorescence intensity decreased through taking advantage of twisted intramolecular charge transfer (TICT) and self-association emission with increasing solvent polarity. Moreover, the spectral red-shift and intensity quench in protic solvents were caused by the excited-state hydrogen bond strengthening effect. Density Functional Theory (DFT) calculations revealed that 1 exhibited a strong TICT character. The AIE mechanism of 1 with casein was due to 1 docked in the hydrophobic cavity between sub-micelles and bound with Tyr and Trp residues, resulting in the aggregation of 1 on the casein surface and emission enhancement. Based on this, a novel casein assay method was developed. The proposed exhibited a good linear range from 0.1 to 22 μg mL-1, with the detection limit of 2.8 ng mL-1. Satisfactory reproducibility, reversibility and a short response time were realized. This method was applied to the determination of casein in milk powder samples and the results were in good agreement with the result of Biuret method.

Imaging of Biological Cells Using Luminescent Silver Nanoparticles

NASA Astrophysics Data System (ADS)

Kravets, Vira; Almemar, Zamavang; Jiang, Ke; Culhane, Kyle; Machado, Rosa; Hagen, Guy; Kotko, Andriy; Dmytruk, Igor; Spendier, Kathrin; Pinchuk, Anatoliy

2016-01-01

The application of luminescent silver nanoparticles as imaging agents for neural stem and rat basophilic leukemia cells was demonstrated. The experimental size dependence of the extinction and emission spectra for silver nanoparticles were also studied. The nanoparticles were functionalized with fluorescent glycine dimers. Spectral position of the resonance extinction and photoluminescence emission for particles with average diameters ranging from 9 to 32 nm were examined. As the particle size increased, the spectral peaks for both extinction and the intrinsic emission of silver nanoparticles shifted to the red end of the spectrum. The intrinsic photoluminescence of the particles was orders of magnitude weaker and was spectrally separated from the photoluminescence of the glycine dimer ligands. The spectral position of the ligand emission was independent of the particle size; however, the quantum yield of the nanoparticle-ligand system was size-dependent. This was attributed to the enhancement of the ligand's emission caused by the local electric field strength's dependence on the particle size. The maximum quantum yield determined for the nanoparticle-ligand complex was (5.2 ± 0.1) %. The nanoparticles were able to penetrate cell membranes of rat basophilic leukemia and neural stem cells fixed with paraformaldehyde. Additionally, toxicity studies were performed. It was found that towards rat basophilic leukemia cells, luminescent silver nanoparticles had a toxic effect in the silver atom concentration range of 10-100 μM.

Identifying the 630 nm auroral arc emission height: A comparison of the triangulation, FAC profile, and electron density methods

NASA Astrophysics Data System (ADS)

Megan Gillies, D.; Knudsen, D.; Donovan, E.; Jackel, B.; Gillies, R.; Spanswick, E.

2017-08-01

We present a comprehensive survey of 630 nm (red-line) emission discrete auroral arcs using the newly deployed Redline Emission Geospace Observatory. In this study we discuss the need for observations of 630 nm aurora and issues with the large-altitude range of the red-line aurora. We compare field-aligned currents (FACs) measured by the Swarm constellation of satellites with the location of 10 red-line (630 nm) auroral arcs observed by all-sky imagers (ASIs) and find that a characteristic emission height of 200 km applied to the ASI maps gives optimal agreement between the two observations. We also compare the new FAC method against the traditional triangulation method using pairs of all-sky imagers (ASIs), and against electron density profiles obtained from the Resolute Bay Incoherent Scatter Radar-Canadian radar, both of which are consistent with a characteristic emission height of 200 km.

Near-saturated red emitters: four-coordinate copper(i) halide complexes containing 8-(diphenylphosphino)quinoline and 1-(diphenylphosphino)naphthalene ligands.

PubMed

Liu, Li-Ping; Li, Qian; Xiang, Song-Po; Liu, Li; Zhong, Xin-Xin; Liang, Chen; Li, Guang Hua; Hayat, Tasawar; Alharbi, Njud S; Li, Fa-Bao; Zhu, Nian-Yong; Wong, Wai-Yeung; Qin, Hai-Mei; Wang, Lei

2018-06-07

Recently, highly emissive neutral copper halide complexes have received much attention. Here, a series of four-coordinate mononuclear Cu(i) halide complexes, [CuX(dpqu)(dpna)] (dpqu = 8-(diphenylphosphino)quinoline, dpna = 1-(diphenylphosphino)naphthalene, X = I (1), Br (2) and Cl (3)), were synthesized, and their molecular structures and photophysical properties were investigated. These complexes exhibit near-saturated red emission in the solid state at room temperature and have peak emission wavelengths at 669-691 nm with microsecond lifetimes (τ = 0.46-1.80 μs). Small S1-T1 energy gaps in the solid state indicate that the emission occurs from a thermally activated excited singlet state at ambient temperature. The emission of the complexes 1-3 mainly originates from MLCT transition. The solution-processed devices of complex 1 exhibit stable red emission with a CIE(x, y) of (0.62, 0.38) for a doped device and (0.63, 0.37) for a non-doped device.

Molecular Self-Assembly of Group 11 Pyrazolate Complexes as Phosphorescent Chemosensors for Detection of Benzene

NASA Astrophysics Data System (ADS)

Ghazalli, N. F.; Yuliati, L.; Lintang, H. O.

2018-01-01

We highlight the systematic study on vapochromic sensing of aromatic vapors such as benzene using phosphorescent trinuclear pyrazolate complexes (2) with supramolecular assembly of a weak intermolecular metal-metal interaction consisting of 4-(3,5-dimethoxybenzyl)-3,5-dimethyl pyrazole ligand (1) and group 11 metal ions (Cu(I), Ag(I), Au(I)). The resulting chemosensor 2(Cu) revealed positive response to benzene vapors in 5 mins by blue-shifting its emission band in 44 nm (from 616 to 572 nm) and emitted bright orange to green, where this change cannot be recovered even with external stimuli. Comparing to 2(Ag) with longer metal-metal distance (473 nm) with same sensing time and quenching in 37%, 2(Au) gave quenching in 81% from its original intensity at 612 nm with reusability in 82% without external stimuli and emitted less emissive of red-orange from its original color. The shifting phenomenon in 2(Cu) suggests diffusion of benzene vapors to inside molecules for formation of intermolecular interaction with Cu(I)-Cu(I) interaction while quenching phenomenon in 2(Au) suggests diffusion of benzene vapors to between the Au(I)-Au(I) interaction. These results indicate that suitable molecular structure of ligand and metal ion in pyrazolate complex is important for designing chemosensor in the detection of benzene vapors.

Heat-induced reorganization of the structure of photosystem II membranes: role of oxygen evolving complex.

PubMed

Busheva, Mira; Tzonova, Iren; Stoitchkova, Katerina; Andreeva, Atanaska

2012-12-05

The sensitivity of the green plants' photosystem II (PSII) to high temperatures is investigated in PSII enriched membranes and in membranes, from which the oxygen evolving complex is removed. Using steady-state 77 K fluorescence and resonance Raman spectroscopy we analyze the interdependency between the temperature-driven changes in structure and energy distribution in the PSII supercomplex. The results show that the heat treatment induces different reduction of the 77 K fluorescence emission in both types of investigated membranes: (i) an additional considerable decrease of the overall fluorescence emission in Tris-washed membranes as compared to the native membranes; (ii) a transition point at 42°C(,) observed only in native membranes; (iii) a sharp reduction of the PSII core fluorescence in Tris-washed membranes at temperatures higher than 50°C; (iv) a 3 nm red-shift of F700 band's maximum in Tris-washed membranes already at 20°C and its further shift by 1 nm at temperature increase. Both treatments intensified their action by increasing the aggregation and dissociation of the peripheral light harvesting complexes. The oxygen-evolving complex, in addition to its main function to produce O(2), increases the thermal stability of PSII core by strengthening the connection between the core and the peripheral antenna proteins and by keeping their structural integrity. Copyright © 2012 Elsevier B.V. All rights reserved.

Analogues of uracil nucleosides with intrinsic fluorescence (NIF-analogues): synthesis and photophysical properties.

PubMed

Segal, Meirav; Fischer, Bilha

2012-02-28

Uridine cannot be utilized as fluorescent probe due to its extremely low quantum yield. For improving the uracil fluorescence characteristics we extended the natural chromophore at the C5 position by coupling substituted aromatic rings directly or via an alkenyl or alkynyl linker to create fluorophores. Extension of the uracil base was achieved by treating 5-I-uridine with the appropriate boronic acid under the Suzuki coupling conditions. Analogues containing an alkynyl linker were obtained from 5-I-uridine and the suitable boronic acid in a Sonogashira coupling reaction. The uracil fluorescent analogues proposed here were designed to satisfy the following requirements: a minimal chemical modification at a position not involved in base-pairing, resulting in relatively long absorption and emission wavelengths and high quantum yield. 5-((4-Methoxy-phenyl)-trans-vinyl)-2'-deoxy-uridine, 6b, was found to be a promising fluorescent probe. Probe 6b exhibits a quantum yield that is 3000-fold larger than that of the natural chromophore (Φ 0.12), maximum emission (478 nm) which is 170 nm red shifted as compared to uridine, and a Stokes shift of 143 nm. In addition, since probe 6b adopts the anti conformation and S sugar puckering favored by B-DNA, it makes a promising nucleoside analogue to be incorporated in an oligonucleotide probe for detection of genetic material.

A computational study of hydrogen-bonded X3CH⋯YZ (X = Cl, F, NC; YZ = FLi, BF, CO, N2) complexes

NASA Astrophysics Data System (ADS)

McDowell, Sean A. C.

2018-03-01

An MP2/6-311++G(3df,3pd) computational study of a series of hydrogen-bonded complexes X3CH⋯YZ (X = Cl, F, NC; YZ = FLi, BF, CO, N2) was undertaken to assess the trends in the relative stability and other molecular properties with variation of both the X group and the chemical hardness of the Y atom of YZ. The red- and blue-shifting propensities of the proton donor X3CH were investigated by considering the Csbnd H bond length change and its associated vibrational frequency shift. The proton donor Cl3CH, which has a positive dipole moment derivative with respect to Csbnd H bond extension, tends to form red-shifted complexes, this tendency being modified by the hardness (and dipole moment) associated with the proton acceptor. On the other hand, F3CH has a negative dipole moment derivative and tends to form blue-shifted complexes, suggesting that as X becomes more electron-withdrawing, the proton donor should have a negative dipole moment derivative and form blue-shifted complexes. Surprisingly, the most polar proton donor (NC)3CH was found to have a positive dipole moment derivative and produces red-shifted complexes. A perturbative model was found useful in rationalizing the trends for the Csbnd H bond length change and associated frequency shift.

Reconstructing the metric of the local Universe from number counts observations

DOE Office of Scientific and Technical Information (OSTI.GOV)

Vallejo, Sergio Andres; Romano, Antonio Enea, E-mail: antonio.enea.romano@cern.ch

Number counts observations available with new surveys such as the Euclid mission will be an important source of information about the metric of the Universe. We compute the low red-shift expansion for the energy density and the density contrast using an exact spherically symmetric solution in presence of a cosmological constant. At low red-shift the expansion is more precise than linear perturbation theory prediction. We then use the local expansion to reconstruct the metric from the monopole of the density contrast. We test the inversion method using numerical calculations and find a good agreement within the regime of validity ofmore » the red-shift expansion. The method could be applied to observational data to reconstruct the metric of the local Universe with a level of precision higher than the one achievable using perturbation theory.« less

Molecular design of TiO2 for gigantic red shift via sublattice substitution.

PubMed

Shao, Guosheng; Deng, Quanrong; Wan, Lin; Guo, Meilan; Xia, Xiaohong; Gao, Yun

2010-11-01

The effects of 3d transition metal doping in TiO2 phases have been simulated in detail. The results of modelling indicate that Mn has the biggest potential among 3d transition metals, for the reduction of energy gap and the introduction of effective intermediate bands to allow multi-band optical absorption. On the basis of theoretical formulation, we have incorporated considerable amount of Mn in nano-crystalline TiO2 materials. Mn doped samples demonstrate significant red shift in the optical absorption edge, with a secondary absorption edge corresponding to theoretically predicted intermediate bands/states. The gigantic red shift achievable in Mn-doped TiO2 is expected to extend the useful TiO2 functionalities well beyond the UV threshold via the optical absorption of both visible and infrared photon irradiance.

White polymeric light-emitting diodes with high color rendering index

NASA Astrophysics Data System (ADS)

Niu, Xiaodi; Ma, Liang; Yao, Bing; Ding, Junqiao; Tu, Guoli; Xie, Zhiyuan; Wang, Lixiang

2006-11-01

The efficient white polymeric light-emitting diodes based on a white emissive polymer doped with a red phosphorescent dopant were fabricated by spin-coating method. The emission spectrum of the device is broadened to cover the full visible region by doping the red phosphorescent dye and thereby realizes white emission with high color-rendering index (CRI). By controlling the contents of the doped electron-transporting 2-(4-biphenylyl)-5-(4-tert-butylphenyl)-1,3,4-oxadiazole and the red phosphorescent dopant, a luminous efficiency as high as 5.3cd/A and a power efficiency of 3lm/W were obtained with a CRI of 92.

Amplified spontaneous emission of pyranyliden derivatives in PVK matrix

NASA Astrophysics Data System (ADS)

Vembris, Aivars; Zarinsh, Elmars; Kokars, Valdis

2016-04-01

One of the well-known red light emitting laser dyes is 4-(dicyanomethylene)-2-methyl-6-(4-dimethylaminostyryl)-4Hpyran (DCM). Amplified spontaneous emission (ASE) has been widely investigated of DCM molecules or its derivatives in polymer or low molecular weight matrix. The main issue for these molecules is aggregation which limits doping concentration in matrix. Lowest ASE threshold values within concentration range of 2 and 4 wt% were obtained. In this work ASE properties of two original DCM derivatives in poly(N-vinylcarbazole) (PVK) at various concentrations will be discussed. One of the derivatives is the same DCM dye with replaced butyl groups at electron donor part with bulky trytiloxyethyl groups (DWK-1). These groups do not influence electron transitions in the dye but prevent aggregation of the molecules. Second derivative (DWK-2) consists of two equal donor groups with the attached trytiloxyethyl groups. All results were compared with DCM:PVK system. Photoluminescence quantum yield (PLQY) is almost three times larger for DWK-1 concentration up to 20wt% with respect to DCM systems. PLQY was saturated on 0.06 at higher DWK-1 concentrations. Bulky trytiloxyethyl groups prevent aggregation of the molecules thus decreasing interaction between dyes and numbers of non-radiative decays. Red shift of photoluminescence and amplified spontaneous emission at higher concentrations were observed due to the solid state solvation effect. Increases of dye density in matrix with smaller lose in PLQY resulted in low ASE threshold energy. The lowest threshold value was obtained around 29 μJ/cm2 in DWK-1:PVK films.

A Comparison of Single-Molecule Emission in Aluminum and Gold Zero-Mode Waveguides

DOE PAGES

Martin, William Elliott; Srijanto, Bernadeta R.; Collier, C. Patrick; ...

2016-08-06

We characterized the effect of gold and aluminum zero-mode waveguides (ZMWs) on the brightness of immobilized single emitters by probing fluorophores that absorb in the green and red regions of the visible spectrum. Aluminum ZMWs enhance the emission of Atto565 fluorophores upon green excitation, but they do not enhance the emission of Atto647N fluorophores upon red excitation. Gold ZMWs increase emission of both fluorophores with Atto647N showing enhancement that is threefold higher than that observed for Atto565. Our work indicates that 200 nm gold ZMWs are better suited for single-molecule fluorescence studies in the red region of the visible spectrum,more » while aluminum appears more suited for the green region of the visible spectrum.« less

A Comparison of Single-Molecule Emission in Aluminum and Gold Zero-Mode Waveguides

DOE Office of Scientific and Technical Information (OSTI.GOV)

Martin, William Elliott; Srijanto, Bernadeta R.; Collier, C. Patrick

We characterized the effect of gold and aluminum zero-mode waveguides (ZMWs) on the brightness of immobilized single emitters by probing fluorophores that absorb in the green and red regions of the visible spectrum. Aluminum ZMWs enhance the emission of Atto565 fluorophores upon green excitation, but they do not enhance the emission of Atto647N fluorophores upon red excitation. Gold ZMWs increase emission of both fluorophores with Atto647N showing enhancement that is threefold higher than that observed for Atto565. Our work indicates that 200 nm gold ZMWs are better suited for single-molecule fluorescence studies in the red region of the visible spectrum,more » while aluminum appears more suited for the green region of the visible spectrum.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Polvonov, B. Z., E-mail: uzferfizika@mail.ru; Yuldashev, N. Kh.

The band of intrinsic (e–h) radiation emission by the subsurface potential barriers of crystal grains and the edge doublet band arising as LO-phonon replicas of the e–h band are observed in the spectra of the low-temperature (4.2 K) photoluminescence of fine-grained (with a grain size of d{sub cr} ≤ 1 µm) CdTe films. Film doping with the In impurity results in quenching of the doublet band, while heat treatment leads to activation of the intrinsic band, a short-wavelength shift of the red boundary (ΔE{sub r} = 16–29 meV) and the halfwidth modulation (Δ{sub A} = 6–17 meV) of which correlatemore » with the height of micropotential barriers and the temperature of recombining hot photocarriers.« less

Herschel Detects a Massive Dust Reservoir in Supernova 1987A

NASA Technical Reports Server (NTRS)

Matsuura, M.; Dwek, E.; Meixner, M.; Otsuka, M.; Babler, B.; Barlow, M. J.; Roman-Duval, J.; Engelbracht, C.; Sandstrom K.; Lakicevic, M.;

Red Emission of SrAl2O4:Mn4+ Phosphor for Warm White Light-Emitting Diodes

NASA Astrophysics Data System (ADS)

Chi, N. T. K.; Tuan, N. T.; Lien, N. T. K.; Nguyen, D. H.

2018-05-01

In this work, SrAl2O4:Mn4+ phosphor is prepared by co-precipitation. The phase structure, morphology, composition and luminescent performance of the phosphor are investigated in detail with x-ray diffraction, field emission scanning electron microscopy, steady-state photoluminescence (PL) spectra, and temperature-dependent PL measurements. The phosphor shows a strong red emission peak at ˜ 690 nm, which is due to the transition between electronic levels and the electric dipole transition 2Eg to 4A2g of Mn4+ ions located at the sites with D3d local symmetry. The sample doped with 0.04 mol.% Mn4+ exhibits intense red emission with high thermal stability and appropriate International Commission on Illumination (CIE) coordinates (x = 0.6959, y = 0.2737). It is also found that the phosphor absorption in an extended band from 250 nm to 500 nm has three peaks at 320 nm, 405 nm, and 470 nm, which match well with the emission band of ultraviolet (UV) lighting emission diode (LED) or blue LED chips. These results demonstrate that SrAl2O4:Mn4+ phosphor can play the role of activator in narrow red-emitting phosphor, which is potentially useful in UV (˜ 320 nm) or blue (˜ 460 nm) LED.

Temperature dependence of excitonic emission in [(CH3)2NH2]3[BiI6] organic-inorganic natural self assembled bimodal quantum dots

NASA Astrophysics Data System (ADS)

Abid, Haitham; Samet, Amira; Mlayah, Adnen; Boughzala, Habib; Abid, Younes

2017-11-01

This paper reports on the optical properties of organic - inorganic natural self assembled bimodal quantum dots (dimetylammonium) hexa-iodobismuthate [(CH3)2NH2]3[BiI6]. The crystal structure consists of isolated BiI6 octahedra, as inorganic ions, surrounded by dimethylamine cations. At room temperature, we investigate the optical properties by: UV/Vis absorption, ellipsometry, diffuse reflectance and photoluminescence. A broad Gaussian-shape luminescence band with a large stokes shift is observed in the red spectral range at 2.15 eV, due to radiative recombination of confined excitons in BiI quantum dots, suggesting that excitons are self trapped. The temperature-dependence of the PL emission is investigated. The observed S-shaped emission behavior is explained by thermal escape occurring at lower temperatures for high-energy dots and carriers being recaptured by dots emitting on the low-energy side of the distribution. A rate equation model, showing agreement with the experimental results, is used to investigate the thermal redistribution of the charge carriers. Exciton binding energies of 149.125 and 295.086 meV were determined from the modified Arrhenius analysis.

Crystalline silicon carbide nanoparticles encapsulated in branched wavelike carbon nanotubes: synthesis and optical properties.

PubMed

Xi, Guangcheng; Yu, Shijun; Zhang, Rui; Zhang, Meng; Ma, Dekun; Qian, Yitai

2005-07-14

A novel nanostructure, cubic silicon carbide (3C-SiC) nanoparticles encapsulated in branched wavelike carbon nanotubes have been prepared by a reaction of 1,2-dimenthoxyethane (CH3OCH2CH2OCH3), SiCl4, and Mg in an autoclave at 600 degrees C. According to X-ray powder diffraction, the products are composed of 3C-SiC and carbon. TEM and HRTEM images show that the as-synthesized products are composed of 3C-SiC nanoparticles encapsulated in branched carbon nanotubes with wavelike walls. The diameter of the 3C-SiC cores is approximately 20-40 nm and the thickness of the carbon shells is about 3-5 nm. In Raman scattering spectroscopy, both the TO (Gamma) phonon line and the LO (Gamma) phonon line have red shifts about 6 cm(-1) relative to that for the bulk 3C-SiC. The photoluminescence (PL) spectrum shows that there are two emission peaks: blue light emission (431 nm) and violet light emission (414 nm). A sequential deposition growth process (with cores as the templates for the shells) for the nanostructure was proposed.

Strong-Field Emission From High Aspect Ratio Si Emitter Arrays

NASA Astrophysics Data System (ADS)

Keathley, Phillip; Swanwick, Michael; Sell, Alexander; Putnam, William; Guerrera, Stephen; Velásquez-García, Luis; Kärtner, Franz

2013-03-01

We discuss photoelectron emission from an arrays of high aspect ratio, sharp Si emitters both experimentally and theoretically. The structures are prepared from highly doped single-crystal silicon having a pencil-like shape with end radii of curvature of around 10 nm. The tips were illuminated at a grazing incidence of roughly 84deg.with a laser pulse having a center wavelength of 800 nm, and a pulse duration of 35 fs from a regenerative amplifier system. Native oxide coated Si tips were characterized using a time of flight (TOF) electron energy spectrometer. An annealing process was observed, resulting in a red shift of the energy spectra along with an increased electron yield. Total current yield from samples having the oxide stripped were also studied. Apeak total emission of 0.68 pC/bunch, corresponding to around 1.5x103 electrons/tip/pulse was observed at a DC bias of 70 V. Both spectral and current characterization results are consistent with a stong-field photoemission process at the surface of the tip apex. This work was funded by Defense Advanced Research Projects Agency (DARPA)/Microsystems Technology Office and the Space and Naval Warfare Systems Center (SPAWAR) under contract N66001-11-1-4192.

Photoluminescence properties of polystyrene-hosted fluorophore thin films

NASA Astrophysics Data System (ADS)

Chakraborty, Subha; Harris, Katherine; Huang, Mengbing

2016-12-01

We report on a photo-luminescence study of four different fluorophores: Coumarin 6, 2,5-Diphenyloxazole (PPO), 1,4-Bis(5-phenyl-2-oxazolyl)benzene (POPOP) and Para-terpehnyl (PTP), doped in a polystyrene-based thin film. All of the samples are prepared by spin coating from a non-polar polymer solution at various concentrations. Their emission spectra and transient properties are characterized by photoluminescence measurements. Red-shifts in the emission spectra are observed for all four types of fluorophores as their concentration increases. We explain this phenomenon based on concentration dependence of solvatochromic effects and the results show good agreement with existing literature. We also show that the singlet-singlet annihilation processes are possibly a prevalent mechanism in the high concentration regime that affects the steady state and transient emission characteristics of the fluors. With the exception of PTP, photoluminescence quenching occurs as the fluorophore concentration in the polymer is increased. Rate equations for excited state decay mechanisms are analysed by considering different radiative and non-radiative energy transfer mechanisms. The results show consistency with our experimental observations. PTP shows the best photoluminescence results as an efficient fluor in the thin film, whereas PPO shows the strongest concentration dependent quenching and an anomalous lifetime distribution.

Red-Shifting versus Blue-Shifting Hydrogen Bonds: Perspective from Ab Initio Valence Bond Theory.

PubMed

Chang, Xin; Zhang, Yang; Weng, Xinzhen; Su, Peifeng; Wu, Wei; Mo, Yirong

2016-05-05

Both proper, red-shifting and improper, blue-shifting hydrogen bonds have been well-recognized with enormous experimental and computational studies. The current consensus is that there is no difference in nature between these two kinds of hydrogen bonds, where the electrostatic interaction dominates. Since most if not all the computational studies are based on molecular orbital theory, it would be interesting to gain insight into the hydrogen bonds with modern valence bond (VB) theory. In this work, we performed ab initio VBSCF computations on a series of hydrogen-bonding systems, where the sole hydrogen bond donor CF3H interacts with ten hydrogen bond acceptors Y (═NH2CH3, NH3, NH2Cl, OH(-), H2O, CH3OH, (CH3)2O, F(-), HF, or CH3F). This series includes four red-shifting and six blue-shifting hydrogen bonds. Consistent with existing findings in literature, VB-based energy decomposition analyses show that electrostatic interaction plays the dominating role and polarization plays the secondary role in all these hydrogen-bonding systems, and the charge transfer interaction, which denotes the hyperconjugation effect, contributes only slightly to the total interaction energy. As VB theory describes any real chemical bond in terms of pure covalent and ionic structures, our fragment interaction analysis reveals that with the approaching of a hydrogen bond acceptor Y, the covalent state of the F3C-H bond tends to blue-shift, due to the strong repulsion between the hydrogen atom and Y. In contrast, the ionic state F3C(-) H(+) leads to the red-shifting of the C-H vibrational frequency, owing to the attraction between the proton and Y. Thus, the relative weights of the covalent and ionic structures essentially determine the direction of frequency change. Indeed, we find the correlation between the structural weights and vibrational frequency changes.

Using DNA to Design Plasmonic Metamaterials with Tunable Optical Properties

DTIC Science & Technology

2014-01-01

using both UV –vis spectroscopy for ensemble measurements and optical micro- spectrophotometry for individual superlattice electric fi elds at...lated data). The red-shift seen between the micro-spectropho- tometer measurements (Figure 3 b) and the UV –vis ensemble measurements (Figure 3 a...the measurements. Using UV –vis spectroscopy ( Figure 3 a), red- shifting of the superlattices’ bulk LSPR with decreased nano- particle spacing is

Predicting solvatochromic shifts and colours of a solvated organic dye: The example of nile red

NASA Astrophysics Data System (ADS)

Zuehlsdorff, T. J.; Haynes, P. D.; Payne, M. C.; Hine, N. D. M.

2017-03-01

The solvatochromic shift, as well as the change in colour of the simple organic dye nile red, is studied in two polar and two non-polar solvents in the context of large-scale time-dependent density-functional theory (TDDFT) calculations treating large parts of the solvent environment from first principles. We show that an explicit solvent representation is vital to resolve absorption peak shifts between nile red in n-hexane and toluene, as well as acetone and ethanol. The origin of the failure of implicit solvent models for these solvents is identified as being due to the strong solute-solvent interactions in form of π-stacking and hydrogen bonding in the case of toluene and ethanol. We furthermore demonstrate that the failures of the computationally inexpensive Perdew-Burke-Ernzerhof (PBE) functional in describing some features of the excited state potential energy surface of the S1 state of nile red can be corrected for in a straightforward fashion, relying only on a small number of calculations making use of more sophisticated range-separated hybrid functionals. The resulting solvatochromic shifts and predicted colours are in excellent agreement with experiment, showing the computational approach outlined in this work to yield very robust predictions of optical properties of dyes in solution.

Effect of Al/Ga substitution on the structural and luminescence properties of Y3(Al1-xGax)5O12: Ce3+ phosphors

NASA Astrophysics Data System (ADS)

Fu, Sheng; Tan, Jin; Bai, Xin; Yang, Shanjie; You, Lei; Du, Zhengkang

2018-01-01

As candidates for display and lighting materials, a series of gallium-substituted cerium-doped yttrium aluminum garnet (Y3(GaxAl1-x)5O12: Ce3+) phosphors were synthesized by high temperature solid-state reaction. The phases, morphology, luminescence spectra and thermal stability of the phosphors were investigated. The volatilization of Ga2O3 induces the constituents out of stoichiometric ratio and different impurities in the system. The excitation and emission spectra occur red shift (339 nm - 351 nm) and blue shift (465 nm - 437 nm), and blue shift (541 nm - 517 nm), respectively. The spectra have no further blue shift and the luminescence intensity decrease with x over 0.4. Combining crystal structure with PL spectrum, the distortion of dodecahedron and crystal field splitting of 5d level of Ce3+ are influenced by Ga3+ in octahedral coordination polyhedron rather than tetrahedron. The crystalline perfection and Ga3+ occupying the tetrahedron induce less garnet phase formation, more impurities and the 5d level located in the conductive bands, thus accounting for the x = 0.4 turning points of the PL and PLE intensity. Based on the thermal quenching and CIE, the Y3(GaxAl1-x)5O12: Ce3+0.06 phosphors have great potential for use on the w-LED.

ANALYSIS OF OPTICAL Fe II EMISSION IN A SAMPLE OF ACTIVE GALACTIC NUCLEUS SPECTRA

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kovacevic, Jelena; Popovic, Luka C.; Dimitrijevic, Milan S., E-mail: jkovacevic@aob.bg.ac.r

We present a study of optical Fe II emission in 302 active galactic nuclei (AGNs) selected from the Sloan Digital Sky Survey. We group the strongest Fe II multiplets into three groups according to the lower term of the transition (b{sup 4} F, a{sup 6} S, and a{sup 4} G terms). These approximately correspond to the blue, central, and red parts, respectively, of the 'iron shelf' around H{beta}. We calculate an Fe II template that takes into account transitions into these three terms and an additional group of lines, based on a reconstruction of the spectrum of I Zw 1.more » This Fe II template gives a more precise fit of the Fe II lines in broad-line AGNs than other templates. We extract Fe II, H{alpha}, H{beta}, [O III], and [N II] emission parameters and investigate correlations between them. We find that Fe II lines probably originate in an intermediate line region. We note that the blue, red, and central parts of the iron shelf have different relative intensities in different objects. Their ratios depend on continuum luminosity, FWHM H{beta}, the velocity shift of Fe II, and the H{alpha}/H{beta} flux ratio. We examine the dependence of the well-known anti-correlation between the equivalent widths of Fe II and [O III] on continuum luminosity. We find that there is a Baldwin effect for [O III] but an inverse Baldwin effect for the Fe II emission. The [O III]/Fe II ratio thus decreases with L {sub {lambda}5100}. Since the ratio is a major component of the Boroson and Green Eigenvector 1 (EV1), this implies a connection between the Baldwin effect and EV1 and could be connected with AGN evolution. We find that spectra are different for H{beta} FWHMs greater and less than {approx}3000 km s{sup -1}, and that there are different correlation coefficients between the parameters.« less

Formation of Long-Lived Color Centers for Broadband Visible Light Emission in Low-Dimensional Layered Perovskites.

PubMed

Booker, Edward P; Thomas, Tudor H; Quarti, Claudio; Stanton, Michael R; Dashwood, Cameron D; Gillett, Alexander J; Richter, Johannes M; Pearson, Andrew J; Davis, Nathaniel J L K; Sirringhaus, Henning; Price, Michael B; Greenham, Neil C; Beljonne, David; Dutton, Siân E; Deschler, Felix

2017-12-27

We investigate the origin of the broadband visible emission in layered hybrid lead-halide perovskites and its connection with structural and photophysical properties. We study ⟨001⟩ oriented thin films of hexylammonium (HA) lead iodide, (C 6 H 16 N) 2 PbI 4 , and dodecylammonium (DA) lead iodide, (C 12 H 28 N) 2 PbI 4 , by combining first-principles simulations with time-resolved photoluminescence, steady-state absorption and X-ray diffraction measurements on cooling from 300 to 4 K. Ultrafast transient absorption and photoluminescence measurements are used to track the formation and recombination of emissive states. In addition to the excitonic photoluminescence near the absorption edge, we find a red-shifted, broadband (full-width at half-maximum of about 0.4 eV), emission band below 200 K, similar to emission from ⟨110⟩ oriented bromide 2D perovskites at room temperature. The lifetime of this sub-band-gap emission exceeds that of the excitonic transition by orders of magnitude. We use X-ray diffraction measurements to study the changes in crystal lattice with temperature. We report changes in the octahedral tilt and lattice spacing in both materials, together with a phase change around 200 K in DA 2 PbI 4 . DFT simulations of the HA 2 PbI 4 crystal structure indicate that the low-energy emission is due to interstitial iodide and related Frenkel defects. Our results demonstrate that white-light emission is not limited to ⟨110⟩ oriented bromide 2D perovskites but a general property of this class of system, and highlight the importance of defect control for the formation of low-energy emissive sites, which can provide a pathway to design tailored white-light emitters.

What does C II lambda 2325 A emission tell us about chromospheres of red supergiants? - A critical test using Zeta Aurigae-type K supergiants

NASA Technical Reports Server (NTRS)

Schroeder, K.-P.; Reimers, D.; Carpenter, K. G.; Brown, A.

1988-01-01

The limitations of the Carpenter et al. (1985) C II intercombination multiplet method of determining the density and geometric extent of red giant chromospheres are presently tested through observation of the C II 2325 A emission of two K-type supergiants whose empirical model chromospheres have been derived by high-resolution IUE observations at eclipse phases. While the observed C II emission fluxes are well reproduced, much of this emission originates in the high-density lower chromosphere.

Red fluorescent proteins: advanced imaging applications and future design.

PubMed

Shcherbakova, Daria M; Subach, Oksana M; Verkhusha, Vladislav V

2012-10-22

In the past few years a large series of the advanced red-shifted fluorescent proteins (RFPs) has been developed. These enhanced RFPs provide new possibilities to study biological processes at the levels ranging from single molecules to whole organisms. Herein the relationship between the properties of the RFPs of different phenotypes and their applications to various imaging techniques are described. Existing and emerging imaging approaches are discussed for conventional RFPs, far-red FPs, RFPs with a large Stokes shift, fluorescent timers, irreversibly photoactivatable and reversibly photoswitchable RFPs. Advantages and limitations of specific RFPs for each technique are presented. Recent progress in understanding the chemical transformations of red chromophores allows the future RFP phenotypes and their respective novel imaging applications to be foreseen. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Negative hyperconjugation and red-, blue- or zero-shift in X-Z∙∙∙Y complexes.

PubMed

Joy, Jyothish; Jemmis, Eluvathingal D; Vidya, Kaipanchery

2015-01-01

A generalized explanation is provided for the existence of the red- and blue-shifting nature of X-Z bonds (Z=H, halogens, chalcogens, pnicogens, etc.) in X-Z∙∙∙Y complexes based on computational studies on a selected set of weakly bonded complexes and analysis of existing literature data. The additional electrons and orbitals available on Z in comparison to H make for dramatic differences between the H-bond and the rest of the Z-bonds. The nature of the X-group and its influence on the X-Z bond length in the parent X-Z molecule largely controls the change in the X-Z bond length on X-Z∙∙∙Y bond formation; the Y-group usually influences only the magnitude of the effects controlled by X. The major factors which control the X-Z bond length change are: (a) negative hyperconjugative donation of electron density from X-group to X-Z σ* antibonding molecular orbital (ABMO) in the parent X-Z, (b) induced negative hyperconjugation from the lone pair of electrons on Z to the antibonding orbitals of the X-group, and (c) charge transfer (CT) from the Y-group to the X-Z σ* orbital. The exchange repulsion from the Y-group that shifts partial electron density at the X-Z σ* ABMO back to X leads to blue-shifting and the CT from the Y-group to the σ* ABMO of X-Z leads to red-shifting. The balance between these two opposing forces decides red-, zero- or blue-shifting. A continuum of behaviour of X-Z bond length variation is inevitable in X-Z∙∙∙Y complexes.

Surface chemistry and density distribution influence on visible luminescence of silicon quantum dots: an experimental and theoretical approach.

PubMed

Dutt, Ateet; Matsumoto, Yasuhiro; Santana-Rodríguez, G; Ramos, Estrella; Monroy, B Marel; Santoyo Salazar, J

2017-01-04

The impact of the surface reconstruction of the density distribution and photoluminescence of silicon quantum dots (QDs) embedded in a silicon oxide matrix (SiO x ) has been studied. Annealing treatments carried out on the as-deposited samples provoked the effusion of hydrogen species. Moreover, depending on the surrounding density and coalescence of QDs, they resulted in a change in the average size of the particles depending on the initial local environment. The shift in the luminescence spectra all over the visible region (blue, green and red) shows a strong dependence on the resultant change in the size and/or the passivation environment of QDs. Density functional theoretical (DFT) calculations support this fact and explain the possible electronic transitions (HOMO-LUMO gap) involved. Passivation in the presence of oxygen species lowers the band gap of Si 29 and Si 35 nanoclusters up to 1.7 eV, whereas, surface passivation in the environment of hydrogen species increases the band gap up to 4.4 eV. These results show a good agreement with the quantum confinement model described in this work and explain the shift in the luminescence all over the visible region. The results reported here offer vital insight into the mechanism of emission from silicon quantum dots which has been one of the most debated topics in the last two decades. QDs with multiple size distribution in different local environments (band gap) observed in this work could be used for the fabrication of light emission diodes (LEDs) or shift-conversion thin films in third generation efficient tandem solar cells for the maximum absorption of the solar spectrum in different wavelength regions.

Intense green and red upconversion emission of Er3+,Yb3+ co-doped CaZrO3 obtained by a solution combustion reaction

NASA Astrophysics Data System (ADS)

Singh, Vijay; Kumar Rai, Vineet; Haase, Markus

2012-09-01

CaZrO3 phosphors co-doped with Er3+ and Yb3+ ions have been prepared by the urea combustion route. The formation of the orthorhombic phase of CaZrO3 was confirmed by powder x-ray diffraction. The absorption in the 280-1800 nm region and excitation spectrum corresponding to the emission at 545 nm for CaZrO3:Er3+/CaZrO3:Er3+,Yb3+ phosphors have been recorded. Upon excitation at 978 nm, the material displays strong energy transfer upconversion emission in the green and red spectral regions. The upconversion emission of the CaZrO3:Er3+,Yb3+ co-doped material shows an increased red-to-green ratio, indicating cross relaxation between Er3+ ions.

Photoconversion in orange and red fluorescent proteins

PubMed Central

Kremers, Gert-Jan; Hazelwood, Kristin L.; Murphy, Christopher S.; Davidson, Michael W.; Piston, David W.

2009-01-01

We report that photoconversion is fairly common among orange and red fluorescent proteins, as a screen of 12 variants yielded 8 that exhibit photoconversion. Specifically, three red fluorescent proteins can be switched into a green state, and two orange variants can be photoconverted to the far red. The orange highlighters are ideal for dual-probe highlighter applications, and they exhibit the most red-shifted excitation of all fluorescent protein described to date. PMID:19363494

A search for soft X-ray emission from red-giant coronae

NASA Technical Reports Server (NTRS)

Margon, B.; Mason, K. O.; Sanford, P. W.

1974-01-01

Hills has pointed out that if red-giant coronae are weak sources of soft X-rays, then the problems of the identification of the local component of the soft X-ray background and the observed lack of gas in globular clusters may be simultaneously resolved. Using instrumentation aboard OAO Copernicus, we have searched unsuccessfully for emission in the 10-100 A band from four nearby red giants. In all cases, our upper limits are of the order of the minimum theoretically predicted fluxes.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Romero, V.H.; De la Rosa, E., E-mail: elder@cio.mx; Salas, P.

In this paper, we report the obtained strong broadband blue photoluminescence (PL) emission centered at 427 nm for undoped BaZrO{sub 3} observed after 266 nm excitation of submicron crystals prepared by hydrothermal/calcinations method. This emission is enhanced with the introduction of Tm{sup 3+} ions and is stronger than the characteristic PL blue emission of such lanthanide. The proposed mechanism of relaxation for host lattice emission is based on the presence of oxygen vacancies produced during the synthesis process and the charge compensation due to the difference in the electron valence between dopant and substituted ion in the host. Brilliant whitemore » light emission with a color coordinate of (x=0.29, y=0.32) was observed by combining the blue PL emission from the host with the green and red PL emission from Tb{sup 3+} and Eu{sup 3+} ions, respectively. The color coordinate can be tuned by changing the ratio between blue, green and red band by changing the concentration of lanthanides. - Graphical abstract: Strong blue emission from undoped BaZrO{sub 3} phosphor and white light emission by doping with Tb{sup 3+} (green) and Eu{sup 3+} (red) after 266 nm excitation. Highlights: Black-Right-Pointing-Pointer Blue emission from BaZrO{sub 3} phosphor. Black-Right-Pointing-Pointer Blue emission enhanced with Tm{sup 3+}. Black-Right-Pointing-Pointer White light from BaZrO{sup 3+} phosphor.« less

Intersubband absorption in GaN nanowire heterostructures at mid-infrared wavelengths.

PubMed

Ajay, Akhil; Blasco, Rodrigo; Polaczynski, Jakub; Spies, Maria; den Hertog, Martien; Monroy, Eva

2018-06-27

In this paper, we study intersubband characteristics of GaN/AlN and GaN/Al0.4Ga0.6N heterostructures in GaN nanowires structurally designed to absorb in the mid-infrared wavelength region. Increasing the GaN well width from 1.5 to 5.7 nm leads to a red shift of the intersubband absorption from 1.4 to 3.4 µm. The red shift in larger quantum wells is amplified by the fact that one of the GaN/AlN heterointerfaces (corresponding to the growth of GaN on AlN) is not sharp but rather a graded alloy extending around 1.5-2 nm. Using AlGaN instead of AlN for the same barrier dimensions, we observe the effects of reduced polarization, which blue shifts the band-to-band transitions and red shifts the intersubband transitions. In heavily doped GaN/AlGaN nanowires, a broad absorption band is observed in the 4.5-6.4 µm spectral region. © 2018 IOP Publishing Ltd.

Mapping the universe in three dimensions

PubMed Central

Haynes, Martha P.

1996-01-01

The determination of the three-dimensional layout of galaxies is critical to our understanding of the evolution of galaxies and the structures in which they lie, to our determination of the fundamental parameters of cosmology, and to our understanding of both the past and future histories of the universe at large. The mapping of the large scale structure in the universe via the determination of galaxy red shifts (Doppler shifts) is a rapidly growing industry thanks to technological developments in detectors and spectrometers at radio and optical wavelengths. First-order application of the red shift-distance relation (Hubble’s law) allows the analysis of the large-scale distribution of galaxies on scales of hundreds of megaparsecs. Locally, the large-scale structure is very complex but the overall topology is not yet clear. Comparison of the observed red shifts with ones expected on the basis of other distance estimates allows mapping of the gravitational field and the underlying total density distribution. The next decade holds great promise for our understanding of the character of large-scale structure and its origin. PMID:11607714

Mapping the universe in three dimensions.

PubMed

Haynes, M P

1996-12-10

The determination of the three-dimensional layout of galaxies is critical to our understanding of the evolution of galaxies and the structures in which they lie, to our determination of the fundamental parameters of cosmology, and to our understanding of both the past and future histories of the universe at large. The mapping of the large scale structure in the universe via the determination of galaxy red shifts (Doppler shifts) is a rapidly growing industry thanks to technological developments in detectors and spectrometers at radio and optical wavelengths. First-order application of the red shift-distance relation (Hubble's law) allows the analysis of the large-scale distribution of galaxies on scales of hundreds of megaparsecs. Locally, the large-scale structure is very complex but the overall topology is not yet clear. Comparison of the observed red shifts with ones expected on the basis of other distance estimates allows mapping of the gravitational field and the underlying total density distribution. The next decade holds great promise for our understanding of the character of large-scale structure and its origin.

Ultrathin nondoped emissive layers for efficient and simple monochrome and white organic light-emitting diodes.

PubMed

Zhao, Yongbiao; Chen, Jiangshan; Ma, Dongge

2013-02-01

In this paper, highly efficient and simple monochrome blue, green, orange, and red organic light emitting diodes (OLEDs) based on ultrathin nondoped emissive layers (EMLs) have been reported. The ultrathin nondoped EML was constructed by introducing a 0.1 nm thin layer of pure phosphorescent dyes between a hole transporting layer and an electron transporting layer. The maximum external quantum efficiencies (EQEs) reached 17.1%, 20.9%, 17.3%, and 19.2% for blue, green, orange, and red monochrome OLEDs, respectively, indicating the universality of the ultrathin nondoped EML for most phosphorescent dyes. On the basis of this, simple white OLED structures are also demonstrated. The demonstrated complementary blue/orange, three primary blue/green/red, and four color blue/green/orange/red white OLEDs show high efficiency and good white emission, indicating the advantage of ultrathin nondoped EMLs on constructing simple and efficient white OLEDs.

The effect of shift work on red blood cell distribution width.

PubMed

Loprinzi, Paul D

2015-04-01

Limited research demonstrates that shift work (e.g., evening shift, night shift, rotating shift) increases the risk of certain health outcomes, such as hypertriglyceridemia and metabolic syndrome. Red blood cell distribution width (RDW), which is commonly assessed and reported by physicians, is a novel biomarker of cardiovascular disease. However, no study has examined the association of shift work on RDW, which was the purpose of this study. Data from the 2005-2010 NHANES were used. RDW was assessed from a blood sample; shift work was assessed from a questionnaire, and various demographic, behavioral/psychological, occupational, and biological parameters were included as covariates. The fully adjusted model showed that the odds of having an elevated RDW for women on rotating shift vs. day shift increased by 46% (OR=1.46; 95% CI: 1.03-2.08). Women on a rotating shift had increased odds of having an elevated RDW, which is concerning as elevated RDW increases the risk of cardiovascular disease and mortality. Health care professionals are encouraged to include questions about organization of work schedules and their tolerance of such schedules during the patient's consultation. Copyright © 2015 Elsevier Inc. All rights reserved.

Light at Night and Measures of Alertness and Performance: Implications for Shift Workers.

PubMed

Figueiro, Mariana G; Sahin, Levent; Wood, Brittany; Plitnick, Barbara

2016-01-01

Rotating-shift workers, particularly those working at night, are likely to experience sleepiness, decreased productivity, and impaired safety while on the job. Light at night has been shown to have acute alerting effects, reduce sleepiness, and improve performance. However, light at night can also suppress melatonin and induce circadian disruption, both of which have been linked to increased health risks. Previous studies have shown that long-wavelength (red) light exposure increases objective and subjective measures of alertness at night, without suppressing nocturnal melatonin. This study investigated whether exposure to red light at night would not only increase measures of alertness but also improve performance. It was hypothesized that exposure to both red (630 nm) and white (2,568 K) lights would improve performance but that only white light would significantly affect melatonin levels. Seventeen individuals participated in a 3-week, within-subjects, nighttime laboratory study. Compared to remaining in dim light, participants had significantly faster reaction times in the GO/NOGO test after exposure to both red light and white light. Compared to dim light exposure, power in the alpha and alpha-theta regions was significantly decreased after exposure to red light. Melatonin levels were significantly suppressed by white light only. Results show that not only can red light improve measures of alertness, but it can also improve certain types of performance at night without affecting melatonin levels. These findings could have significant practical applications for nurses; red light could help nurses working rotating shifts maintain nighttime alertness, without suppressing melatonin or changing their circadian phase. © The Author(s) 2015.

New transparent flexible nanopaper as ultraviolet filter based on red emissive Eu(III) nanofibrillated cellulose

NASA Astrophysics Data System (ADS)

Zhang, Zhao; Chang, Hui; Xue, Bailiang; Han, Qing; Lü, Xingqiang; Zhang, Sufeng; Li, Xinping; Zhu, Xunjin; Wong, Wai-kwok; Li, Kecheng

2017-11-01

A new kind of highly red emissive and transparent nanopapers as ultraviolet filter are produced from lanthanide complex Eu(TTA)3(H2O)2 grafted nanofibrillated cellulose (NFC) by a filtration process using a Buchner funnel. The nanopapers Eu-NFC 1-4 with different thickness (0.023 mm, 1; 0.04 mm, 2; 0.081 mm, 3 and 0.1 mm, 4) possess a fibres with dimensions of approximately 50 nm in diameter and several micrometres in length. Those nanopapers exhibit excellent ultraviolet A (UVA; 320-400 nm) filter property and high optical transmittance (>73% at wavelength of 600 nm). The presence of Eu(TTA)3(H2O)2 in Eu-NFC nanopapers can block 97% UVA (at 348 nm) light and convert it into pure red emission (CIE: x = 0.663, y = 0.333) through the efficient triplet-triplet energy transfer process. The efficient red emission can significantly improve the photo-stability of β-diketones type UVA filter. It can sustain for 10 h without decomposition under UV irradiation at 365 nm, which makes it possible to be applied in UVA filters. Moreover, its low coefficient of thermal expansion (CTE: 6.39 ppm K-1 of nanocellulose), is superior to petroleum-based materials for red organic light-emitting devices.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chu, Yaoqing; School of Materials Science and Engineering, Shanghai Institute of Technology, Shanghai 201418; Zhang, Qinghong

A new silicate garnet phosphor, Lu{sub 2−x}CaMg{sub 2}Si{sub 2.9}Ti{sub 0.1}O{sub 12}:xCe was synthesized by a high temperature solid-state reaction under reductive atmosphere. X-ray diffraction (XRD) showed that the powder was pure garnet phase. The emission and excitation spectrum indicated that the Lu{sub 2−x}CaMg{sub 2}Si{sub 2.9}Ti{sub 0.1}O{sub 12}:xCe phosphors could absorb blue light in the spectral range of 400–550 nm efficiently and exhibit bright yellow–orange emission in the range of 520–750 nm. With the increase of Ce{sup 3+} concentration, the emission band of Ce{sup 3+} showed a red shift. Interestingly, the concentration quenching occurred when the Ce{sup 3+} concentration exceeded 4more » mol%. The temperature-dependent luminescent properties of the phosphors were discussed and the Lu{sub 1.96}CaMg{sub 2}Si{sub 2.9}Ti{sub 0.1}O{sub 12}:0.04Ce phosphors showed good performances in color temperature (2430 K) and potential applications for warm white LEDs. - Graphical Abstract: This image shows that the phosphor of Lu{sub 1.96}CaMg{sub 2}Si{sub 2.9}Ti{sub 0.1}O{sub 12}:0.04Ce can generate a uniform yellow tint under natural light illumination and emit orange–red light when excited by blue light. With a fixed 467 nm emission light, warm white light can be produced by this phosphor, which indicates that the phosphor is potentially applicable in warm white light emitting diodes based on GaN chips. - Highlights: • A new silicate garnet phosphor was synthesized by solid-state method. • Secondary phases can be avoided when a small amount of Si{sup 4+} were replaced by Ti{sup 4+}. • A broad emission band of Ce{sup 3+} in the phosphors was described. • The phosphors are potentially applicable in warm white light emitting diodes.« less

The Evolution of Stellar Chromospheres

NASA Astrophysics Data System (ADS)

Simon, Theodore

1984-07-01

59 Vir (GO V) and 31 Com (GO III) are among the youngest G stars for which high dispersion spectra can be obtained with the short-wavelength camera of IUE. Their ages are estimated to be 0.2 Gyr (31 Com is a member of the Coma cluster). 59 Vir was observed at low resolution in a study of the relation between ultraviolet chromospheric activity and age in solar dwarf stars. 31 Com was observed as an example of a young yellow giant making its first crossing of the Hertzsprung Gap. Their spectra show bright chromospheric and transition region emission lines. We request observing time in this proposal to secure doubleshift (up to 16 hours) high dispersion exposures of each star with the SWP camera. These observations will allow us to resolve the profiles of individual chromospheric and transition region emission lines. From radiative transfer calculations, emission measure analyses, and line flux ratios, we will derive temperature, density, and velocity field models in the chromosphere and transition region. We will investigate the energy balance of these atmospheres in order to compare their non-thermal energy requirements with results derived for older solar-type dwarfs and more highly evolved yellow and red giants. With precautions to ensure the fidelity of the wavelength scale, we will also look far differential velocity shifts between TR and chromospheric lines, which may arise from global atmospheric circulation patterns. We have shown in previous work that redshifted TR lines are most clearly seen in giant stars and that the downflows causing the line shifts may affect the energy balance of giant atmospheres. As one of the very few normal G giants whose spectrum can be studied at high dispersion, 31 Com is important to such studies.

Preparation, structural, photoluminescence and magnetic studies of Cu doped ZnO nanoparticles co-doped with Ni by sol-gel method

NASA Astrophysics Data System (ADS)

Theyvaraju, D.; Muthukumaran, S.

2015-11-01

Zn0.96-xNi0.04CuxO nanoparticles have been synthesized by varying different Cu concentrations between 0% and 4% using simple sol-gel method. X-ray diffraction studies confirmed the hexagonal structure of the prepared samples. The formation of secondary phases, CuO (111) and Zn (101) at higher Cu content is due un-reacted Cu2+ and Zn2+ ions present in the solution which reduces the interaction between precursor ions and surfaces of ZnO. Well agglomerated and rod-like structure noticed at Cu=4% greatly de-generate and enhanced the particle size. The nominal elemental composition of Zn, Cu, Ni and O was confirmed by energy dispersive X-ray analysis. Even though energy gap was increased (blue-shift) from Cu=0-2% by quantum size effect, the s-d and p-d exchange interactions between the band electrons of ZnO and localized d electrons of Cu and Ni led to decrease (red-shift) the energy gap at Cu=4%. Presence of Zn-Ni-Cu-O bond was confirmed by Fourier transform infrared analysis. Ultraviolet emission by band to band electronic transition and defect related blue emission were discussed by photoluminescence spectra. The observed optical properties concluded that the doping of Cu in the present system is useful to tune the emission wavelength and hence acting as the important candidates for the optoelectronic device applications. Ferromagnetic ordering of Cu=2% sample was enhanced by charge carrier concentration where as the antiferromagnetic interaction between neighboring Cu-Cu ions suppressed the ferromagnetism at higher doping concentrations of Cu.

Down- and up-conversion emissions in Er-doped transparent fluorotellurite glass-ceramics

NASA Astrophysics Data System (ADS)

Miguel, A.; Morea, R.; Gonzalo, J.; Fernandez, J.; Balda, R.

2015-03-01

In this work, we report the near infrared and upconversion emissions of Er3+-doped transparent fluorotellurite glassceramics obtained by heat treatment of the precursor Er-doped TeO2-ZnO-ZnF2 glass. Structural analysis shows that ErF3 nanocrystals nucleated in the glass-ceramic sample are homogeneously distributed in the glass matrix with a typical size of 45±10 nm. The comparison of the fluorescence properties of Er3+-doped precursor glass and glass-ceramic confirms the successful incorporation of the rare-earth into the nanocrystals. An enhancement of the red upconversion emission due to 4F9/2→4I15/2 transition together with weak emission bands due to transitions from 2H9/2, 4F3/2,5/2, and 4F7/2 levels to the ground state are observed under excitation at 801 nm in the glass-ceramic sample. The temporal evolution of the red emission together with the excitation upconversion spectrum suggest that energy transfer processes are responsible for the enhancement of the red emission.

An Atomically Precise Au10 Ag2 Nanocluster with Red-Near-IR Dual Emission.

PubMed

Lei, Zhen; Guan, Zong-Jie; Pei, Xiao-Li; Yuan, Shang-Fu; Wan, Xian-Kai; Zhang, Jin-Yuan; Wang, Quan-Ming

2016-08-01

A red-near-IR dual-emissive nanocluster with the composition [Au10 Ag2 (2-py-C≡C)3 (dppy)6 ](BF4 )5 (1; 2-py-C≡C is 2-pyridylethynyl, dppy=2-pyridyldiphenylphosphine) has been synthesized. Single-crystal X-ray structural analysis reveals that 1 has a trigonal bipyramidal Au10 Ag2 core that contains a planar Au4 (2-py-C≡C)3 unit sandwiched by two Au3 Ag(dppy)3 motifs. Cluster 1 shows intense red-NIR dual emission in solution. The visible emission originates from metal-to-ligand charge transfer (MLCT) from silver atoms to phosphine ligands in the Au3 Ag(dppy)3 motifs, and the intense NIR emission is associated with the participation of 2-pyridylethynyl in the frontier orbitals of the cluster, which is confirmed by a time-dependent density functional theory (TD-DFT) calculation. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Novel europium (III)-gatifloxacin complex structure with dual functionality for pH sensing and metal recognition in aqueous environment

NASA Astrophysics Data System (ADS)

Chen, Muhua; Zheng, Yuhui; Gao, Jinwei; Wang, Qianming

2016-10-01

A new type of Eu(III)-gatifloxacin complex with characteristic red luminescence has been prepared. Due to the presence of ionization effect linked to the organic chromophore, the molecular fluorescent sensor demonstrated variable pH-sensitive absorption and emission curves. The red emission derived from europium ions was strong during pH range 8-10. Between pH = 7 and 4, the europium emission remained relatively stable and fluorescence signals of gatifloxacin has been improved substantially. Under acidic conditions (pH = 1 to 3), the dramatic changes in the emission colors (from red, yellow to green) were clearly observed. Moreover, the excitation wavelength can be extended into the visible light range (Ex = 411 nm) by using the concentration effect experiment. Importantly, it gave turn-off emissions in the presence of Cu2+ or Fe3+ and the detection limits were determined to be 6.5 μM for Cu2+ and 6.2 μM for Fe3+ respectively.

Application of concentrating plasmonic luminescent down-shifting layers for photovoltaic devices

NASA Astrophysics Data System (ADS)

Ahmed, H.; Rafiee, M.; Chandra, S.; Sethi, A.; McCormack, S. J.

2017-02-01

In this paper, concentrating structures of plasmonic luminescent downshifting composite layers (c-pLDS) containing lumogen yellow dye and silver nanoparticles (Ag NPs) to increase the efficiency of Photovoltaic (PV) devices were investigated. The c-pLDS structures allowed for a wider absorption range of both wavelength shifting and light concentration with a strong energy transfer that red shifts photons to wavelengths which gives greater spectral response of solar cells. The optimum dye concentration in a poly(methyl,methacrylate) polymer of a thin layer 10μm spin coated on glass substrate was established. Subsequently, plasmonic coupling with Ag NPs was introduced for the c-pLDS composite structures. Plasmonic coupling has been observed to produce fluorescence emission enhancement of up to 20% for the dye c-pLDS layer. The c-pLDS layer was modelled for CdTe mini modules (15x15 cm) and compared with a blank PMMA/GLASS and dye c-LDS structure. It has been demonstrated that the addition of c-pLDS layers containing lumogen yellow dye increases the optical efficiency and the Short circuit current (Jsc) of CdTe solar cells. An increase of 7.3% in the optical efficiency has been achieved and a 30% in the Jsc was obtained when a c-pLDS composite layer is used.

Impulsive EUV bursts observed in C IV with OSO-8. [UV solar spectra

NASA Technical Reports Server (NTRS)

Athay, R. G.; White, O. R.; Lites, B. W.; Bruner, E. C., Jr.

1980-01-01

Time sequences of profiles of the 1548 A line of C IV containing 51 EUV bursts observed in or near active regions are analyzed to determine the brightness, Doppler shift and line broadening characteristics of the bursts. The bursts have mean lifetimes of approximately 150 s, and mean increases in brightness at burst maximum of four-fold as observed with a field of view of 2 x 20 arc sec. Mean burst diameters are estimated to be 3 arc sec, or smaller. All but three of the bursts show Doppler shifts with velocities sometimes exceeding 75 km/s; 31 are dominated by red shifts and 17 are dominated by blue shifts. Approximately half of the latter group have red-shifted precursors. The bursts are interpreted as prominence material, such as surges and coronal rain, moving through the field of view of the spectrometer.

The Effect of Dietary Replacement of Ordinary Rice with Red Yeast Rice on Nutrient Utilization, Enteric Methane Emission and Rumen Archaeal Diversity in Goats.

PubMed

Wang, L Z; Zhou, M L; Wang, J W; Wu, D; Yan, T

2016-01-01

Twenty castrated Boer crossbred goats were used in the present study with two treatments to examine the effect of dietary replacement of ordinary rice with red yeast rice on nutrient utilization, enteric methane emission and ruminal archaea structure and composition. Two treatment diets contained (DM basis) 70.0% of forage, 21.8% of concentrates and 8.2% of either ordinary rice (control) or red yeast rice (RYR). Nutrient utilization was measured and enteric methane emissions were determined in respiration chambers. Results showed that RYR had significantly lower digestibility of N and organic matter compared to control group. However, feeding red yeast rice did not affect N retention as g/d or a proportion of N intake, and reduced heat production as MJ/d or as a proportion of metabolizable energy intake, thus leading to a higher proportion of metabolizable energy intake to be retained in body tissue. RYR also had significantly lower methane emissions either as g/d, or as a proportion of feed intake. Although feeding red yeast rice had no negative effect on any rumen fermentation variables, it decreased serum contents of total cholesterol, triglycerides, HDL-cholesterol and LDL-cholesterol. In the present study, 75616 archaeal sequences were generated and clustered into 2364 Operational Taxonomic Units. At the genus level, the predominant archaea in the rumen of goats was Methanobrevibacter, which was significantly inhibited with the supplementation of red yeast rice. In conclusion, red yeast rice is a potential feed ingredient for mitigation of enteric methane emissions of goats. However, caution should be taken when it is used because it may inhibit the digestibility of some nutrients. Further studies are required to evaluate its potential with different diets and animal species, as well as its effects on animal health and food safety.

Multicolor tuning towards single red-emission band of upconversion nanoparticles for tunable optical component and optical/x-ray imaging agents via Ce(3+) doping.

PubMed

Yi, Zhigao; Zeng, Tianmei; Xu, Yaru; Lu, Wei; Qian, Chao; Liu, Hongrong; Zeng, Songjun; Hao, Jianhua

2015-09-25

A simple strategy of Ce(3+) doping is proposed to realize multicolor tuning and predominant red emission in BaLnF5:Yb(3+)/Ho(3+) (Ln(3+) = Gd(3+), Y(3+), Yb(3+)) systems. A tunable upconversion (UC) multicolor output from green/yellow to red can be readily achieved in a fixed Yb(3+)/Ho(3+) composition by doping Ce(3+), providing an effective route for multicolor tuning widely used for various optical components. Moreover, compared with Ce(3+)-free UC nanoparticles (UCNPs), a remarkable enhancement of the red-to-green (R/G) ratio is observed by doping 30% Ce(3+), arising from the two largely promoted cross-relaxation (CR) processes between Ce(3+) and Ho(3+). UCNPs with pure red emission are selected as in vivo UC bioimaging agents, demonstrating the merits of deep penetration depth, the absence of autofluorescence and high contrast in small animal bioimaging. Moreover, such fluorescence imaging nanoprobes can also be used as contrast agents for three-dimensional (3D) x-ray bioimaging by taking advantage of the high K-edge values and x-ray absorption coefficients of Ba(2+), Gd(3+), and Ce(3+) in our designed nanoprobes. Thus, the simultaneous realization of multicolor output, highly enhanced R/G ratio, and predominant red emission makes the Ce(3+)-doped UCNPs very useful for widespread applications in optical components and bioimaging.

Chromatic response of polydiacetylene vesicle induced by the permeation of methotrexate.

PubMed

Shin, Min Jae; Kim, Ye Jin; Kim, Jong-Duk

2015-07-07

The noble vesicular system of polydiacetylene showed a red shift using two types of detecting systems. One of the systems involves the absorption of target materials from the outer side of the vesicle, and the other system involves the permeation through the vesicular layers from within the vesicle. The chromatic mixed vesicles of N-(2-aminoethyl)pentacosa-10,12-diynamide (AEPCDA) and dimethyldioctadecylammonium chloride (DODAC) were fabricated by sonication, followed by polymerization by UV irradiation. The stability of monomeric vesicles was observed to increase with the polymerization of the vesicles. Methotrexate was used as a target material. The polymerized mixed vesicles having a blue color were exposed to a concentration gradient of methotrexate, and a red shift was observed indicating the adsorption of methotrexate on the polydiacetylene bilayer. In order to check the chromatic change by the permeation of methotrexate, we separated the vesicle portion, which contained methotrexate inside the vesicle, and checked chromatic change during the permeation of methotrexate through the vesicle. The red shift apparently indicates the disturbance in the bilayer induced by the permeation of methotrexate. The maximum contrast of color appeared at the equal molar ratio of AEPCDA and DODAC, indicating that the formation of flexible and deformable vesicular layers is important for red shift. Therefore, it is hypothesized that the system can be applicable for the chromatic detection of the permeation of methotrexate through the polydiacetylene layer.

High colloidal stability of gold nanorods coated with a peptide-ethylene glycol: Analysis by cyanide-mediated etching and nanoparticle tracking analysis.

PubMed

Free, Paul; Conger, Gao; Siji, Wu; Zhang, Jing Bo; Fernig, David G

2016-10-01

The stability of gold nanorods was assessed following coating with various charged or uncharged ligands, mostly peptides. Highly stable monodispersed gold nanorods were obtained by coating CTAB-stabilized gold nanorods with a pentapeptide with C-terminal ethylene glycol units (peptide-EG). UV-vis spectroscopy of these nanorods suspended in saline solutions indicated no signs of aggregation, and they were easily purified using size-exclusion chromatography. A more stringent measure of nanorod stability involved observing changes in the UV-vis absorbance of gold nanorods subjected to etching with cyanide. The λmax absorbance of peptide-EG coated nanorods red-shifted in etchant solution. The hypothesis that changes in the nanorod aspect ratio led to this red-shift was confirmed by TEM analysis, which showed pit formation along the transverse axis. The etching process was followed in solution using nanoparticle tracking analysis. The red-shift was shown to occur while the particles remained mono-dispersed, and so was not due to aggregation. Adding both etchant solution and peptide-EG to the nanorods was further shown to allow modulation of the Δλmax red-shift and increase the etchant resistance of peptide-EG nanorods. Thus, very stable gold nanorods can be produced using the peptide-EG coating approach and their optical properties modulated with etchant. Copyright © 2016 Elsevier B.V. All rights reserved.

Novel push-pull fluorescent dyes - 7-(diethylamino)furo- and thieno[3,2-c]coumarins derivatives: structure, electronic spectra and TD-DFT study

NASA Astrophysics Data System (ADS)

Akchurin, Igor O.; Yakhutina, Anna I.; Bochkov, Andrei Y.; Solovjova, Natalya P.; Medvedev, Michael G.; Traven, Valerii F.

2018-05-01

Novel push-pull fluorescent dyes - 7-(diethylamino)furo- and 7-(diethylamino)thieno[3,2-c]coumarins derivatives have been synthesized using formyl derivatives of furo- and thieno[3,2-c]coumarins as starting materials. Electron absorption and fluorescent spectra of the dyes have been recorded in different solvents. Structure and solvent effects on the dyes spectral characteristics were analyzed. The fusion of five-membered heterocycle to coumarin provides a definite increase of Stokes shifts in all solvents and results in higher quantum yields of fluorescence. The absorption and emission bands of thieno[3,2-c] coumarin derivatives are definitely shifted to the red region (3-30 nm) compared to similar derivatives of furo[3,2-c]coumarin. TD-DFT calculations of some of the studied compounds have shown that hybrid DFT functionals and adequate representation of molecular environment are essential for obtaining accurate UV-Vis absorption spectra for the dyes with extended π-system. The longest-wave electron transitions in the studied compounds were computationally shown to be of push-pull nature.

Highly Stable Near-Infrared Fluorescent Organic Nanoparticles with a Large Stokes Shift for Noninvasive Long-Term Cellular Imaging.

PubMed

Zhang, Jinfeng; Chen, Rui; Zhu, Zelin; Adachi, Chihaya; Zhang, Xiaohong; Lee, Chun-Sing

2015-12-02

Fluorescent organic nanoparticles based on small molecules have been regarded as promising candidates for bioimaging in recent years. In this study, we report a highly stable near-infrared (NIR) fluorescent organic nanoprobes based on nanoparticles of an anthraquinone derivate with strong aggregation-induced emission (AIE) characteristics and a large Stokes shift (>175 nm). These endow the nanoprobe with high fluorescent brightness and high signal-to-noise ratio. On the other hand, the nanoprobe also shows low cytotoxicity, good stability over a wide pH range, superior resistance against photodegradation and photobleaching comparing to typical commercial fluorescent organic dyes such as fluorescein sodium. Endowed with such merits in term of optical performance, biocompatibility, and stability, the nanoprobe is demonstrated to be an ideal fluorescent probe for noninvasive long-term cellular tracing and imaging applications. As an example, it is shown that strong red fluorescence from the nanoprobe can still be clearly observed in A549 human lung cancer cells after incubation for six generations over 15 days.

A panel of Trypanosoma brucei strains tagged with blue and red-shifted luciferases for bioluminescent imaging in murine infection models.

PubMed

Van Reet, Nick; Van de Vyver, Hélène; Pyana, Patient Pati; Van der Linden, Anne Marie; Büscher, Philippe

2014-08-01

Genetic engineering with luciferase reporter genes allows monitoring Trypanosoma brucei (T.b.) infections in mice by in vivo bioluminescence imaging (BLI). Until recently, luminescent T.b. models were based on Renilla luciferase (RLuc) activity. Our study aimed at evaluating red-shifted luciferases for in vivo BLI in a set of diverse T.b. strains of all three subspecies, including some recently isolated from human patients. We transfected T.b. brucei, T.b. rhodesiense and T.b. gambiense strains with either RLuc, click beetle red (CBR) or Photinus pyralis RE9 (PpyRE9) luciferase and characterised their in vitro luciferase activity, growth profile and drug sensitivity, and their potential for in vivo BLI. Compared to RLuc, the red-shifted luciferases, CBR and PpyRE9, allow tracking of T.b. brucei AnTaR 1 trypanosomes with higher details on tissue distribution, and PpyRE9 allows detection of the parasites with a sensitivity of at least one order of magnitude higher than CBR luciferase. With CBR-tagged T.b. gambiense LiTaR1, T.b. rhodesiense RUMPHI and T.b. gambiense 348 BT in an acute, subacute and chronic infection model respectively, we observed differences in parasite tropism for murine tissues during in vivo BLI. Ex vivo BLI on the brain confirmed central nervous system infection by all luminescent strains of T.b. brucei AnTaR 1, T.b. rhodesiense RUMPHI and T.b. gambiense 348 BT. We established a genetically and phenotypically diverse collection of bioluminescent T.b. brucei, T.b. gambiense and T.b. rhodesiense strains, including drug resistant strains. For in vivo BLI monitoring of murine infections, we recommend trypanosome strains transfected with red-shifted luciferase reporter genes, such as CBR and PpyRE9. Red-shifted luciferases can be detected with a higher sensitivity in vivo and at the same time they improve the spatial resolution of the parasites in the entire body due to the better kinetics of their substrate D-luciferin.

A Panel of Trypanosoma brucei Strains Tagged with Blue and Red-Shifted Luciferases for Bioluminescent Imaging in Murine Infection Models

PubMed Central

Van Reet, Nick; Van de Vyver, Hélène; Pyana, Patient Pati; Van der Linden, Anne Marie; Büscher, Philippe

2014-01-01

Background Genetic engineering with luciferase reporter genes allows monitoring Trypanosoma brucei (T.b.) infections in mice by in vivo bioluminescence imaging (BLI). Until recently, luminescent T.b. models were based on Renilla luciferase (RLuc) activity. Our study aimed at evaluating red-shifted luciferases for in vivo BLI in a set of diverse T.b. strains of all three subspecies, including some recently isolated from human patients. Methodology/Principal findings We transfected T.b. brucei, T.b. rhodesiense and T.b. gambiense strains with either RLuc, click beetle red (CBR) or Photinus pyralis RE9 (PpyRE9) luciferase and characterised their in vitro luciferase activity, growth profile and drug sensitivity, and their potential for in vivo BLI. Compared to RLuc, the red-shifted luciferases, CBR and PpyRE9, allow tracking of T.b. brucei AnTaR 1 trypanosomes with higher details on tissue distribution, and PpyRE9 allows detection of the parasites with a sensitivity of at least one order of magnitude higher than CBR luciferase. With CBR-tagged T.b. gambiense LiTaR1, T.b. rhodesiense RUMPHI and T.b. gambiense 348 BT in an acute, subacute and chronic infection model respectively, we observed differences in parasite tropism for murine tissues during in vivo BLI. Ex vivo BLI on the brain confirmed central nervous system infection by all luminescent strains of T.b. brucei AnTaR 1, T.b. rhodesiense RUMPHI and T.b. gambiense 348 BT. Conclusions/Significance We established a genetically and phenotypically diverse collection of bioluminescent T.b. brucei, T.b. gambiense and T.b. rhodesiense strains, including drug resistant strains. For in vivo BLI monitoring of murine infections, we recommend trypanosome strains transfected with red-shifted luciferase reporter genes, such as CBR and PpyRE9. Red-shifted luciferases can be detected with a higher sensitivity in vivo and at the same time they improve the spatial resolution of the parasites in the entire body due to the better kinetics of their substrate D-luciferin. PMID:25144573

Color-tunable up-conversion emission from Yb{sup 3+}/Er{sup 3+}/Tm{sup 3+} tri-doped T-AgGd(W,Mo){sub 2}O{sub 8} phosphors

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Jijian; Liu, Ni; Xu, Ling, E-mail: xuling@snnu.edu.cn

Graphical abstract: The doping ions tune the UC luminescence of the T- AgGd(W,Mo){sub 2}O{sub 8}:Yb{sup 3+}/Er{sup 3+}/Tm{sup 3+} material. - Highlights: • AgGd(W,Mo){sub 2}O{sub 8}:Yb{sup 3+}/Er{sup 3+}/Tm{sup 3+} phosphors show color-tunable blue, green, and red UC emissions. • The samples’ UC emission color can be switched with the concentrations of doped ions. • The blue, green and red UC mechanisms are interpreted reasonably as three- and two- photon process. - Abstract: Tetragonal Yb{sup 3+}/Er{sup 3+}/Tm{sup 3+} tri-doped AgGd(W,Mo){sub 2}O{sub 8} phosphors were prepared by the high-temperature solid-state method. When the phosphors were excited at 980 nm, the UC emission ofmore » blue at 475 nm, green at 525 and 550 nm, and red at 656 nm were corresponding to the {sup 1}G{sub 4} → {sup 3}H{sub 6} transition of Tm{sup 3+} ions, the {sup 2}H{sub 11/2},{sup 4}S{sub 3/2} → {sup 4}I{sub 15/2} transitions of Er{sup 3+} ions, and the {sup 4}F{sub 9/2} → {sup 4}I{sub 15/2} transition of Er{sup 3+} ions, respectively. The blue UC emissions originate from a three-photon mechanism, while the green and red ones of Er{sup 3+} from two-photon process. The UC emission color of the Yb{sup 3+}/Er{sup 3+}/Tm{sup 3+} tri-doped AgGdW{sub 2}O{sub 8} samples switched from green to white, and then to red depending on the concentrations of Er{sup 3+} and Tm{sup 3+}. After doping with Mo(VI), tetragonal AgGdW{sub 2}O{sub 8} was transformed into tetragonal AgGdMo{sub 2}O{sub 8}, resulting in a slightly enhanced UC luminescence intensity with the favor of the red emission of Er{sup 3+} ion.« less

Effect of red blood cells on the growth of Porphyromonas endodontalis and microbial community development.

PubMed

Zerr, M A; Cox, C D; Johnson, W T; Drake, D R

1998-04-01

Establishment of a microbial community in the root canal system depends on numerous factors, of which nutrient availability may be one of the most important. We hypothesized that the presence of red blood cells or hemoglobin in this environment could cause shifts in microbial composition of communities, resulting in organisms such as Porphyromonas endodontalis becoming more dominant. An in vitro model system using mixed, batch cultures was performed with the bacteria P. endodontalis, Fusobacterium nucleatum, Peptostreptococcus micros and Campylobacter rectus. Bacteria were cultured in media with or without the addition of washed red blood cells, hemoglobin, or serum. Cyclic growth studies revealed that P. endodontalis was lost from the community of organisms after three cycles. However, inclusion of red blood cells resulted in establishment of this organism. Moreover, red blood cells added to pure cultures of P. endodontalis substantially enhanced growth and protected the organisms from oxygen. We conclude that the presence of red blood cells could result in shifts of microbial communities of organisms within the root canal system.

Simulations of absorption spectra of conjugated oligomers: role of planar conformation and aggregation in condensed phase

NASA Astrophysics Data System (ADS)

Yuan, Xiang-Ai; Wen, Jin; Zheng, Dong; Ma, Jing

2018-04-01

This Review highlights the structure/property relationship underlying the morphology modulation through various factors towards the exploration of light-absorbing materials for efficient utilisation of solar power. Theoretical study using a combination of molecular dynamics imulations and the time-dependent density functional theory demonstrated that the planarity plays an important role in tuning spectral properties of oligomer aggregates. The aggregation-induced blue-shift in absorption spectra of oligothiophenes and the red-shift for oligofluorenols were rationalised in a unified way from the reduced (and increased) content of planar conformations in molecular aggregates. The planarity versus non-planarity of oligomers can be modulated by introduction of alkyl side chain or steric bulky substituents. The substitution with various groups in the ortho-position of azobenzene leads to the distorted backbone, breaking symmetry, and hence the red-shift in spectra, expanding the application in biological systems with visible light absorption. The donor-acceptor substituent groups in conjugated oligomers can increase the degree of planarity, electron delocalisation and polarisation, and charge separation, giving rise to the red-shift in spectra and enhancement in polarisability and charge mobility for device applications. The solvent dependent and pH-sensitive properties and intramolecular hydrogen bonds also caused the shift of absorption spectra with the appearance of planar conformers.

A SIMPLE CONNECTION BETWEEN THE NEAR- AND MID-INFRARED EMISSION OF GALAXIES AND THEIR STAR FORMATION RATES

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mentuch, Erin; Abraham, Roberto G.; Zibetti, Stefano

2010-12-20

We have measured the near-infrared colors and the fluxes of individual pixels in 68 galaxies common to the Spitzer Infrared Nearby Galaxies Survey and the Large Galaxy Atlas Survey. Pixels from each galaxy are grouped into regions of increasingly red near-infrared colors. As expected, the majority of pixels are shown to have relatively constant NIR flux ratios (log{sub 10} I{sub 3.6}/I{sub 1.25} = -0.30 {+-} 0.07 and log{sub 10} I{sub 4.5}/I{sub 3.6} = -0.19 {+-} 0.02), representing the blackbody continuum emission of main sequence stars. However, pixels with red NIR colors correspond to pixels with higher H{sub {alpha}} emission andmore » dust extinction. We show that the NIR colors are correlated to both quantities, with the strongest correlation to the intrinsic H{sub {alpha}} emission. In addition, in regions of high star formation, the average intensity of pixels in red-excess regions (at 1.25 {mu}m, 3.6 {mu}m, 4.5 {mu}m, 5.6 {mu}m, 8.0 {mu}m and 24 {mu}m) scales linearly with the intrinsic intensity of H{alpha} emission, and thus with the star formation rate (SFR) within the pixel. This suggests that most NIR-excess regions are not red because their light is being depleted by absorption. Instead, they are red because additional infrared light is being contributed by a process linked to star formation. This is surprising because the shorter wavelength bands in our study (1.25 {mu}m-5.6 {mu}m) do not probe emission from cold (10-20 K) and warm (50-100 K) dust associated with star formation in molecular clouds. However, emission from hot dust (700-1000 K) and/or polycyclic aromatic hydrocarbon (PAH) molecules can explain the additional emission seen at the shorter wavelengths in our study. The contribution from hot dust and/or PAH emission at 2 {mu}m-5 {mu}m and PAH emission at 5.6 {mu}m and 8.0 {mu}m scales linearly with warm dust emission at 24 {mu}m and the intrinsic H{alpha} emission. Since both are tied to the SFR, our analysis shows that the NIR excess continuum emission and PAH emission at {approx}1-8 {mu}m can be added to spectral energy distribution models in a very straightforward way, by simply adding an additional component to the models that scales linearly with SFR.« less

Advances in engineering of fluorescent proteins and photoactivatable proteins with red emission.

PubMed

Piatkevich, Kiryl D; Verkhusha, Vladislav V

2010-02-01

Monomeric fluorescent proteins of different colors are widely used to study behavior and targeting of proteins in living cells. Fluorescent proteins that irreversibly change their spectral properties in response to light irradiation of a specific wavelength, or photoactivate, have become increasingly popular to image intracellular dynamics and superresolution protein localization. Until recently, however, no optimized monomeric red fluorescent proteins and red photoactivatable proteins have been available. Furthermore, monomeric fluorescent proteins, which change emission from blue to red simply with time, so-called fluorescent timers, were developed to study protein age and turnover. Understanding of chemical mechanisms of the chromophore maturation or photoactivation into a red form will further advance engineering of fluorescent timers and photoactivatable proteins with enhanced and novel properties. 2009 Elsevier Ltd. All rights reserved.

Red:far-red light conditions affect the emission of volatile organic compounds from barley (Hordeum vulgare), leading to altered biomass allocation in neighbouring plants

PubMed Central

Kegge, Wouter; Ninkovic, Velemir; Glinwood, Robert; Welschen, Rob A. M.; Voesenek, Laurentius A. C. J.; Pierik, Ronald

2015-01-01

Background and Aims Volatile organic compounds (VOCs) play various roles in plant–plant interactions, and constitutively produced VOCs might act as a cue to sense neighbouring plants. Previous studies have shown that VOCs emitted from the barley (Hordeum vulgare) cultivar ‘Alva’ cause changes in biomass allocation in plants of the cultivar ‘Kara’. Other studies have shown that shading and the low red:far-red (R:FR) conditions that prevail at high plant densities can reduce the quantity and alter the composition of the VOCs emitted by Arabidopsis thaliana, but whether this affects plant–plant signalling remains unknown. This study therefore examines the effects of far-red light enrichment on VOC emissions and plant–plant signalling between ‘Alva’ and ‘Kara’. Methods The proximity of neighbouring plants was mimicked by supplemental far-red light treatment of VOC emitter plants of barley grown in growth chambers. Volatiles emitted by ‘Alva’ under control and far-red light-enriched conditions were analysed using gas chromatography–mass spectrometry (GC-MS). ‘Kara’ plants were exposed to the VOC blend emitted by the ‘Alva’ plants that were subjected to either of the light treatments. Dry matter partitioning, leaf area, stem and total root length were determined for ‘Kara’ plants exposed to ‘Alva’ VOCs, and also for ‘Alva’ plants exposed to either control or far-red-enriched light treatments. Key Results Total VOC emissions by ‘Alva’ were reduced under low R:FR conditions compared with control light conditions, although individual volatile compounds were found to be either suppressed, induced or not affected by R:FR. The altered composition of the VOC blend emitted by ‘Alva’ plants exposed to low R:FR was found to affect carbon allocation in receiver plants of ‘Kara’. Conclusions The results indicate that changes in R:FR light conditions influence the emissions of VOCs in barley, and that these altered emissions affect VOC-mediated plant–plant interactions. PMID:25851141

Red:far-red light conditions affect the emission of volatile organic compounds from barley (Hordeum vulgare), leading to altered biomass allocation in neighbouring plants.

PubMed

Kegge, Wouter; Ninkovic, Velemir; Glinwood, Robert; Welschen, Rob A M; Voesenek, Laurentius A C J; Pierik, Ronald

2015-05-01

Volatile organic compounds (VOCs) play various roles in plant-plant interactions, and constitutively produced VOCs might act as a cue to sense neighbouring plants. Previous studies have shown that VOCs emitted from the barley (Hordeum vulgare) cultivar 'Alva' cause changes in biomass allocation in plants of the cultivar 'Kara'. Other studies have shown that shading and the low red:far-red (R:FR) conditions that prevail at high plant densities can reduce the quantity and alter the composition of the VOCs emitted by Arabidopsis thaliana, but whether this affects plant-plant signalling remains unknown. This study therefore examines the effects of far-red light enrichment on VOC emissions and plant-plant signalling between 'Alva' and 'Kara'. The proximity of neighbouring plants was mimicked by supplemental far-red light treatment of VOC emitter plants of barley grown in growth chambers. Volatiles emitted by 'Alva' under control and far-red light-enriched conditions were analysed using gas chromatography-mass spectrometry (GC-MS). 'Kara' plants were exposed to the VOC blend emitted by the 'Alva' plants that were subjected to either of the light treatments. Dry matter partitioning, leaf area, stem and total root length were determined for 'Kara' plants exposed to 'Alva' VOCs, and also for 'Alva' plants exposed to either control or far-red-enriched light treatments. Total VOC emissions by 'Alva' were reduced under low R:FR conditions compared with control light conditions, although individual volatile compounds were found to be either suppressed, induced or not affected by R:FR. The altered composition of the VOC blend emitted by 'Alva' plants exposed to low R:FR was found to affect carbon allocation in receiver plants of 'Kara'. The results indicate that changes in R:FR light conditions influence the emissions of VOCs in barley, and that these altered emissions affect VOC-mediated plant-plant interactions. © The Author 2015. Published by Oxford University Press on behalf of the Annals of Botany Company. All rights reserved. For Permissions, please email: journals.permissions@oup.com.

Effect of Molecular Coupling on Ultrafast Electron-Transfer and Charge-Recombination Dynamics in a Wide-Gap ZnS Nanoaggregate Sensitized by Triphenyl Methane Dyes.

PubMed

Debnath, Tushar; Maity, Partha; Dana, Jayanta; Ghosh, Hirendra N

2016-03-03

Wide-band-gap ZnS nanocrystals (NCs) were synthesized, and after sensitizing the NCs with series of triphenyl methane (TPM) dyes, ultrafast charge-transfer dynamics was demonstrated. HRTEM images of ZnS NCs show the formation of aggregate crystals with a flower-like structure. Exciton absorption and lumimescence, due to quantum confinement of the ZnS NCs, appear at approximately 310 and 340 nm, respectively. Interestingly, all the TPM dyes (pyrogallol red, bromopyrogallol red, and aurin tricarboxylic acid) form charge-transfer complexes with the ZnS NCs, with the appearance of a red-shifted band. Electron injection from the photoexcited TPM dyes into the conduction band of the ZnS NCs is shown to be a thermodynamically viable process, as confirmed by steady-state and time-resolved emission studies. To unravel charge-transfer (both electron injection and charge recombination) dynamics and the effect of molecular coupling, femtosecond transient absorption studies were carried out in TPM-sensitized ZnS NCs. The electron-injection dynamics is pulse-width-limited in all the ZnS/TPM dye systems, however, the back electron transfer differs, depending on the molecular coupling of the sensitizers (TPM dyes). The detailed mechanisms for the above-mentioned processes are discussed. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Development of Eu3+ activated monoclinic, perovskite, and garnet compounds in the Gd2O3-Al2O3 phase diagram as efficient red-emitting phosphors

NASA Astrophysics Data System (ADS)

Li, Jinkai; Li, Ji-Guang; Li, Jing; Liu, Shaohong; Li, Xiaodong; Sun, Xudong; Sakka, Yoshio

2013-10-01

Eu3+ doped Gd4Al2O9 (GdAM), GdAlO3 (GdAP), and Gd3Al5O12 (GdAG, containing 10 at% of Lu3+ for lattice stabilization) have been developed in this work as efficient red-emitting phosphors. With coprecipitated carbonate precursors, phase evolution studies found minimum processing temperatures of ~1000, 1100, and 1300 °C for the three phosphors to crystallize as pure phases, respectively. Compared with their yttrium aluminate counterparts, the gadolinium-based phosphors exhibit red-shifted O2--Eu3+ charge transfer excitation band (CTB) centers due to the lower electronegativity of Gd3+ and appreciably higher quantum yields of photoluminescence owing to the occurrence of efficient Gd3+→Eu3+energy transfer. The optimal Eu3+ contents were determined to be ~7.5 at% for GdAM and 5.0 at% for both GdAP and GdAG, and concentration quenching of luminescence was suggested to be due to exchange interactions. Fluorescence decay analysis found a shorter lifetime for the phosphor powder processed at a higher temperature or with a higher Eu3+ content, and the underlying mechanism was discussed. Fluorescence lifetimes were also compared between the yttrium and gadolinium phosphor systems for the dominant emissions.

Observation of radio-wave-induced red hydroxyl emission at low altitude in the ionosphere.

PubMed

Kagan, L M; Nicolls, M J; Kelley, M C; Carlson, H C; Belikovich, V V; Bakhmet'eva, N V; Komrakov, G P; Trondsen, T S; Donovan, E

2005-03-11

We report the discovery of radio-wave-induced red emission of OH Meinel rotation-vibrational bands at 629.79 nm. These are the first measurements of artificial aurora below 100 km. We believe that the 629.79-nm OH emission was due to radio-wave focusing by sporadic ionization clouds near 80-85 km altitude, thus giving a technique to visualize the low-altitude sporadic ionization and providing insight into ionospheric interactions at these low altitudes.

Photophysical Behavior and Computational Investigation of Novel 1,4-Bis(2-(2-Phenylpyrimido[1,2-a]Benzimidazol-4-Yl)Phenoxy)Butan (BPPB) Macromolecule.

PubMed

Saleh, Tamer S; Hussein, Mahmoud A; Osman, Osman I; Alamry, Khalid A; Mekky, Ahmed E M; Asiri, Abdullah M; El-Daly, Samy A

2016-09-01

A new macromolecule pyrimido[l,2-a]benzimidazole derivative named 1,4-bis(2-(2-phenylpyrimido[1,2-a]benzimidazol-4-yl)phenoxy)butan (BPPB) has been synthesized in accepted yield using microwave assistance. The new compound BPPB has been formed by the interaction of 3,3'-((butane-1,4-diylbis(oxy))bis(2,1-phenylene))bis(1-phenylprop-2-en-1-one) (3) with 2- aminobenzimidazole (4) in the presence of potassium hydroxide as a basic catalyst in dimethylformamide (DMF) under microwave radiation for 20 min. The chemical structure of this novel compound was elucidated by elemental and spectral techniques including: FT-IR, (1)H-NMR, (13)C-NMR and mass spectra. The electronic absorption and emission spectra of BPPB were measured in different solvents. BPPB displayed a solvatochromic effect of the emission spectrum that is reflected by red shifts of its fluorescence emission maxima on increasing the solvent polarity, indicating a change of electronic charge distribution upon excitation. BPPB crystalline solids gave excimer-like emission at 535 nm with a bandwidth of ca. 60 nm. Ground and excited states electronic geometry optimizations using density functional theory (DFT) and time-dependent density functional theory (TD-DFT), respectively, complemented these spectral findings. The intramolecular charge transfer was investigated by natural bond orbital (NBO) technique.

The influence of the pressure and temperature on the light emission of the ZnO

NASA Astrophysics Data System (ADS)

Dantas, N. O.; Couto dos Santos, M. A.; Cunha, F.; Macêdo, M. A.

2007-09-01

A new route for the preparation of zinc oxide powder is described along with its characterization. A proteic sol was prepared dissolving zinc nitrate in filtered coconut water. After calcination at 1000 °C, the powder was compressed to 1.3×10 8 Pa and ZnO pellets were obtained. The emission spectra were recorded under UV excitation at 325 and 400 nm. The powder showed no spectroscopic response, whereas one peak around 396 nm was observed for the pressed powder (pellet with no heat treatment). The pellets were then annealed for 24 h at 500, 800 and 1000 °C. In the first case, bands at 396 and 440 nm and a structure of narrow peaks around 480 nm (oxygen vacancies) were observed. Increasing the annealing temperature led to a decrease in the intensity of the emissions at 440 and 480 nm. We propose that the high pressure induces a red-shift in the UV region of the ZnO nanopowder emission peaks to 396 nm. This is an indication that the ZnO nanopowder treated under pressure and sintering temperature exhibits the spectroscopic behavior characteristic of the ZnO single crystal. The disappearance of the 440 and 480 nm lines indicate the reduction of oxygen vacancies. The atomic force micrographs suggest a coalescence thermal point.

Influence of succinylation on the conformation of yak casein micelles.

PubMed

Yang, Min; Cui, Na; Fang, Yan; Shi, Ying; Yang, Jitao; Wang, Jiangyu

2015-07-15

Succinylation modifies the physicochemical characteristics and improves the functional properties of proteins. This study assessed the effects of succinylation on the conformation of yak casein micelles with seven degree of modification. The results revealed that succinylation contributed to the dissociation of casein micelles. With the increase of succinylated degree, soluble nitrogen and minerals content increased, while casein micelle size and polydispersity index of micelles decreased. Succinylation affected the spatial conformation of yak casein micelles: turn decreased, ß-sheet and α-helix increased, and irregular structure were non-significantly affected. The intrinsic and ANS fluorescence intensity decreased and the maximum emission wavelength shifted red with increasing succinylation. Based on the results, the structure of yak casein micelles was characteristic of the sub-micelle model. Copyright © 2015 Elsevier Ltd. All rights reserved.

Heterocrystal and bicrystal structures of ZnS nanowires synthesized by plasma enhanced chemical vapour deposition

NASA Astrophysics Data System (ADS)

Jie, J. S.; Zhang, W. J.; Jiang, Y.; Meng, X. M.; Zapien, J. A.; Shao, M. W.; Lee, S. T.

2006-06-01

ZnS nanowires with heterocrystal and bicrystal structures were successfully synthesized using the DC-plasma chemical vapour deposition (CVD) method. The heterocrystalline ZnS nanowires have the zinc blende (ZB) and wurtzite (WZ) zones aligned alternately in the transverse direction but without an obvious period. The bicrystal ZnS nanowires are composed of two ZB fractions separated by a clear grain boundary along the length. Significantly, the grain boundaries in both the heterocrystal and bicrystal structures are atomically sharp without any visible lattice distortion. The effects of plasma species, ion bombardment, and silicon impurities in the formation of these distinctive structures are discussed. A defect-induced red-shift and broadening of the band-gap emission are revealed in photoluminescence (PL) and cathodoluminescence (CL) measurements.

Alteration of fluorescent protein spectroscopic properties upon cryoprotection.

PubMed

von Stetten, David; Batot, Gaëlle O; Noirclerc-Savoye, Marjolaine; Royant, Antoine

2012-11-01

Cryoprotection of a protein crystal by addition of small-molecule compounds may sometimes affect the structure of its active site. The spectroscopic and structural effects of the two cryoprotectants glycerol and ethylene glycol on the cyan fluorescent protein Cerulean were investigated. While glycerol had almost no noticeable effect, ethylene glycol was shown to induce a systematic red shift of the UV-vis absorption and fluorescence emission spectra. Additionally, ethylene glycol molecules were shown to enter the core of the protein, with one of them binding in close vicinity to the chromophore, which provides a sound explanation for the observed spectroscopic changes. These results highlight the need to systematically record spectroscopic data on crystals of light-absorbing proteins and reinforce the notion that fluorescent proteins must not been seen as rigid structures.

Strain-compensated (Ga,In)N/(Al,Ga)N/GaN multiple quantum wells for improved yellow/amber light emission

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lekhal, K.; Damilano, B., E-mail: bd@crhea.cnrs.fr; De Mierry, P.

2015-04-06

Yellow/amber (570–600 nm) emitting In{sub x}Ga{sub 1−x}N/Al{sub y}Ga{sub 1−y}N/GaN multiple quantum wells (QWs) have been grown by metal organic chemical vapor deposition on GaN-on- sapphire templates. When the (Al,Ga)N thickness of the barrier increases, the room temperature photoluminescence is red-shifted while its yield increases. This is attributed to an increase of the QW internal electric field and an improvement of the material quality due to the compensation of the compressive strain of the In{sub x}Ga{sub 1−x}N QWs by the Al{sub y}Ga{sub 1−y}N layers, respectively.

Intramolecular Charge-Transfer Interaction of Donor-Acceptor-Donor Arrays Based on Anthracene Bisimide.

PubMed

Iwanaga, Tetsuo; Ogawa, Marina; Yamauchi, Tomokazu; Toyota, Shinji

2016-05-20

We designed anthracene bisimide (ABI) derivatives having two triphenylamine (TPA) groups as donor units at the 9,10-positions to form a novel π-conjugated donor-acceptor system. These compounds and their analogues with ethynylene linkers were synthesized by Suzuki-Miyaura and Sonogashira coupling reactions, respectively. In UV-vis spectra, the linker-free derivatives showed broad absorption bands arising from intramolecular charge-transfer interactions. Introducing ethynylene linkers resulted in a considerable red shift of the absorption bands. In fluorescence spectra, the ethynylene derivatives showed intense emission bands at 600-650 nm. Their photophysical and electrochemical properties were compared with those of the corresponding mono TPA derivatives on the basis of theoretical calculations and cyclic voltammetry to evaluate the intramolecular electronic interactions between the donor and acceptor units.

Coexistence of strongly and weakly confined energy levels in (Cd,Zn)Se quantum dots: Tailoring the near-band-edge and defect-levels for white light emission

NASA Astrophysics Data System (ADS)

Das, Tapan Kumar; Ilaiyaraja, P.; Sudakar, C.

2017-05-01

We demonstrate white light emission (WLE) from (Cd,Zn)Se system, which is a composite of Zn alloyed CdSe quantum dot and ZnSe-amorphous (ZnSe-a) phase. Detailed structural and photoluminescence emission studies on pure CdSe and (Cd,Zn)Se show cubic zinc blende structure in the size range of 2.5 to 5 nm. (Cd,Zn)Se quantum dots (QDs) also have a significant fraction of ZnSe-a phase. The near-band-edge green-emission in crystalline CdSe and (Cd,Zn)Se is tunable between 500 to 600 nm. The (Cd,Zn)Se system also exhibits a broad, deep defect level (DL) red-emission in the range 600 to 750 nm and a sharp ZnSe near-band-edge blue-emission (ZS-NBE) between 445 to 465 nm. While DL and CdSe near-band-edge (CS-NBE) emissions significantly shift with the size of QD due to strong confinement effect, the ZS-NBE show minimal change in peak position indicating a weak confinement effect. The intensities of ZS-NBE and DL emissions also exhibit a strong dependence on the QD size. A gamut of emission colors is obtained by combining the CS-NBE with the ZS-NBE emission and broad DL emission in (Cd,Zn)Se system. Interestingly, we find the convergence of Commission Internationale de l'Eclairage (CIE) coordinates towards the white light with increasing Zn concentration in CdSe. We demonstrate by combining these three emissions in a proper weight ratio WLE can be achieved. Cd1-yZnySe (y = 0. 5; QD size ˜4.9 nm) alloy with a maximum quantum yield of 57% exhibits CIE coordinates of (0.39, 0.4), color rendering index (CRI) of 82, correlated color temperature (CCT) of 3922 K, and Duv of 0.0078 which is very promising for white light applications.

Multicolor upconversion emission from Tm3++Ho3++Yb3+ codoped tellurite glass on NIR excitations

NASA Astrophysics Data System (ADS)

Giri, N. K.; Rai, D. K.; Rai, S. B.

2008-06-01

Multicolor emission has been produced using 798 nm and 980 nm laser excitation in a Tm3++Ho3++Yb3+ codoped tellurite based glass. This glass generates simultaneously red, green and blue (RGB) emission on 798 nm excitation. Multicolor emission thus obtained was tuned to white luminescence by adjusting the Ho3+ ion concentration. There is a close match between the calculated color coordinate for the white luminescence obtained here and the point of equal energy which represents white in the 1931 CIE chromaticity diagram. The 980 nm excitation of the same sample on the other hand gives intense green and red emission and the glass appears greenish.